METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI

SIXTH INTERNATIONAL CONFERENCE ON METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY – MARC VI

ABSTRACTS OF PAPERS TO BE PRESENTED AT MARC VI

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI HEVESY AWARD ADDRESS: MEMORIES FROM A FORTY-YEAR PERIOD IN RADIOANALYTICAL, RADIO- & NUCLEAR CHEMISTRY. J.J.M. de Goeij. Department of Radiochemistry, Interfaculty Reactor Institute, Delft University of Technology, Mekelweg 15, 2629 JB Delft, THE NETHERLANDS. A brief overview will be given on the work carried out in the past 40 years, related to (i) various nuclear analytical and radioanalytical techniques, (ii) production of radionuclides, radiotracers and radiopharmaceuticals, with both nuclear reactor and cyclotron, and (iii) natural radioactivity. In addition to research and development in these fields, the work comprised many applications in various disciplines. These covered mainly chemical analysis, environmental compartments, medicine & biology, general chemistry and technology. Two main topics will be highlighted in particular. First, development and application of radiochemical neutron activation analysis of mercury in a variety of biological materials, later on gradually extended to about 20 trace elements. Second, the development of two routine production methods with the cyclotron for large amounts of iodine-123 for use in nuclear diagnostic medicine. 101 USING INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS (INAA) IN BIOTECHNOLOGY. N. M. Mukhamedshina*1, A. A. Mirsagatova1, N. M. Bekmukhamedova2, Kh. M. Khamidova2. 1Institute of Nuclear Physics, Ulugbek, Tashkent, Uzbekistan. 2Institute of Microbiology, Tashkent, UZBEKISTAN. Capacity of microorganisms to accumulate metal ions can be used for extraction of metals from technological solutions and for water purification of different productions. INAA applied for search more effective biosorbents U and Ag among 9 and 47 strains of actinomyces, respectively. Biomass of strains were tested on the U and Ag sorption capacity from model solutions, contained 50 mg/l ions U and Ag, respectively. Interaction between biomass and solutions took place for 15-60 min. 0.1ml solutions after sorption were dropped on the strips of ash free filter paper, which were dried (samples) and then in the aluminium packets were put in container for irradiation in nuclear reactor. The U and Ag samples were irradiated for 5 hours and 20 hours at fission spectra neutron flux of the density of 5.3·1013 cm-2s-1, respectively. The content of the Ag was calculated from gamma-line intensities of radionuclide 110Ag(T1/2 = 255d, Eγ = 657.7KeV). The content of the U was calculated from gamma-lines (228.2KeV, 277.8KeV) intensities of radionuclide 239Np. The U and Ag error of determining (Sr=relative standard deviation) was 0.07-0.1. It was shown, that all strain of actinomyces absorbed the U and Ag from solutions to a different extent. More effective strains with activities 80.4-90.0% were 7 of 47, absorbing Ag. Two of 9 strains, absorbing U, had activity 99.0%, the rest had from 20.0% to 50.0%. The study is supported by STCU grant UZB-26. 102 DETERMINATION OF ZnSe(Te) STOICHOMETRY AND DOPANT CONTENT BY X-RAY ANALYSIS. N. M. Mukhamedshina*, A. A. Mirsagatova, V. G. Zinov′ev. Institute of Nuclear Physics, Ulugbek, Tashkent, 702132, UZBEKISTAN. The light output and pulse duration in isovalently doped zinc selenide single crystals depend on its element composition as well as on dopant content and distribution. Thus, the instrumental and accurate method is necessary for monitoring of these parameters. For this purpose, X-ray analysis having high accuracy, quickness, reliability, simplicity and availability suits best of all and was developed here. Taking into account the contribution of secondary excitation, the ratio of Kα line intensities of Se and Zn was derived for the determination of ZnSe stoichometry. The linear dependence of the TeKα intensity on the Te content was used for determining the latter. The proportionality coefficient between the TeKα and the Te content was estimated from the set of different samples with the known Te contents. Annular 109Cd source was used for

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI the excitation of the Zn and Se Kα-lines. The Kα line of Te was excited by three 241Am sources arranged as a triangle in circle. The measurement error (Sr) of ZnSe elemental composition was 0.01. The measurement error of the Te content was 0.06-0.09 in the range of 0.01-0.5% Te. The Zn and Se contents in all the studied single crystals were found to change within 50.0-51.0% and 49.0-49.5%, respectively. The isovalent Te dopant ions were distributed in the crystal volume quite regularity, when the concentration was about 0.01 and 0.2% Te in different series of samples. When the doping level was about 0.5% Te, the impurity ions were distributed non-evenly over the bulk, so that one half of the samples had about 0.5% Te and the other only ∼0.25% on average. The study is supported by STCU grant UZB-26. 103 SIMULTANEOUS 68Ge AND 88Zr RECOVERY FROM PROTON IRRADIATED Ga/Nb CAPSULES. M. Faßbender, D.J. Jamriska, V.T. Hamilton, F.M. Nortier and D.R. Phillips, Radioisotope Application and Production Team, C-INC, MS J514, Los Alamos National Laboratory, Los Alamos, NM 87545, U.S.A. 68

68

+

Ge (271 d, EC 100%) serves as a parent nuclide for the daughter Ga, a β emitter important to Positron Emission Tomography (PET). 68Ge is obtained by (p,x) nuclear reactions on natural Ga. A typical Ga target assembly consists of liquid Ga contained in a Nb capsule, Nb being one of the few metals resistant to liquid Ga. One longer-lived radioisotope generated by the proton irradiation of naturally mono-isotopic 93Nb, is 88Zr 90 (83.4 d, via 93Nb(p, α2n)), decaying into 88Y, which, in turn, has been considered a useful surrogate for Y as a label in the investigation of Y-labeled compounds for cancer radioimmunotherapy. Experience reveals that irradiated Nb target capsules often contain Ga residuals not to be removed easily by mechanical operations in the hot cell. Furthermore, 68Ge activity losses were observed during capsule opening. In order to improve the 68Ge activity yield and simultaneously recover the by-product 88Zr, a wet chemical procedure has been developed where the Nb/Ga target capsule is dissolved in HF containing media as a whole, and both 68 Ge and 88Zr are extracted from the solution utilizing CCl4 liquid-liquid extraction and alumina absorption/ anion exchange in a sequence. (LA-UR #02-5202) 104 USE OF A FRISCH GRID DETECTOR TO RAPIDLY IDENTIFY ALPHA EMITTERS IN WATER, AIR-FILTER AND SOLID MATRICES. S. C. Scarpitta*1, R. Miltenberger2, R. Gaschott1, N. Carte3 and K. Clifford1. 1Radiological Control Division, Brookhaven National Laboratory, Upton, NY 11973-5000, USA. 2Sandia National Laboratory, Albuquerque, NM 87185-0651, USA. 3University of Connecticut, Storrs, 06289, USA. A commercially available Frisch Grid (FG) gas-proportional ionization chamber is being successfully utilized at Brookhaven National Laboratory to rapidly characterize and semi-quantify α-emitters in unprocessed water, air-filter and solid matrices. Matrix specific energy calibrations were performed using NIST# traceable 230Th, 232U, 236Pu and 243Am. Detection efficiencies were 15-20% for samples with < 900 ug cm-2 mass on 2” planchets and 45% for mass-less water samples (FWHM < 75 KeV). Background over an α-energy range of 3-8 MeV is very low at 0.01 cps. One hour MDLs of 0.56 mBq Kg-1 , 74 mBq L-1 and 14.8 mBq filter-1 were achievable for 40 mg soil, 1 mL tap-water and 4.5 cm cellulose-nitrate airfilters, respectively. Precision and accuracy were within 20% using a finely pulverized, homogeneous U.S. DOE/RESL# soil standard containing 15 Bq g-1 each of 239Pu, 241Am and 233U. Spectral results are presented from actual (unspiked) samples containing Bq to mBq amounts of 239/40Pu, 241Am or 238U. For 5 air-filters containing < 0.5 Bq 241Am, FG results were within a factor of two of results obtained by Gross alpha/beta or HPGe counting. Although this technique has it’s limitations, the advantages are: (1) minimal sample preparation, (2) no separation chemistry required (3) no chemical/hazardous waste generated and (4) ability to alpha-characterize samples and semi-quantify results within one day. # Purified NIST tracers provided by Dr. Isabel M. Fisenne, U.S. DOE Environmental Measurements Laboratory (EML); spiked homogeneous soil provided by Dr. David Sill, U.S. DOE Radiological and Environmental Sciences Lab (RESL).

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI

105 SORPTION OF PLUTONIUM (VI) BY HYDROXYAPATITE Mona Gasser(1), Nasser Awwad(1), Robert C. Moore(2), Kathleen Holt(2), Charles Sanchez(3), and Fred Salas(2) (1) Sandia National Laboratories Albuquerque, NM 87185-0779 (2) Egyptian Atomic Energy Authority Cairo, Egypt (3) Department of Soil, Water and Environmental Sciences The University of Arizona Yuma, AZ 85364 The sorption of Pu(VI) to synthetic hydroxyapatite was determined in batch experiments in a 0.1M KNO3 solution. Kinetic data indicate the sorption process is relatively fast with more than 95% of the Pu being sorbed to the hydroxyapatite in less than 2 hours. Equilibrium experiments indicated sorption is pH dependent with equilibrium constants are extremely high ranging from the lowest measured value of 2.7 x 106 L/mole at pH 6 to the highest value of 7.6 x 106 L/mole at pH 9. Data points over a range of initial Np concentration were collected at pH 8 and were accurately modeled using the Langmuir isotherm model for simple adsorption. These data along with the fact that hydroxyapatite is environmentally friendly, very stable, and has a very low water solubility indicate hydroxyapatite is an excellent candidate for use as permeable barriers for treating contaminated groundwater and as a repository backfill for containment of Np(V). 106 APPLICATION OF ENERGY DISPERSIVE X-RAY FLUORESCENCE TECHNIQUES TO STUDY OF LEAVES INFECTED BY CITRIC CANCKER. Pedro Henrique Arruda Aragão1(*); Eduardo Di Mauro1; Natasha Midori Suguihiro1; Suene Bernardes dos Santos1, Marcelo Estevam1, Elizabeth Cristina Soares da Costa1,Gaudino Andrade2, Luís Gustavo de Lázaro Rampazo2; Maurício Antonio C de Melo3; Andréa Paesano Junior3 and Virgílio do Franco Nascimento Filho4. (∗) e-mail: [email protected]. 1 Departamento de Física. CCE. Universidade Estadual de Londrina. Campus Universitário. 86.051-990. Londrina, PR, Brasil . 2Departamento de Microbiologia. CCB. Universidade Estadual de Londrina. Campus Universitário. Londrina, PR, 3Departamento de Física . CCE. UEM, Maringá, PR and 4Laboratório de Metodologia de Radioisótopos. CENA/USP, Piracicaba, SP. BRASIL In this work, we made use of energy depressive X ray fluorescence to study leaves of citric of the region of Londrina - Paraná - Brazil (23°56.S, 52°3.W), infected for the citric cancker. The Citric Cancker is caused for the Xanthomonas bacterium axonopodis pv. Citric. This is of easy dissemination and one of its vectors is the man. Contagious and highly resistant. One year lives for more than in some environments. If the environment will be the fruit, leaf or branch of a contaminated plant, the bacterium survives still more. In this work, we study leaves of orange infected by the citric cancer we use the technique of X ray fluorescence. Our results show that leaves infected present one high concentration of micronutrients and low concentration of macronutrients. Leaves not infected show low to a concentration of micronutrients and one high concentration of macronutrients. Using the technique of energy depressive X ray fluorescence we determine a competition between macronutrients (K, Ca) and micronutrients (Ti, Mn, Fe, Ni, Cu, Zn). Principally between the elements Iron and Calcium in infected leaves when compared the leaves not infected. We observe that this competition also occurs with another fitopalogia, for example, the sooty moulds. The high concentration of iron in leaves infected was used to determine the state of oxidation of this metal. For this study, us we use the techniques of electronic paramagnetic resonance and spectroscopy of Mössbauer. Our results show that it is about a organic oxide, in the state Fe3+ oxidation. 107 IAEA STUDY OF EDUCATION IN NUCLEAR AND RADIOCHEMISTRY: USA. Gregory R. Choppin, Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 323064390 Under the auspices of the IAEA, a survey was conducted of the status of education in the USA in nuclear and radiochemistry. Nineteen universities responded. The survey found a continuing decline in the number of graduate programs, graduate students and faculty. Several responses were pessimistic about the future of the program in those universities. At present, there are 5 - 10 Ph.D's per year graduated in the USA in these

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI research fields. In the USDOE laboratories several hundred Ph.D.'s are expected to be hired in the next 2 - 3 years. This does not include personnel needed in the nuclear industry, medicine, etc. The shortage of nuclear scientists will not be solved, as in the past by foreign Ph.D.'s as the decline in young scientists in the field is universal. The problem is very serious as further decreases in programs and faculty will seriously decrease the ability to reverse the trends and provide an adequate supply of Ph.D.'s in nuclear/radiochemistry when needed in the future for R&D in the expansion of nuclear power to counter the Greenhouse effect by replacement of fossil fuel. 108 REDOX SPECIATION OF PLUTONIUM. Gregory R. Choppin, Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390 USA To successfully model the behavior of surface and subsurface plutonium contamination at DOE sites, it is necessary to have a good understanding of the species present. The speciation is a function of a complex interaction of the redox behavior, hydrolytic effects and interaction with residual separation agents in the waste and/or the natural ligands in the environment as well as of the sorptive and solubility characteristics of the various species formed in solution. The insolubility of Pu(OH)4 is often the limiting factor of the net solubility of plutonium in oxic natural waters where Pu(V)O2+ is the most stable oxidation state. Perturbations to the oxidation state speciation due to the complexation chemistry of the different oxidation states of plutonium and to the insolubility of plutonium(IV) in neutral aquatic systems are discussed. The merits and limitations of some chemical separation techniques used to study redox speciation of plutonium are presented. The choice and use of oxidation analogs to evaluate the behavior of plutonium are also discussed. Preparation of this preparation was possible by a contract from the USDOE-OBES Division of Chemical Sciences. 109 DIFFERENTIATION AND MEASUREMENT OF SIMILAR GAMMA RAYS PRODUCED BY 47 Ti(n,p)47Sc AND 197Au(n, )198Au(n, )199Au. C. C. Swanson*1, A. J. Filo1, and J. P. Lavine2. Imaging Materials and Media, R&D, Eastman Kodak Company, Rochester, NY 14650-2155, USA. 2Digital and Applied Imaging, Eastman Kodak Company, Rochester, NY 14650-2008, USA. As performance and yield demands for all types of electronic devices constantly increase, the presence of ultratrace level, metallic impurities in silicon wafers has become extremely important to the semiconductor industry. Because neutron activation analysis (NAA) has excellent sensitivities for many of the contaminants of interest, it has become the analytical method of choice for their quantitative measurement. Our detection limits currently range from 1011 Fe atoms cm-3 of Si to 107 Au atoms cm-3 of Si with estimated errors of 2030%. The presence of a gamma ray in the 159 keV region of the spectra of these samples has proven challenging because it can be produced by the neutron activation of both titanium and gold. The means of production are 47Ti(n,p)47Sc and 197Au(n, )198Au(n, )199Au. Gamma-ray energies and half-lives are 159.4 keV, 3.3d and 158.4 keV, 3.1d, respectively. The similar half-lives of 47Sc and 199Au make it difficult to use decay rates to attribute the peak to Ti or Au. We have attempted to resolve this problem by calculating the theoretical number of 158.4 keV emissions, relative to the number of 411.7 keV emissions of the more prominent 198Au isotope. In addition, we experimentally measured the emissions using NAA of silicon wafers implanted with 197Au ions. This paper will present a detailed description of the analytical procedure used for the analyses of the implanted wafers, as well as comparisons of the observed and calculated data. 110 LYOPHILIZATION AS PRECONCENTRATION PROCEDURE IN K0-NEUTRON ACTIVATION ANALYSIS OF BRAZILIAN ANIMAL TISSUES. A.A.Canella*1, M.A.B.C.Menezes2 , A.L.Abdalla1 . 1Laboratory of Animal Nutrition - LANA, Centro de Energia Nuclear na Agricultura, Universidade de Sao Paulo, Caixa Postal 96 CEP 13400-970 Piracicaba, Brazil. 2CDTN/CNEN, Caixa Postal 941, CEP 30123.900 Belo Horizonte, Brazil

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI The success attainable in k0-NAA using a relative low neutron fluxes reactor (about 1011 neutron.cm-2.s-1) - Triga Mark-I IPR-R1, CDTN/CNEN, Brazil - is to a large degree dependent on the detection sensitivity. In practice, carrying out investigations on essential and non-essential elements in just-fresh animal tissues (muscle, liver, kidney, blood and faeces), only concentrations of major elements could be obtained by virtue of their relative concentrations, higher than the limits of detection. Thus, to evidence more elements in level below the limit of detection, it is necessary to preconcentrate the biological matrices before applying k0NAA. Among nondestructive processes, the lyophilization has been chosen in the present study due to minimal losses of chemical elements as previously discussed by Zaichick (1997). After the process, the relative mass in biological matrices gives rise to 100%-300% amounts of each element. There is a remarkable achievement in k0-NAA using preconcentrated biological matrices obtaining a great number of elements not evidenced in just-fresh analysis. Details will be presented. 111 DETERMINATION OF HEAVY METALS AND OTHER TRACE ELEMENTS IN LAKE SEDIMENTS FROM A SEWAGE TREATMENT PLANT BY NEUTRON ACTIVATION ANALYSIS A. P. Ribeiro1, A.M.G. Figueiredo1* and J.B. Sgolo2 1Instituto de Pesquisas Energticas e Nucleares, Sao Paulo, Brazil. 2Instituto de Geocincias, Universidade de Sao Paulo, Sao Paulo, BRAZIL. The Sewage Treatment Plant (STP) in Barueri, Sao Paulo, Brazil, processes a significant part of sewages generated in Sao Paulo city. Due to economic and technical problems, all the residual sludges produced in the STP in Barueri from 1988 to 1996 were cumulatively disposed over the land, in piles and in open areas, deposited directly on the soil. The STP has two ponds, which were built to landscape the place. In the present work, instrumental neutron activation analysis (INAA) was used to determine metals (Ba, Co, Cr, Cs, Fe, Hf, Rb, Sc, Zn), semi-metals (As, Sb), actinides (U, Th) and rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) in bottom sediments from one of the ponds, in order to verify whether it was contaminated due to the wastes generated by the plant. The results obtained were compared to the concentration determined in a soil profile and in a sample of rock, in natura, representing the litologies of the region, and showed a homogeneous distribution of the elements all along the pond and indicated that only As, Cr and Zn can have their origin associated with the residues disposed around the pond. 112 THE PREPARATION OF A SYNTHETIC-URINE MATRIX CONTAINING ULTRA-LOW CONCENTRATIONS OF URANIUM WITH VARYING ISOTOPIC RATIOS. J.S. Morton*, D.S. Sill, M.C. Verwolf. United States Department of Energy, Radiological and Environmental Sciences Laboratory, Idaho Falls, Idaho, 83402 The use of depleted uranium in various projectiles and as the vital component of protective battle armament has prompted an evaluation by various governmental bodies of the analytical capability employed to identify and quantify varying isotopic ratios of the element that may be present in urine. As the result of an international meeting held in Santa Fe, New Mexico, the technical criteria of a proposed study were designed to evaluate the capability of mass spectrometric instrumentation to quantify ultra-low concentrations of isotopic uranium in bioassay samples. At the proposed levels, the use of quantitative analytical radiochemical methods as a concentration and separation step is a necessity. The study requires that the emerging technologies have the capability of quantifying varying 235U/238U ratios at a concentration of 5 nanograms/L of urine. In order to prepare meaningful performance-test samples at these concentrations, the indigenous uranium must first be removed from the salts comprising the synthetic urine matrix. The Radiological and Environmental Sciences Laboratory (RESL) of the United States Department of Energy has developed the expertise and capability to prepare the unique test samples. The methods employed to produce synthetic-urine salts with a remaining concentration of indigenous uranium in the low picogram range will be discussed. 113 THE USE OF Zr-Au-Lu ALLOY FOR CALIBRATING THE IRRADIATION FACILITY IN k0NAA AND FOR GENERAL NEUTRON SPECTRUM MONITORING. F. De Corte* and A. De Wispelaere.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI Laboratory of Analytical Chemistry, Institute for Nuclear Sciences, Ghent University, Proeftuinstraat 86, B9000 Gent, BELGIUM. Zr-Au-Lu alloyed wire or foil with a well-balanced, homogeneous and accurately known composition allows from one single irradiation, followed by a well-designed gamma-spectrometry protocol, the simultaneous determination of the following neutron spectrum characteristics of an irradiation facility: the “subcadmium” thermal neutron flux and the thermal-to-epithermal neutron flux ratio in the Högdahl-convention, the “total” neutron flux and the modified spectral index in the Westcott-convention, the epithermal flux shape parameter alpha and the Maxwellian neutron temperature; in addition it gives – via the 90Zr(n,2n)89Zr reaction - an estimate of the fast neutron flux component. Consequently, this type of alloyed monitor is likely to be quite useful not only in the practice of k0-NAA, but in general neutron metrology as well. The present paper reports both on the fundamentals (underlying theoretical considerations; desired composition; gammaspectrometry protocol) of this “all-in-one” alloy and on the experimental results (radiation stability and homogeneity tests) obtained for a variety of materials that were produced by some firms specialized in alloying technology. From this study, it can be concluded that at present all criteria are fulfilled to proceed with the next logical step, being the development of a Zr-Au-Lu alloy as a certified reference material. 114 A PERFORMANCE COMPARISON OF k0-BASED ENAA AND NAA IN THE (K, Th, U) RADIATION DOSE RATE ASSESSMENT FOR THE LUMINESCENCE DATING OF SEDIMENTS. F. De Corte*1, S.M. Hossain1, D. Vandenberghe1 and P. Van den haute2. 1Laboratory of Analytical Chemistry, Institute for Nuclear Sciences, Ghent University, Proeftuinstraat 86, B-9000 Gent, Belgium. 2 Laboratory for Mineralogy, Petrography and Micropedology, Geological Institute, Ghent University, Krijgslaan 281, B9000 Gent, Belgium. An essential step in luminescence dating is the determination of the annual radiation dose, mainly arising from the decay of 40K, 232Th and 235,238U + daughters (with some contribution from 87Rb and cosmic radiation). It is common practice to use a few methods such as direct alpha, beta or gamma-counting, and also an elemental determination method such as NAA. Recently, in our lab an intercomparison was made of these methods applied to loess and sand sediment [1,2], whereby - when evaluating the dose rates obtained the emphasis was put on their precision and accuracy. Although these properties are quite important – being linearly transferred to the dating result –, the duration of the measurement is also a practically relevant aspect. Indeed, direct radiation countings can last a week or more – especially for low-active sand – and the determination of K, Th and U via NAA can take up to three weeks to allow proper gamma-ray spectrometry of the long-lived 233Th/ 233Pa. With this in mind, in the present work the performance of k0-based epiCd-NAA when applied to sediments is compared to NAA. Among the topics experimentally evaluated are the improvement of the sample throughput, the accuracy and precision of the results and the determination sensitivity. [1] S.M. Hossain et al., NIM A, 490 (2002) 598. [2] F. De Corte et al., (proceed. RMA-10, Ann Arbor, MI, 2002), NIM A, in press. 115 THE ANALYSIS OF METALLIC COMPOSITIONS IN ASIAN DUST PARTICLES USING INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS. J. H. Lee*1, J. M. Lim1, H. S. Lee1, M. S. Jang1, K. H. Kim2, Y. S. Chung3, K. Y. Lee4. 1Department of Environmental Engineering, Chungnam National University, Daejeon 305-764, KOREA. 2Department of Geoinformation Sciences, Sejong University, Seoul 143-747, KOREA. 3HANARO Center, Korea Atomic Energy Research Institute, Daejeon 305-600, KOREA. 4Environmental Geology Division, Korea Institute of Geoscience & Mineral Resources, Daejeon 305-345, KOREA.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI In this study, quantitative analysis of about 30 metallic elements was made using instrumental neutron activation analysis on aerosol samples collected in Daejeon city, Korea during the Asian Dust (AD) period of 2002. Results of our analysis between the AD and NAD period indicated that the concentrations of REEs (metals of crustal origin such as La, Ce, Sm, Dy, and Lu) were higher during the AD than the NAD period by more than 8.5 times. In addition, the major crustal elements (such as Al, Ca, Co, Fe, K, Mg, and Ti) showed more than about 3 to 11 times higher concentration levels during the AD period; this enrichment during the AD period helped raise the levels of PM 10 and all metals during the AD period by about 3.0 and 4.8 times higher, respectively. However, the concentrations of anthropogenically derived metals (such as As, Br, Cl, I, In, Sb, Se, and Zn) exhibited moderate increases during the AD period. Uncertainty evaluation of metal concentrations determined by instrumental neutron activation analysis was followed by applying ISO guide precisely. The mean and expanded uncertainty of the sample for March 17, 2002 was 24730±1531µ/g for Al and 28.87±1.97µ/g for As, respectively. Their expanded uncertainties were 6.19 and 6.83% for Al and As, respectively. The overall results of our study suggest that there exist certain patterns of metallic composition of aerosol particles between the AD and NAD period. 116 GEL DETECTOR FOR 222RADON GAS. G. Espinosa*. Instituto de Física, UNAM. Apartado Postal 20-364; 01000 México, D.F. México. [email protected] In this paper, a new radiation detection method is introduced which uses a commercial gel material for the measurement of radon (222Rn) gas. This method is based on the diffusion of radon gas into the gel material and the measurement of the radioactive daughters resulting the radon decay. The 214Bi daughter gamma-ray, with a photopeak of energy of 0.609 MeV, was chosen for these measurements, and the gamma-ray photopeak was analyzed via a HPGe multichannel system. The results indicated a linear relationship between the integrated area of the 214Bi photopeak and the concentration of radon that had diffused into the gel material. Two very well defined radon response levels were observed: (1) from 150 to 1500 Bq m-3 and (2) from 1500 to 7400 Bq m-3. This method gives highly reproducible and reliable results in the measurements of radon concentrations. This new technique opens the door to future studies of different gel materials in order to obtain better sensibility and new applications in the measurement of radioactive gases. 117 TL RESPONSE OF COMMERCIAL SiO2 OPTICAL FIBER TO GAMMA RADIATION. G. Espinosa*1 and R.J. Silva2. 1Instituto de Física, UNAM, Apdo. Postal 20-364, 01000, México, D.F. 2 Lawrence Livermore National Laboratory, PO. Box 808, Livermore 94550 CA, USA. [email protected] Commercial SiO2 optical fiber has been found to be a Thermoluminiscent (TL) material in investigations to develop new radiation detection materials within the Dosimetry Applications project at the Instituto de Fisica, UNAM. This paper presents preliminary results of a study of the TL response to gamma radiation. The material shows a glow curve between the 30°C and 390°C, with one glow peak at 210°C. The intensity of the peak has a linear response to the quantity of 60Co gamma radiation over the milliroentgen to kiloroentgen range. The SiO2 optical fiber exhibits a high reproducibility and low fading in the TL signal. The material can be reused after a thermal treatment. These characteristics make commercial optical fiber a possible TL dosimeter material. They could be used at the micro-size level (150 µm diameter) and have a high potential for use in several applications in the fields of medicine, industry and research. Work performed under the auspices of the US Department of Energy by Lawrence Livermore National Laboratory under contract W-7405-ENG-48 118 PRODUCTION OF THERAPEUTIC RADIOISOTOPES IN THE ORNL HIGH FLUX ISOTOPE REACTOR (HFIR) FOR APPLICATIONS IN NUCLEAR MEDICINE, ONCOLOGY AND INTERVENTIONAL CARDIOLOGY. F. F. (Russ) Knapp, Jr.*, S. Mirzadeh, A. L. Beets and M. Du. Nuclear Medicine Program, Nuclear Science and Technology Division, Oak Ridge National Laboratory (ORNL), Oak Ridge, TN 77831.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI Research reactors play an important role for production of therapeutic radioisotopes which have increasing clinical applications for treatment of metastatic bone pain, cancer, arthritis and restenosis therapy. The ORNL High Flux Isotope Reactor (HFIR) has a maximal thermal neutron flux of 2.5 x 1015 neutrons/cm2/sec (100 MW) and is a unique resource for production of a wide variety of medical radioisotopes. HFIRproduced therapeutic radioisotopes of current interest include tungsten-188 (double neutron capture on W186), holmium-166, lutetium-177 and platinum-195m. Rhenium-188 from the ORNL W-188/Re-188 generator is now used in over 60 clinical trials worldwide. Lutetium-177 and holmium-166 are produced directly or via beta-decay of reactor-produced precursors by the Yb-176(n,γ)Yb-177(β-→)Lu-177 and Dy164(n,γ)Dy-165(n,γ)Dy-166(β-→)Ho-166 routes, which provide no-carrier-added products free of the longerlived Lu-177m and Ho-166m metastable contaminants. Our new separation technique efficiently separates Lu-177 and Yb. We have also developed a unique new route for HFIR production of platinum-195m - an important Auger-emitter - available for the first time with a specific activity of 70-100 mCi/mg by the Ir193(n,γ)Ir-194(n,γ)Ir-195(β-→)Pt-195m. This paper will discuss the current and projected production capabilities of these and other important therapeutic radioisotopes in the ORNL HFIR. ORNL is managed by UT Battelle, LLC, for the U.S. Department of Energy, under contract No. DE-AC0500OR22725. 119 APPLICATION BY ENERGY DISPERSSIVE X-RAY FLUORESCENCE TECHNIQUE IN THE STUDY OF HEAVY METALS IN THE SEDIMENTS OF THE LAKE IPÊ –MATO GROSSO DO SUL BRAZIL. Sônia Regina G. Barreto1, Wagner J. Barreto1, Jorge Nozaki2, Pedro Henrique A. Aragão3* and Virgílio F. do Nascimento Filho4 .1Departamento de Química. CCE. Universidade Estadual de Londrina. Campus Universitário. 86.051-990. Londrina, PR, Brasil 2Departamento de Química. CCE. Universidade Estadual de Maringá, Maringá, PR , 3Departamento de Física. Universidade Estadual de Londrina, Londrina, PR, (*) [email protected] or [email protected], 4Laboratório de Metodologia de Radioisótopos CENA/USP, Piracicaba, SP, BRASIL. Lake Ipê, located in a floodplain area of Parana River, is an ecosystem that apparently does not show signs of pollution. The samplings of sediments in this lake, with a surface area of approximately 10,700 m2, were taken at the central point. Sediments are highly complex mixtures of minerals and organic compounds, in which ions are associated by adsorption, absorption, or complexation. Lake sediments are basically formed by materials coming from adjacent terrestrial areas, and also produced by soluble or suspended materials in water. Therefore, the chemical structure depends on the chemical and physical characteristics of terrestrial area and water column. The metals are naturally introduced in the environment through rocks harshness, and also by a variety of human activities through industrial, cattle raising or agricultural, and domestic wastewaters. Fe, Zn, Cu, and Mn are essential micronutrients to the growing of aquatic organisms. While metals such Cd, Pb, and Hg are not necessary to the growing of these organisms, they are toxic even in trace amounts. However, above the allowed limit of each element, all metals have a high degree of toxicity in the environment. Chemical analyses of metals in sediment by Energy Dispersing X-Ray Fluorescence technique, is very versatile, and may be applied in solid samples without any preliminary steps of digestion, being nondestructive and also multielemental. The powder samples show high intensity of fluorescence and, in addition, samples or standard may be used as solid tablets. The application of EDXRF technique to compare qualitatively the metals in marginal soils and sediments of Lake Ipê, MS, Brazil, was the main objective of this study. 120 CHEMODYNAMICS OF EDTA IN A SIMULATED, MIXED WASTE: CHEMODEGRADATION VS. γ-RADIOLYSIS (REVISITED). A. P. Toste*1, K. J. Polach1 and T. Ohnuki2. 1 Department of Chemistry, Southwest Missouri State University, Springfield, MO 65804, USA. 2Japan Atomic Energy Research Institute, Tokai-mura, Ibaraki-ken 319-1195, Japan

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI The chemo-degradation of EDTA in a simulant of a Hanford mixed waste, a new study, is examined, and compared with the γ-radiolysis of EDTA in the simulant, an earlier study, which has been reanalyzed, yielding new insights. To study chemo-degradation, the simulant was stored in the dark at ambient temperature for up to 175 days. EDTA disappeared gradually, but steadily, with 40.8% remaining. The process was fairly nondispersive, i. e., most of the total organic carbon (TOC) (81.6 %) remained. Eleven degradation products were identified: glyoxylic acid; and 10 chelator fragments, notably iminodiacetic acid (IDA); N-Methylethylenediamine-N,N'-diacetic Acid (MEDD'A); ethylenediaminetriacetic acid (ED3A); and nitrosated derivatives of these species. The inorganic matrix of the simulated waste is clearly harsh enough to cause significant EDTA degradation. To study radiolysis, the simulant was irradiated with γ-doses of 0 7.5 x 106 R. Compared to chemo-degradation, radiolysis degraded EDTA much more rapidly, with only 10.9 % remaining. Moreover, EDTA's radiolysis was dispersive, with only 34.7% of the TOC remaining. Ten degradation products were identified. Like chemo-degradation, radiolysis produced glyoxylic acid, ED3A, as well as nitrosated derivatives of IDA, ED3A, and MEDD'A. However, several species were unique to radiolysis: N-Ethyl-N,N'-dinitroso-propylenediamine-N'-acetic acid (EtDNPD'A); NMethylethylenediamine-N',N'-diacetic Acid (MEDDA); and 3 dicarboxylic acids (C2,C3 andC7). 121 REMOVAL OF RADIOACTIVE IODIDE BY SURFACTANT MODIFIED ZEOLITES. H. Faghihian, A. Malekpour, Department of Chemistry, University of Isfahan, Isfahan, IRAN. During fission of uranium several iodine species are produced. Whereas I-129 with 0.9% yield has the longest half-life of 1.59 x 107 yrs, I-131 (t1/2 = 8.04 days) with 2.77% yield is the predominant radioisotope. Because of high selectivity, stability and low price, zeolites are frequently used for separation of radioactive cations. These materials are radiation resistive and compatible with cementation and vitrification. Cations in fact can interact with zeolites via ion exchange on negatively charged internal and external surface, but anions are not readily taken up by zeolites because zeolites possess a net negative structural charge resulting from isomorphic substitution of cations in their crystal lattices. The modification of zeolites is then necessary prior to anion adsorption. In this work, two natural zeolites were treated with different quaternary alkylammonium ions to replace the exchangeable metal cations on zeolite surface. Experiments were conducted both in batch and continuous conditions. Treatment of natural clinoptilolite and natrolite were carried out with hexadecyltrimethylammonium (HD), tetradecyltrimethylammonium (TD), dodecyltrimethylammonium (DD), tetrabutylammonium (TBA) and tetramethylammomium (TMA) ions. Some of modified forms exhibited adsorption capacities, which are several times higher than those of natural samples. Adsorption isotherms for the iodide solution/ modified zeolite were constructed. The effect of interfering anions on the adsorption capacity of modified zeolites was investigated. The breakthrough behaviors of radioiodide in the column charged with the adsorbent was studied. Desorption of iodide into different medium was also investigated. On the basis of the results, some of the modified zeolites can remove and immobilize the radioactive iodide very efficiently. 122 ROUTINE RADIOCHEMICAL METHOD DETERMINATION OF 90Sr, 238Pu, 239+240Pu, 241Am and 244 Cm IN THE DIFFERENT ENVIRONMENTAL SAMPLES V.A. Ageyev1, O. O. Odintsov* 2and A. D. Sajeniouk1 . 1Institute for Nuclear Research, Kiev, 03028, Ukraine. 2State Specialized Company “Technocentre”, Chernobyl, 07270, UKRAINE. The routine analytical procedures are being developed for the reliable simultaneous determination of 90Sr, Pu, 239+240Pu, 241-243Am and 242-244Cm Chernobyl derived and fallout after nuclear weapon tests in a wide range of environmental samples: soil (100 - 300g), sediments, water and vegetation. The main steps of radiochemical procedure are the next: 1 - ash of sample at 5500C; 2 – add tracers 236Pu, 243 Am and carriers stable La, Sr; 3 - acid leaching with HNO3; 4 - precipitation oxalates; 6 - ash of oxalates at 6000C; 7 - dissolution of residue in 6 M HCl; 8 – precipitation Fe(OH)3 with NH4OH no contain CO2 (A – precipitate Pu, Am and Cm, B – solution 90Sr); 5 – precipitation LaF3 with Pu, Am and Cm; 6 – dissolution 238

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI of precipitate LaF3 in 8M HNO3 + H3BO3 (solution - C); 7 – pass solution (C) through anion exchanger column Dowex 1x8 (∅ 0,2cm, h 10cm); 8 – wash column 8M HNO3 and 10M HCL; 9 – elutriate Pu with 9M HCL + NH4I; 10 – electrodepositing of Pu (alpha spectrometry of 236Pu, 238Pu, 239+240Pu); 11 – after step 7 Am and Cm are separated from rare earths by cation exchange column Dowex 50x8, Am and Cm were eluted with 20% C2H5OH saturated HCl; 12 – final purification and concentration of Am and Cm by cation exchanger column Dowex 50x8 (∅ 0,2cm, h 10cm); 13 – strip Cm and Am by 2 – hydroxy – iso - butyric acid; 16 - electrodepositing of Am and Cm together (alpha spectrometry of 241Am, 243Am, 244Cm). Solution B reprocessing for determination of 90Sr as Sr-Ca separation by fuming HNO3; Sr - purification by precipitation Fe(OH)3, BaCrO4; final source measured as a SrCO3; β-counting 90Sr. This procedure has been applied to thousands soil and sediment samples and hundreds biological and water samples taken in the exclusive zone of Chernobyl NPP and different regions of Ukraine at 1989 to the present tense. The methods developments are described. During projects by AQCS IAEA "Evaluation of Methods for 90Sr in a Mineral Matrix" and “Proficiency test for 239Pu, 241Pu and 241Am measurement in a Mineral matrix” accuracy and precision results measurement 90Sr, 239Pu and 241Am by present procedure was evaluate. Final status all results measurement 239Pu and 241Am in six samples mineral matrix with low, medium and high activity and two standard solutions are “passed”. Relative bias between reported results 239 Pu, 241Am and IAEA data were in range ±(4 ÷ 12) percentage. Average chemical yield of Pu was 70±10% and Am 60±5%. Advantages, difficulties and limitations of the method are discussed. 123 DETERMINATION OF U, Pu, Am and Cm IN THE “HOT” PARTICLES AND IRRADIATED FUEL BY RADIOCHEMICAL METHOD AND ALPHA-PARTICLE SPECTROMETRY. O.O.Odintsov. State Specialized Company “ Technocentre”, Chernobyl, 07270, UKRAINE. A method for determination of 234-238U, 238-242Pu, 241-243Am and 242-244Cm content in fuel “hot” particles was investigated. The method based on the quantitative measurement of the α activity in the sample followed by α spectrometry where the relative contributions of individual nuclides or groups of radionuclides to the total α activity are identified. For present investigation, “hot” particles were taken in the near-field region of Chernobyl NPP. The “hot” particles were dissolved by 8M HNO3 and 8M HNO3 + 0,1M HF acid digestion, evaporated to dryness, 234-238U, 238-242Pu, 241-243Am and 242-244Cm simultaneous electrodepositing on stainless steel disk and measured by sensitive alpha spectrometry. The chemical yield of U, Pu and Am during simultaneous electrodepositing was studied with known activity of 238U, 242Pu and 243Am as an internal yield tracers. After first alpha spectrometry measurement U, Pu, Am and Cm strips from stainless steel disk with 8M HNO3 and than separate to individual fractions: Plutonium by anion exchange column Dowex-1x8; Uranium, Americium and Curium by cation exchange column Dowex-50x8, Uranium elute with 1 M NH4CNS, Cm and Am elute with 0.33 M 2 – hydroxy – iso - butyric acid pH 4,75. Actinide isotopes were then determined by second alpha spectrometry following electrodeposition. The typical alpha spectrums obtained with sources of fuel «hot» particles are given in paper. Analytical results are presented for the activity concentrations of 234U, 235U, 236U, 238U, 238Pu, 239+240Pu, 241Pu, 242Pu, 241Am, 242mAm, 243Am, 242Cm and 244 Cm in the «hot» particles with different burnup of fuel. It is defined that the detection limit of these radioisotopes is 0,001Bq per particle. The application of this method for measurement U, Pu, Am and Cm in irradiated nuclear fuel discussed. 124 THE COMPLEX ANALYSIS OF THE PLUTONIUM ISOTOPE RATIO BY ALPHA-PARTICLE SPECTROMETRY. O.O. Odintsov *1, A.P. Lashko2, V.P. Khomenkov2. 1 State Specialized Company “Technocentre”, Chernobyl, 07270, Ukraine. 2Institute for Nuclear Research, Kiev, 03028, UKRAINE. High-resolution α- spectrometry from soil samples begins with radiochemical separation and α-particle source-preparation procedures by electrodeposition Pu on the stainless steel disk. The radiochemical preconcentration and isolation of Pu from soil samples by leaching with HNO3, precipitate with Ca oxalate and LaF3 and anion exchange column Dowex-1x8 (NO3-form) has been developed. The alpha-spectra that are

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI obtained from a soil sample can be used for measurement of activity 238Pu, 239Pu, 240Pu, 241Pu and 242Pu by αspectrometry. Program package for analyzing of alpha-spectra for separation of contribution activity 239Pu and 240Pu to the 5.105, 5.123, 5.143, 5.155 and 5.168 - MeV peaks is proposed. At the heart of this program underlie the method to insert an "apparatuses line" in to the interesting part of α- spectrum. The "apparatuses line" is the single α- line of obtaining α- spectra measured with high statistics accuracy. The complete isotope content of plutonium in the Chernobyl accident zone was determined by means of this package. Isotopes ratio in relative units are 238Pu - 0.78±0.07, 239Pu - 0.63±0.04, 240Pu - 1.0, 241Pu - 59±7 and 242Pu 0.0013±0.0003 on the 26 April 1998. 125 NUCLEAR SCIENCE IN BRAZILIAN CLASSROOMS - A VIEW FROM THE INSIDE. A.A.Canella*1 . 1 Laboratory of Animal Nutrition - LANA, Centro de Energia Nuclear na Agricultura, Universidade de Sao Paulo, Caixa Postal 96 CEP 13400-970 Piracicaba, BRAZIL Certainly two research jobs in Nuclear Field may differ as black differs from white. Accordingly, the development of a common academic background for different scientists involved in Nuclear Field has been a challenge for the boards of Universities where Master or Doctoral programs are available in Nuclear or related field. Concerning Brazilian Experience, one of leading educational institution, Universidade Federal de Minas Gerais, which offer postgraduation on Nuclear Science (Curso de Ciencias e Tecnicas Nucleares), there is only one compulsory - 60 hours workload - subject to introduce and to form the foundations of Nuclear Science for a wide range of professional backgrounds - physicists, engineers, biologists, geneticists, physicians, agronomists, veterinarians and chemists. It is a hard choice made to improve more free time for non-nuclear studies. As a result of that, the content on Nuclear Theory barely reaches a review of principles. The concepts and ideas have been presented on a superficial level, mainly due to a lack of time in classroom preventing especially physicists, chemists and engineers from applying their skills to deepen their knowledge on Nuclear Science. Rarely deeper subjects in Nuclear Theory have been taught due to their non-compulsory status, what results in low demand, not enough to set up a class. Although these programs vary from University to University, they have a common question to be replied: What actions should be taken to improve on quality of Brazilian postgraduation programs in teaching and creating knowledge on Nuclear Science ? 126 CRITERIA FOR THE CERTIFICATION OF NON-RADIOACTIVE HAZARDOUS WASTE. S.D. Gagner*1, J. Dominick1, R. Gaylord1, R.A. Govers2, M.J. Grasalfi3, W.E. Kennedy, Jr.4, R.S. Pastor2. 1 Lawrence Livermore National Laboratory, 7000 East Ave., Livermore, CA 94550, USA. 2Chamberlain Group, 3Consultant, 14506 Ascot Square, Boyds, MD 20841, 4Dade Moeller & Associates, Inc., 1845 Terminal Dr., Suite 140, Richland, WA 99352, USA In 1991, the Secretary of Energy issued a restriction on the shipment of waste to disposal sites until a Department of Energy (DOE) site-specific program could be developed to assure that no radioactive waste would be disposed as hazardous. Lawrence Livermore National Laboratory (LLNL) developed a process to use a combination of generator knowledge and/or sampling and analyses to certify waste as non-radioactive. The analytical process used the minimum detectable activity (MDA) as the de minimus value. As technology developed, the MDAs have been lowered. Also, waste matrices tend to interfere with the MDAs. LLNL, in conjunction with the Chamberlain Group and Dade Moeller & Associates, Inc., is pursuing a riskbased approach to determine whether waste is non-radioactive, consistent with DOE guidance. This paper discusses the approach, which includes defining the radionuclides considered, establishing the exposure scenarios for the critical groups identified for each of four waste streams, defining the exposure pathways and key input data or assumptions, presenting radiation doses for unit concentrations of radionuclides in each waste stream, presenting the authorized limits for each waste stream, and discussing the results. Analytical values which fall below these authorization limits will be considered non-radioactive, with any individual dose maintained below 1 mrem/yr.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 127 COLLOID-FACILITATED TRANSPORT OF PLUTONIUM. A.B. Kersting*1, P. Zhao1, M. 2 Zavarin , E. R. Sylwester1, P. G. Allen1, and R. M. Maxwell2. 1Chemistry and Material Science and 2Energy and Environment Directorates at Lawrence Livermore National Laboratory, L-231, PO Box 808, Livermore, CA 94550, USA. Increasing concerns have been raised recently regarding the subsurface fate and transport of actinides, such as plutonium (Pu). Batch sorption/desorption, x-ray absorption spectroscopy (XAS), multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) and surface complexation modeling of plutonium sorption to various colloids was performed to evaluate colloid-facilitated Pu transport at the Nevada Test Site. The oxidation states of Pu(IV) and Pu(V) were studied as these are the dominant oxidation states under equilibrium conditions at the NTS. The major findings are: Pu sorbed to all minerals investigated, although the extent, rates and mechanisms are dependent on specific colloids, XAS showed that Pu sorbed as Pu(IV) on all minerals regardless of initial oxidation state of Pu in solution, Sorption of Pu(IV) on the zeolite, clinoptilolite, was rapid, significant (70-90%), and desorption was low, 2-8%, and Sorption of Pu(V) was slow and occurred by two different mechanisms, direct sorption and subsequent reduction, and Pu disproportionation in solution prior to rapid Pu(IV) sorption We conclude that Pu strongly sorbs to common minerals and sorbs as Pu(IV) on mineral surfaces. The desorption rate for clinoptilolite is low suggesting that the majority of sorbed Pu(IV) will remain on the mineral available for transport. This work was performed under the auspices of the U.S. Department of Energy by University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48 128 THE RAPID RADIOCHEMICAL METHOD DETERMINATION OF 238Pu, 239+240Pu, 241Am and Cm IN THE AEROSOL FILTER BY ION-EXCHANGE CHROMATOGRAPHY. V.A. Ageyev1, O. O. Odintsov *2and A. D. Sajeniouk1 .1Institute for Nuclear Research, 03028, Kiev, Ukraine. 2State Specialized Company “ Technocentre”, Chernobyl, 07270, Ukraine. 244

The rapid radiochemical procedure developed for the determination of 238Pu, 239+240Pu, 241Am and 244Cm in the aerosol filter is described in the paper. The main steps of radiochemical procedure are the next: 1 - ash of aerosol filters at 4500C; 2 – add tracers 236Pu, 243Am and carrier stable La; 3 - the ashed sample disintegration with (HNO3 + HF) and dry ashed, and then dissolved in 6 M HCl; 4 – precipitation Fe(OH)3 with NH4OH no contain CO2 (precipitate La, Pu, Am and Cm); 5 – add to precipitate of Fe(OH)3 22M HF saturated with SO2 for stabilization of Pu in Pu3+ and precipitation LaF3 with Pu, Am and Cm; 6 – dissolution of precipitate LaF3 in 1M HNO3 + H3BO3; 7 – precipitate La(OH)3 with NH4OH; 8 - dissolution of hydroxides La, Pu, Am and Cm in 0,5 M HNO3; 9 - oxidizing of the Pu3+ to Pu6+ by heating of solution 0,5 M HNO3 with (NH4)2Cr2O7; 10 – pass solution through cation exchanger column Dowex 50x8 (∅ 0,2 cm, h 10 cm); 11 - wash column 1M NH4NO3; 12 – for separation of actinides sequentially elutriate Pu, Cm, Am and La in 4-5 drops by different fraction 2 – hydroxy – iso - butyric acid pH 4,75 with special concentration from 0.16 M to 0.5 M; 13 - electrodepositing of Pu (alpha spectrometry of 236Pu, 238Pu, 239+240Pu) and electrodepositing of Am and Cm together (alpha spectrometry of 241Am, 243Am, 244Cm). This procedure has been applied to small (5 -10 g) soil samples, some biological and water samples. The methods developments are described. During project by AQCS IAEA “Proficiency test for 239Pu, 241Pu and 241Am measurement in a Mineral matrix” accuracy and precision results measurement 239Pu and 241Am by present procedure was evaluate. 129 SEDIMENTATION RATE IN BRACKISH LAKE OBUCHI, ROKKASHO VILLAGE, JAPAN, BORDERED BY NUCLEAR FUEL CYCLE FACILITIES. S. Ueda, Y. Ohtsuka, K. Kondo And J. Inaba. Department Of Radioecology, Institute For Environmental Sciences, 1-7, Ienomae, Obuchi, Rokkasho, Kamikita, Aomori 039-3212, JAPAN A nuclear fuel reprocessing facility is currently under construction in Rokkasho Village Aomori, Japan. After completion start-up (scheduled in 2005), this facility will discharge radionuclides into the Pacific Ocean through an outlet pipe set on the seafloor off the coast of Rokkasho Village. For future assessments of the

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI stability of these radionuclides in the environment, a sufficient understanding of the behavior of radionuclides in the ocean and estuary ecosystem before the start-up of the facility is necessary. In order to clarify the sedimentation rate of brackish Lake Obuchi, bordered by the facility, approximately 50-cm depth sediment cores were collected at three points in the lake, and the sedimentation rate was calculated by the chronological measurement method using 137Cs and 210Pb. In addition, vertical distribution characteristics of physical properties, and concentrations of U, Th, stable elements and organic substance in the sediment were clarified. The sedimentation rates calculated by the 137Cs and 210Pb method were 0.29 to 0.31 g/cm2/yr in the estuary of Futamata River (depth of 1 to 1.5 m), 0.13 to 0.14 g/cm2/yr in the 3 m water depth area, and 0.12 to 0.13 g/cm2/yr in the deepest area (depth of 4.5 m), respectively. The sedimentation rate in the estuary of the Futamata River was larger than that in water area of 3 m to 4.5 m water depth, and the effect of the inflow load on the estuary from the land was found to be strong. 130 DISCUSSION OF PROBLEMS ENCOUNTERED DURING THE COLLECTION AND SUBMISSION OF WIPE/LEAK TEST SAMPLES. G. W. Wright*, United States Army Soldier and Biological Chemical Command, Aberdeen Proving Ground, MD 21010, USA The focus of this paper will be on the collection and submission problems encountered while analyzing area wipe and leak test samples taken on devices containing radioactive materials. The area wipe and leak test sample analysis are for either gross alpha counting by gas-flow proportional counting or low-level beta counting by liquid scintillation counting. These area wipe and leak test samples are received from United States Army field and maintenance units. Technical Manuals, as well as safety and maintenance messages, provide established policies for the collection and submission of the area wipe and leak test samples. The problems range from incorrect sampling media to improper packaging and shipping of the samples. Since quality starts with sample collection, and area wipe and leak test samples are not being collected or submitted correctly, the counting laboratory may not be able to provide meaningful results to the customer. A discussion of the problems and how to address them will be presented. 131 WHAT DO WE UNDERSTAND BY THE CONCEPTS OF SPECIFIC ACTIVITY, RADIOACTIVITY CONCENTRATION, CARRIER, CARRIER-FREE AND NO-CARRIER-ADDED? AND HOW CAN THESE BE DEFINED PROPERLY? J.J.M. de Goeij*1 and M.L. Bonardi2. 1Department of Radiochemistry, Interfaculty Reactor Institute, Delft University of Technology, Mekelweg 15, NL-2629 JB Delft, THE NETHERLANDS. 2Universita degli Studi and INFN-Milano, LASA, Via F.lli Cervi 201, I20090 Segrate, Milano, ITALY. In nuclear and radiochemistry and the related fields of radiopharmaceutical and radioanalytical chemistry the concept of (isotopic) carrier plays a crucial role. In combination with the concept of radioactivity it leads to the concept of specific activity, linking the amount of radioactivity to that of the carrier. For many applications there is an increasing need for high to very high specific activities, or said otherwise, the requirement of a minimum amount of carrier present in the radionuclide preparation. In this frame two other concepts are relevant, viz. the concept of carrier-free and that of no-carrier-added. Although the concepts mentioned are basically simple, it turns out that they involve various - and sometimes rather conflicting definitions and interpretations. This may lead to confusing and/or false conclusions. Some current definitions will be given and discussed as to their correctness, relevance, clarity, and consistency. Special attention will be paid to the provisional recommendations for the Nomenclature for Isotopic, Nuclear and Radioanalytical Techniques (IUPAC, final draft version, 12 January 2001). On basis of this discussion, some tentative suggestions will be given for more proper definitions of the concepts of specific activity, radioactive concentration, carrier, carrier-free and no-carrier-added. 132 HOW DO WE ASCERTAIN SPECIFIC ACTIVITIES IN NO-CARRIER ADDED RADIONUCLIDE PREPARATIONS? M.L. Bonardi*1 and J.J.M. de Goeij2. 1Universita degli Studi and INFN-Milano, LASA, Via F.lli Cervi 201, I-20090 Segrate, Milano, ITALY. 2Department of

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI Radiochemistry, Interfaculty Reactor Institute, Delft University of Technology, Mekelweg 15, NL-2629 JB Delft, THE NETHERLANDS. In nuclear and radiochemistry and the related fields of radiopharmaceutical and radioanalytical chemistry the specific activity is a crucial parameter, linking the amount of radioactivity to that of the carrier, the amount of other isotopes of the associated element. For many applications there is an increasing need for high to very high specific activities, or said otherwise, a requirement of a minimum amount of carrier. Fulfilment of this requirement is generally indicated with the terminology no-carrier-added. Although here intentional addition of carrier is absent, still appreciable amounts of carrier may be present. Generally the carrier amount in preparations with a very high specific activity is not known, sometimes not even its order of magnitude. Moreover, due to further handling a very high specific activity may decrease due to contamination with carrier element. For quality control of radionuclide preparations as well as for assessment and development of appropriate routes to very high specific activities dedicated analytical techniques are required. Various analytical techniques as applied to specific radionuclides will be presented. These examples highlight the need for the actual determination of specific activities of no-carrier-added radionuclide preparations. Finally, the speciation of radionuclide and carrier is discussed. 133 CHARACTERIZATION AND BIODISTRIBUTION OF A NOVEL MRI MOLECULAR IMAGING AGENT BY NEUTRON ACTIVATION ANALYSIS. J.D. Robertson1,2, S.B. Crane1, S.A. Wickline3, and G.M. Lanza3. 1University of Missouri Research Reactor and 2Department of Chemistry, University of Missouri, Columbia, MO 65211. 3Department of Cardiology, Washington University Medical School, St. Louis, MO 63110, USA. Angiogenesis is integral to the development and progression of atherosclerotic disease and solid tumor growth. New microvessels form in atherosclerotic plaque and the presence of new vessels has been associated with carotid plaque instability. Likewise, solid tumor growth depends upon angiogenesis to provide tumor cells with oxygen and nutrients. Recently, Lanza et al. have demonstrated molecular imaging of angiogenesis both in human melanoma xenografts in nude mice and atherosclerotic rabbits by magnetic resonance imaging (MRI) with clinical magnet strengths using 3-targeted nanoparticles developed in their lab. 3-integrin is a selective molecular epitope expressed by angiogenic endothelium and the MRI contrast agent consists of a lipid-encapsulated, liquid perfluorocarbon nanoparticle directly coupled to a selective 3 ligand. The nanoparticle also contains the paramagnetic contrast agent gadolinium covalently linked to the nanoparticle as Gd-DTPA-bis-oleate. In this work we report on the use of neutron activation analysis to confirm the Gd content of the nanoparticle formulations and determine the biodistribution of Gd post injection. 134 DETERMINATION OF THE CHEMICAL COMPOSITION OF WATERS OF PRECIPITATION IN SUBTROPICAL CONTINENTAL AREA BY EDXRF. Maria Cristina Solci1 , Alscio Fachim Pelicho1, Pedro Henrique Arruda Aragao2(*) & Virglio Franco Nascimento Filho3. 1. Universidade Estadual de Londrina - Departamento de Qumica - Londrina - Paran - Brasil, 2. Universidade Estadual de Londrina Departamento de Fsica - Londrina - Paran - Brasil, 3. Laboratrio de Metodologia de Radioistopos - CENA Universidade de Sao Paulo - Piracicaba - Sao Paulo - BRASIL. (*) ([email protected] or [email protected]). The characterization of soluble and insoluble compositions in suspension in the atmosphere can provide direct and important information about the quality of the air. Being possible to verify the origin of the metals traces. The humid deposition of particles is larger than the deposition dries. The atmospheric deposition of the particles is responsible for one drag of the metals traces resulting in a close deposition to their sources. We used the technique of X-Ray Fluorescence for the determination of the insoluble metals traces in the precipitation waters. We studied the residual layer after the filtration in membrane for it makes possible important correlations among metals traces presents in the phases soluble and insoluble of the atmospheric depositions. Our samples were excited with a tube of rays X of Phillips, model PW 1830 operating to 10,0

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI mA and 25 kV and irradiated during 300s. The spectra were stored in floppy disks and analyzed being used the software AXIL/QXAS of IAEA. Our results show high correlations between Fe - Ti, Fe - Mn and Fe Ca. Indicating the same origin, coming of the crust of the earth and introduced in the atmosphere through the soil. The metals Ass, Zn, Pb, Cd and Ni are present in fine particles emitted by anthropological activities usually mobile. High correlations between Pb-Zn, Pb-Br and Pb-Cr evidence the contribution of the deposition of material particulate in suspension. Like this, the technique of EDXRF was shown effective in the determination of insoluble components in the precipitation waters. Making possible to do important correlations between elements traces presents in the phases soluble and insoluble of the atmospheric depositions. 135 A TECHNIQUE FOR STRONTIUM-90, PLUTONIUM AND AMERICIUM ISOTOPE CONTENT DETERMINATION IN ENVIRONMENTAL SAMPLES. A.N.Berlizov, A.D.Sazhenyuk*, V.V.Tryshyn, Institute for Nuclear Research, National Academy of Sciences of Ukraine, UKRAINE A technique is proposed for determining contents of 90Sr as well as Pu and Am isotopes in different objects: soil, water, aerosol filters, and biological samples. An acid concentrate is obtained by employing of widely utilized techniques depending on the type of the object. From the obtained solution carbonates are precipitated by applying (NH4)2CO3+NH4OH reagent and then dissolved in 6M HCl, following which hydroxides are precipitated by applying of carbon-free ammonia. As a result, the solution contains 90Sr, while Pu and Am isotopes are in precipitate. 90Sr is precipitated as SrCO3, then dissolved in HNO3, evaporated to wet salts and converted to 2M HNO3 solution. Extraction of 90Sr is carried out by two 10 ml portions of 5% solution of bicyclohexyl-18-crown-6 in CHCl3. After double rinsing of organic phase of 2M HNO3, 90Sr is re-extracted by hot water. Chemical yield is determined gravimetrically by weghing SrCO3.The precipitate Fe(OH)3 is dissolved in HNO3 and reduced to 7.5M HNO3. The obtained solution passes through column with BP-1P anionite (similar to DW-1) in NO3− form (Hmax=300 mm, D=5 mm). After that the column is washed out successively by 7.5M HNO3, 10M HCl, and 9M HCl. As a result, Am isotopes are concentrated in nitrate solution, while Pu remains in anion exchanger. It is eluted with 0.5M HCl with addition of NH2OH⋅HCl and its electrolytic deposition is carried out. 242Pu is used as a tracer. Am is purified on ion exchange column with KU-2×8 cation exchanger (analogous to DW-50) in NO3− form. After that it is eluted with 0.27M α-hydroxyisobutyric acid and its electrolytic deposition onto polished stainless disks is carried out. 243Am is used as a tracer. 136 A MONTE CARLO APPROACH TO TRUE-COINCIDENCE SUMMING CORRECTION FACTOR CALCULATION FOR GAMMA-RAY SPECTROMETRY APPLICATIONS. A.N.Berlizov*, V.V.Tryshyn, Institute for Nuclear Research, National Academy of Sciences of Ukraine, UKRAINE True-coincidence summing in/out effect represents a serious problem in many applications of gamma-ray spectrometry that may strongly influence accuracy of obtained analytical results. A computational approach to the problem, based on Monte Carlo simulation technique, has been elaborated, providing flexible and accurate a tool applicable to a wide range of practical situations. For evaluating of true-coincidence correction factors an extended version of the versatile MCNP code was developed allowing simulating of gamma-ray spectrum for arbitrary cascade gamma-ray source and spectrometer configuration, including Compton-suppression systems. Two gamma-ray spectra, with and without taking into account of the emitted quanta cascading, are simulated simultaneously. Their comparison yields correction factors for photopeaks, which correspond to actually emitted gamma-rays. Intensities of the ghost peaks, present due to summing of the coincident gamma-rays, are evaluated also. The MCNP input is generated by a specially developed utility on the basis of routinely updateable ENSDF library files. Also necessary information is automatically added to allow accurate simulating of emission of coincident annihilation quanta as well as K- and LX-rays, originated from internal conversion and electron capture processes. The elaborated technique uses no special approximations so that the accuracy of the obtained results depends only upon the accuracy of the

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI measurement geometry definition (which can be defined very exactly owing to the exceptional capabilities of the MCNP code) and the completeness and accuracy of the latest nuclear data. 137 A CODE FOR PREDICTING RESULTS AND PERFORMANCE OF NEUTRON ACTIVATION ANALYSIS. V.K.Basenko, A.N.Berlizov, I.A.Malyuk, V.V.Tryshyn*, Institute for Nuclear Research, National Academy of Sciences of Ukraine, UKRAINE A code has been developed for predicting results and main characteristics (detection limits and precision) of NAA on the basis of analysis of a simulated gamma-ray spectrum of activation products, calculated for defined time mode, elemental composition, mass and dimensions of an analyzed sample, characteristics of irradiating neutron flux and irradiation conditions, measurement geometry and background conditions, as well as detector and spectrometry system parameters. Gamma-ray dose rates for different points of time after sample irradiating and input count rate of a spectrometry system are predicted also. Gamma-ray yields of activation products are calculated taking into account of burnout and buildup of both radioactive and stable isotopes, as well as attenuation of irradiating neutron flux by the sample. The code uses neutron cross-section and radionuclide libraries, built on the basis of recent activation data libraries as well as ENDF/B-VI and ENSDF evaluated nuclear data libraries. Integrated means for supplementing and updating of the libraries are provided. For gamma-ray spectrum modeling, an analytical and, more precise, statistical (obtained by Monte Carlo simulation) gamma-ray detector response presentations have been elaborated. Detectors with NaI, BGO, and HPGe crystals with arbitrary dimensions, thickness of non-active layers and additional absorbers can be considered. The code has a modern user interface, providing possibility for tabular and graphical output of calculation results, simulated spectrum, detector response functions, cross-section energy dependences etc. It can be applied for predicting of performance of a wide range of instrumental and radiochemical NAA techniques, utilizing reactor, isotopic source or monoenergetic neutrons. 138 OPTIMIZATION OF A RADIOCHEMICAL TECHNIQUE USED IN MEASUREMENT OF URANIUM AND THORIUM IN DIFFERENT MATRICES BY α-SPECTROMETRY. M. M-A. ALBokari*, K. A. AL-Eissa, and E. I. Shabana.,Institute of Atomic Energy Research, King Abdulaziz City for Science & Technology, P.O. Box 6086, Riyadh 11442, SAUDI ARABIA In a radioanalytical technique, (AG® 1-X8) anion exchanger (Cl--form, 100- 200 mesh, from Bio Rad) is used to separate uranium or thorium from all other components of the sample by ion exchange chromatography. The separated element is chemically eluted from the ion exchange column and coprecipitated with Nd3+ as a thin film of fine fluoride particles on a membrane filter for measurement by αspectrometry. Regeneration of the exchanger is tested for column reuse, in a purpose of reducing cost. Equal fractions of the same sample were used in each run. A blank sample was loaded after every three sample runs in the same regenerated column and prepared for counting. The performance of the regenerated exchanger was tested by following the change in the sample recovery, and the blank sample counting rate. The obtained data showed that the column could be reused several times in separating uranium from environmental samples (10-30 pCi/L) using 10M HCl media, before observing any change in the performance of the exchanger. For separating almost the same levels of thorium from aqueous solutions using 8M HNO3 media, the column could be also reused several times. On the other hand, the stability of the fine fluoride particles of the prepared source is also tested, by constructing the peak resolution / ageing time curves, for the source spectrum. The obtained data is discussed in detail. 139 GROSS ALPHA/BETA ANALYSIS OF WATER SAMPLES BY LIQUID SCINTILLATION COUNTING. C. T. Wong*1,2, V. M. Soliman1, and S. K. Perera1. 1California Department of Health Services, Sanitation & Radiation Laboratories Branch, 2151 Berkeley Way, Berkeley, CA 94704, USA. 2Presently at Lawrence Livermore National Laboratory, Hazards Control Department, P.O. Box 808, Livermore, CA 94551, USA.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI

The standard procedure for analysis of gross alpha and beta in water is evaporation of the sample and radioactivity determination of the resultant solids by proportional counting. This technique lacks precision, and lacks sensitivity for samples with high total dissolved solids. Additionally, the analytical results are dependent on the choice of radionuclide calibration standard as well as the sample matrix. Direct analysis by liquid scintillation counting has the advantages of high counting efficiencies and minimal sample preparation time. However, due to the small sample aliquots used for analysis, long count times are required to reach required detection limits. A procedure where a sample aliquot is evaporated to dryness, the resultant solids taken up in a small volume of dilute acid, followed by radioactivity determination by liquid scintillation counting is proposed. Sample aliquots containing up to 500 mg of dissolved solids may be handled in this manner. Various acids, scintillation cocktail mixtures, instrument discriminator settings and regions of interest were evaluated to determine optimum counting conditions. Precision is improved and matrix effects are reduced as compared to proportional counting. Tests indicate that this is a viable alternative to proportional counting for gross alpha and beta analysis of water samples. 140 RAPID SEPARATION OF FRESH FISSION PRODUCTS. D. E. Dry1, 1Chemistry Division – Isotope & Nuclear Chemistry, C-INC, Los Alamos National Laboratory, Los Alamos, NM 87544, USA The fission of highly enriched uranium by thermal neutrons creates dozens of isotopic products. The Isotope and Nuclear Chemistry Group participates in programs that involve analysis of “fresh” fission products by beta counting following radiochemical separations. This is a laborious and time-consuming process that can take several days to generate results. Gamma spectroscopy can provide a more immediate path to isotopic activities, however short-lived, high-yield isotopes can swamp a gamma spectrum, making difficult the identification and quantification of isotopes on the wings and valley of the fission yield curve. The gamma spectrum of a sample of newly produced fission products is dominated by the many emissions of a very few high-yield isotopes. Specifically, 132Te (3.2 d), its daughter, 132I (2.28 h), 140Ba (12.75 d), and its daughter 140 La (1.68) emit at least 18 gamma rays above 100 keV that are greater than 5% abundance. Additionally, the 1596 keV emission from 140La imposes a Compton background that hinders the detection of isotopes that are neither subject to matrix dependent fractionation nor gaseous or volatile precursors. Some of these isotopes of interest are 99Mo, 95Zr, and the rare earths, 141Ce, 144Ce, and 147Nd. C-INC has performed several HEU irradiations to determine methods for rapid and reliable separations that may be used to detect and quantify low-yield fission products by gamma spectroscopy. Results and progress will be presented. 141 INDOOR RADON RISK POTENTIAL OF HAWAII G. M. Reimer*1 and S.L. Szarzi2, 1Colorado School of Mines, Golden, Colorado 80401; 2U.S. Geological Survey, Denver, Colorado 80225, USA A comprehensive evaluation of radon risk potential in the State of Hawaii indicates that the potential for Hawaii is low. Using a combination of factors including geology, soils, source-rock type, soil-gas radon concentrations, and indoor measurements throughout the state, a general model was developed that permits prediction for various regions in Hawaii. Lawrence Berkeley National Laboratory and Columbia University developed a probability indicator for most of the nearly 3,000 counties in the coterminous U.S. National Uranium Resource Evaluation (NURE) aerorad data was the primary input factor for the predictive system. However, NURE aerorad data was not collected in Hawaii; therefore, this current study used geology and soil type as the primary and secondary components of potential prediction. In some areas of Hawaii, the radon potential of the soils is equivalent to that of moderate risk areas in other states. Even though the oceanic basalts that comprise the bulk of the Islands are extremely low in average uranium concentration, the development of lateritic soils enhances the chemical attachment of uranium and radium (the immediate progenitor of radon) to the surface of the soil particles. However, because most houses are built elevated from ground level, the radon soil potential is effectively decoupled from the house. Only underground facilities with closed or recirculating ventilation systems might have elevated radon potential.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 142 EXTREMELY LOW BACKGROUND MEASUREMENTS OF 137CS IN SEAWATER SAMPLES USING AN UNDERGROUND FACILITY (OGOYA). K. Hirose*1, M. Aoyama1, Y. Igarashi1 and K. Komura2. 1Geochemical Research Department, Meteorological Research Institute, Nagamine 1-1, Ibaraki 305-0052, Japan. 2Low Level Radioactivity Laboratory, Kanazawa University, Wake, Tatsunokuchi, Ishikawa 923-1224, JAPAN. 137

Cs is one of the most important anthropogenic radionuclides due to long physical half-life of 30 years and a major fission product. 137Cs in seawater is a powerful chemical tracer of water mass motion at the time scale of several decades because most of the 137Cs in water columns is present as a dissolved form. However, large-volume sampling of more than 100 L has been required to determine 137Cs concentrations in seawater because of very low concentrations of 137Cs in seawater. Especially, it is difficult to determine accurate 137Cs concentrations in deep waters (> 1000 m). In order to be able to use 137Cs as a chemical tracer, there are two objectives; one is to achieve higher sensitivity, and another is easier measurement. Recently, Komura has established an underground facility (Ogoya), whose background corresponds to 270 m water depth, to achieve extremely low background γ–spectrometry using Ge detectors with high efficiency and low background shield. We have improved the 137Cs adsorption technique from seawater using ammonium phosphomolybdate (AMP). We have succeed the 137Cs determination in seawater with a smaller sample volume of less than 10 L for shallow water (< 1000 m) and obtain more accurate values of deep 137Cs with a sample volume of 200 L. 143 SURVEILLANCE OF WORKING CONDITIONS IN A GAMMA-RAY SPECTROMETRY COUNTING ROOM. D. Glavic-Cindro*, M. Korun, B. Vodenik, J. Stefan Institute, Ljubljana, SLOVENIA The standard ISO/IEC 17025 requests monitoring, control and recording of all quantities which have any influence on the quality of test results. For measurements of low-level activities of radionuclides in environmental samples by gamma-ray spectrometry the quantities fall into two categories: quantities describing the conditions which must be fulfilled for keeping the spectrometers running (electricity and compressed air needed for refilling the detector Dewars) and environmental conditions. The later are temperature, humidity and concentrations of oxygen and radon and its daughters in the air in the counting room of the Gamma-ray Spectrometry Group at the "Jozef Stefan Institute". The voltage, pressure of compressed air and the temperature are controlled by the UPS power supply, auxiliary compressor and air conditioner, respectively. However, the voltage, frequency and pressure of compressed air are monitored continuously together with the temperature in the counting room, outdoor temperature, humidity and oxygen concentration. Fifteen-minutes averages with their variances are calculated and stored in QA data files of a Genie ESP spectrometry system. At the end of each day the data are checked if the values of the parameters did not transcend their predefined limit values. If the compliance with requested conditions during the whole day was found, daily averages and their variances are calculated and stored in the computer file together with the maximal and minimal values recorded during the day. If compliance could not be established, the full set of fifteen-minute averages is stored and warnings are issued by e-mail to QA manager, laboratory head and manager of the counting room. The radon concentration in the air is not measured regularly although it influences directly the measurement results. However test measurements were performed several times in different seasons and the correlation between the background and the outdoor temperature was established. The background of radon daughters in the spectrometers is calculated from the correlation. Namely, the concentration of radon daughters in the air depends on the outdoor temperature since the difference between the outdoor temperature and the temperature in the counting room defines the rate at which the air in the counting room is replaced by the outdoor air. In the contribution the monitoring and control of the environmental parameters will be presented as well time dependencies and correlations among them and correlations with the components of the background in the spectrometers.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 144 ANALYSIS OF TOTAL DIET STUDY FOODS FOR GAMMA-RAY EMITTING RADIONUCLIDES. D. L. Anderson* and W. C. Cunningham. Elemental Research Branch (HFS-338), FDA, College Park, MD 20740-3835, USA. Each year, 30 of about 260 foods collected for radionuclide analysis under the Food and Drug Administration's (FDA's) Total Diet Study (TDS) are analyzed by the Center for Food Safety and Applied Nutrition (CFSAN) as quality control for gamma-ray emitter analyses performed at FDA's Winchester Engineering and Analytical Center (WEAC). At CFSAN, 200-mL portions in cylindrical plastic screw-top containers are analyzed for 40K, 137Cs, and other fission products and naturally occurring radionuclides. For this portion size and geometry, absorption corrections are small (≤1.2%) for typical food densities (0.6 to 1.1 kg/L). Ge detector efficiency calibration is performed by analyzing 200-mL dilutions of three aliquots of NIST SRM 4276C Mixed-Radionuclide Solution Standard. Accuracy is assessed by analyzing KNO3 and KCl solutions, National Institute of Standards and Technology Standard Reference Material 1570 Trace Elements in Spinach, and six International Atomic Energy Agency Certified Reference Materials. Based on z-score analysis, results agree well with certificate and nominal values. CFSAN's TDS food 40K results agree well with those from WEAC gamma-ray emitter, CFSAN instrumental neutron activation, and FDA's Kansas City District Office Laboratory's inductively coupled plasma atomic emission spectrometry analyses, and are consistent with historical TDS values. 145 IMPROVEMENTS IN FOOD ANALYSIS BY THERMAL NEUTRON CAPTURE PROMPT GAMMA-RAY SPECTROMETRY. D. L. Anderson*1 and Elizabeth A. Mackey2. 1Elemental Research Branch (HFS-338), FDA, College Park, MD 20740-3835, USA. 2NIST, 100 Bureau Drive, MS 8395, Gaithersburg MD, 20899-8395, USA. The thermal neutron prompt gamma-ray activation analysis (PGAA) facility at the National Institute of Standards and Technology (NIST) Center for Neutron Research, jointly operated by the Food and Drug Administration and NIST, has been redesigned to lower background radiation levels and improve analytical capabilities. Standards prepared in a variety of matrices for 26 elements were irradiated and sensitivities were determined. These measurements and analysis of 15 food and food-related certified reference materials revealed significant sensitivity increases and lower limits of detection (LODs) for H, B, C, N, Na, P, S, Cl, K, Ca, Cd, and other elements. Most improved were LODs for elements (e.g., H, B, C, N, Al, and Fe) with gamma-ray background contributions from air and the apparatus. For example, LODs for B and N ranged, depending primarily on Cl content, from 40 to 90 ng/g and 0.08 to 0.2%, respectively, factors of 2 to 3 better than achieved with the old PGAA facility. Three multivitamin/multimineral, 1 bone meal, and 4 botanical dietary supplements were also analyzed. In addition to the elements listed above, Al, Si, Ti, Mn, Fe, Cu, Zn, Sm, and Gd were observed in one or more of the supplements. 146 CALCULATION OF PEAK-TO-TOTAL RATIOS FOR HIGH PURITY GERMANIUM DETECTORS USING MONTE-CARLO MODELING. R.Venkataraman*1, S. Croft1, and W.R. Russ1. 1 Canberra Industries, 800 Research Parkway, Meriden, CT 06514, USA. In order to estimate by calculation the magnitude of the true coincidence summing losses that may be affecting the observed gamma ray spectrum of a given nuclide measured using a spectrometer, knowledge of the total detection efficiencies at the gamma ray energies within the cascades is essential. The total efficiency can be determined provided the peak-to-total ratio is known. For a given High Purity Germanium (HPGe) detector, one can establish an intrinsic peak-to-total (P/T) efficiency curve using a set of measurements performed with “single” (ideally monoenergetic) gamma emitting nuclides (e.g. 241Am, 109Cd, 57Co, 113Sn, 137 Cs, 65Zn). Some of these nuclides are short lived and so have to be replaced periodically. Moreover, the presence of low energy gamma rays and X-rays in most of the decay schemes complicate the empirical determination of the P/T ratios. The problem is especially severe if measurements are made using HPGe detectors that have a very thin dead layer. The problems posed by low energy gamma rays and X-rays can be

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI avoided by using absorbers, but then one has to be careful not to perturb the intrinsic value of the P/T ratio being sought. This paper addresses these problems. Measurement related limitations are avoided if one can use a computational technique instead. In the work presented here, the feasibility of using a Monte-Carlo based technique to determine the P/T ratios at a wide range of energies (60 keV to 2000 keV) is explored. The Monte-Carlo code MCNP (version 4C) is used to simulate gamma ray spectra from various nuclides. Measured P/T ratios are compared to calculated ratios for several HPGe detectors to demonstrate the generality of the approach. Reasons for any disagreement between the two are discussed. True Coincidence Summing correction factors are calculated using both measured and MCNP based P/T calibrations and the results are discussed. 147 ANALYSIS OF MCGUIRE AFB BOMARC MISSILE SITE SOIL SAMPLES. Craig A. Refosco. Radiation Protection Division, USAF Radioisotope Committee Secretariat, Air Force Medical Operations Agency, AFMOA/SGZR, 110 Luke Avenue, Room 405, Bolling AFB, DC 20032-7050, USA Gamma spectrometry and radiochemistry were performed on McGuire AFB BOMARC Missile Site soil samples. The purpose was to: determine the mean activity concentration of plutonium (239,240Pu) and americium (241Am) by gamma spectrometry (γ-spec); to investigate whether the 239,240Pu activity concentration could be discerned from the 239,240Pu x-rays at 17 keV for a thin soil sample; to analyze small number of selected samples using radiochemical procedures to quantify the activity concentration 239,240Pu and 241Am; to determine the amount of leachable versus nonleachable 239,240Pu and 241Am; to determine the activity ratio of 239,240Pu to 241Am. All samples were analyzed using a sodium-iodide detector, and some samples were further analyzed and counted via alpha spectrometry (α-spec). Comparison of the γ-spec and α-spec results indicates good agreement for 241Am activity concentrations. The 239,240Pu to 241Am ratio ranges from 5.2 to 7.0 when determined via radiochemical separations. Gamma spectrometry is acceptable for determining the soil activity concentration of bulk samples; however mean values may be off by up to 29% for samples with “hot particles”. Radiochemical analysis indicates that for these soil samples, complete soil dissolution to include pyrosulfate fusion is necessary, otherwise over 50% of the insoluble plutonium and americium may be unaccounted for by leaching alone. 148 ASSESSMENT OF SOIL CONTAMINATION IN THE VICINITY OF A RESEARCH REACTOR DURING THE DECOMMISSIONING PROCESS. E. Hrnecek*1, J. Feichtinger1, T. Benesch1. 1Austrian Research Centers Seibersdorf, 2444 Seibersdorf, AUSTRIA After the shut-down of the 10 MW ASTRA research reactor at the Austrian Research Centers Seibersdorf in 1999, the research center was required by the competent authorities to verify that no significant contaminations on the site of the research center have occurred during operation of the reactor and during conditioning of nuclear and radiological waste. Thus a programme has been started to assess the radiological situation of the terrain in vicinity of the reactor and waste conditioning buildings. For screening of the sites, in situ gamma spectrometry with a collimated p-type HPGe detector (30% relative efficiency, Canberra) in combination with Insikont 2.2 software was used. On selected sites, soil profiles were sampled and depth profiles were established by gamma spectrometric measurements. For assessment of actinides, soil profiles were analysed for Pu and Am by separation of Pu on Dowex 1X8 from 8 M HNO3, elution of Th by 10 M HCl and elution of Pu with 0,1 M NH4I / 9 M HCl. Subsequent separation of Americium was performed on a TRU® column (Eichrom) from 2 M HNO3. Following a wash with 9 M HCl, Am was eluted with 4 M HCl. Samples for alpha spectrometry were prepared by microrecipitation with NdF3. The applied methodology is discussed with regard to the analytical performance and implications for the assessment of selected sites are given. 149 USE OF COMBINED NAA AND SIMS ANALYSES FOR IMPURITY LEVEL ISOTOPE DETECTION. G. H. Miley*, G. Narne, and T. Woo. University of Illinois at Urbana-Champaign,

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI Department of Nuclear, Plasma, and Radiological Engineering, 103 S. Goodwin, Urbana, Illinois 61801, USA. Neutron Activation Analysis (NAA) has many advantages for detection of impurity level isotopes in various media such as metals. These include a high sensitivity and a broad volume coverage. However, a number of isotopes of interest may not have suitable neutron cross-sections for such analysis. Secondary Ion Mass Spectrometry (SIMS) on the other hand detects most isotopes, but suffers from various molecular interferences and coverage of only a small interaction beam size volume per run. Both methods were applied by the authors in studies of a large number of isotopic impurities in electrolytic cell electrodes using thin films of palladium on a plastic substrate. In this case, 9 isotopes were covered by NAA and over 50 with SIMS, including an overlap of the SIMS measurements with the NAA elements to provide a normalization of the two data sets. This combined NAA-SIMS technique, it's advantages and limitations, will be discussed. 150 IEC-BASED NEUTRON GENERATOR FOR SECURITY INSPECTION SYSTEM, G. H. Miley*, L. Wu, and H. J. Kim. University of Illinois at Urbana-Champaign, Fusion Studies Laboratory, Department of Nuclear, Plasma, and Radiological Engineering, 103 S. Goodwin, Urbana, Illinois 61801, USA The use of a small neutron source for airport security inspections based on Inertial Electrostatic Confinement (IEC) fusion of accelerated deuterium ions is discussed. Current inspection systems are strongly based on Xray techniques, but neutron activation including Thermal Neutron Analysis (TNA) and Fast Neutron Analysis (FNA) are more powerful for detecting certain types of explosives in luggage and in cargoes. The IEC neutron generator meets the neutron source requirements, and compared with other candidates such as 252 Cf, is simpler, can be switched on or off, and requires minimal maintenance. A key feature of our approach is the use of a unit comprised of three separate IEC sources: one producing 14 MeV D-T neutrons, a second producing 2.5 MeV D-D neutrons, and a third producing soft x-rays. This combination allows multiple detection methods with composite signal analysis being done by a fuzzy logic system. This combination can significantly reduce false signals. 151 APPLICATION OF A LARGE WELL GERMANIUM DETECTOR FOR THE MEASUREMENT OF ENVIRONMENTAL LEVELS OF RADIOACTIVITY. R. J. Lagomarsino, Environmental Measurements Laboratory, U.S. Department of Energy, 201 Varick St., New York, NY 10014, USA A state-of-the-art, large well germanium detector, has been employed for the quantitative measurement of low levels of radioactivity in a variety of martices. The detector, fabricated by Princeton Gamma Tech in accordance to our specifications, is a 63 mm dia. x 60 mm. height germanium crystal with a 25.4 dia. x 50.0 mm. deep well. This detector, with a well sample volume of approximately 15 mL, exhibits high gamma efficiences because of its near 4 geometry. Calibration curves, gamma energy versus efficiency, have been developed for samples counted in a ½ oz. poly bottle at fill (height) levels ranging from 5.0 mm. to 45.0 mm. Experimental results indicate that self-adsorption corrections for the radionuclides of interest in soils and vegetation sample matrices, are not required. Detector applications were developed for: the verification of sample homogeneity in 0.2). The highest radon level, 55 – 235 Bq/m3, was observed in detached houses made of clay and unburnt bricks that are widely used in suburb areas in Uzbekistan. This can be explained by rather high content of radium in clays and a high radon emanation. In addition, such houses have higher permeation for underground radon than buildings made of burnt bricks and reinforced concrete. Also, they are more susceptible to effect of ground water variations, moisture of soil underneath the houses. The works were conducted according to the grant awarded by Fund of MacArthurs, and the author expresses sincere gratitude to the Fund for financial support. 342 EFFECT OF CLIMATIC FACTORS ON RADON ACTIVITY. A. Yafasov, Research & Industrial Association “Akademasbob”, Akademgorodok, Tashkent, UZBEKISTAN Territory of Uzbekistan is characterized by strongly continental climate, and evaporation prevails over precipitation. In summer time the temperature of the soil surface reaches to +75oC, and air temperature rises up to +50oC, while at night the temperature falls down to +25oC – +30oC. 80% of the territory is plain. The most densely populated part is a foothill plain zone with numerous streams and man made channels giving rise to the irrigation system of our country. In territory of the Central Asia, there are several hundreds uranium deposits and glebes in different stages of development. On the debris cones of mountain rivers flowing on the areas of former uranium mining and processing tailings and waste burials, the radionuclide concentrations significantly exceed acceptable limits. Uranium, thorium, radium transported by the streams, channels and sub-riverbeds are accumulated in stagnant and waterlogged lands forming the uranium (thorium) and accompanying heavy metal contamination areas. Since the water-solubility of radon is rather high (its equilibrium concentration in water is ksol = 0.53, following to the formula ksol = 0.1057+0.405 е–0.0502⋅Т), at warming up of moist soils the radon exhalation abruptly rises, thus, when temperature changes from 20 oC to 50 oC, the radon solubility decreases twice (from 0.25 to 0.13). Therefore, the daily radon fluctuations, caused by inversion effect, are characterized by a high amplitude. The measurements have shown that average background radon activity in atmosphere under intensive air ventilation was 9 – 12 Bq/m3, in a stable atmosphere it was 28-35 Bq/m3, and at early morning ground inversion it became 67 Bq/m3. The works were conducted according to the grant awarded by Fund of MacArthurs. Author expresses sincere gratitude to the Fund for financial support. 343 CHEMICAL CHARACTERIZATION OF RUTHERFORDIUM BY ATOM-AT-A-TIME IONEXCHANGE CHROMATOGRAPHY. H. Haba*1, K. Tsukada2, M. Asai2, A. Toyoshima2,3, K. Akiyama2, I.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI Nishinaka2, M. Hirata2, T. Yaita2, S. Ichikawa2, Y. Nagame2, A. Shinohara3, S. Goto4, T. Kaneko4, H. Kudo4, Y. Oura5, H. Nakahara5, K. Sueki6, A. Yokoyama7, M. Sakama8, M.Schädel9, and J. V. Kratz10, 1RIKEN, Cyclotron Center, Wako, Saitama 351-0198, Japan, 2Advanced Science Research Center, Japan Atomic Energy Research Institute, Tokai, Ibaraki 319-1195, Japan, 3Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, 4Department of Chemistry, Niigata University, Niigata, Niigata 9502181, Japan, 5Graduate School of Science, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan, 6Department of Chemistry, Tsukuba University, Tsukuba 305-8571, Japan, 7Department of Chemistry, Kanazawa University, Kanazawa, Ishikawa 920-1192, Japan, 8School of Health Sciences, University of Tokushima, Tokushima, Tokushima 770-8509, Japan, 9Gesellschaft für Schwerionenforschung, D-64291 Darmstadt, Germany, 10Institut für Kernchemie, Universität Mainz, D-55099 Mainz, Germany Chemical properties of element 104, rutherfordium (Rf), have been investigated together with those of the group-4 elements Zr and Hf by an anion-exchange chromatography at an atom-at-a-time scale. The isotopes 261 Rf, 85Zr, and 169Hf were produced in the 248Cm(18O,5n), natGe(18O,xn), and natGd(18O,xn) reactions, respectively, at the JAERI tandem facility. Their on-line anion exchange separations were performed in the 4.0–11.5 M HCl, 1.9–13.9 M HF, and 8.0 M HNO3 solutions using the Automated Ion exchange separation apparatus coupled with the Detection system for Alpha spectroscopy (AIDA). It was found that the sorption behavior of Rf in the HCl and HNO3 systems is very similar to that of Zr and Hf, indicating that Rf is typically the member of the group-4 elements. On the other hand, a notable difference in the sorption behavior between Rf and its homologues Zr and Hf was found in the HF system. In the conference, the complex formation of Rf will be discussed by referring to the structural analyses of the X-ray Absorption Fine Structure (XAFS) spectra of Zr and Hf solutions and also to the relativistic density functional calculations of Rf, Zr, and Hf complexes. 344 NEUTRON ACTIVATION ANALYSIS OF ABSOLUTELY-DATED TREE RINGS. K. Ünlü1*, P. I. Kuniholm2, J. J. Chiment2, D. K. Hauck1. 1Radiation Science and Engineering Center, The Pennsylvania State University, University Park, PA 16802 USA, 2The Malcolm and Carolyn Wiener Laboratory for Aegean and Near Eastern Dendrochronology, Cornell University, Ithaca, NY 14853 USA. Uptake of metal ions by plant roots is a function of the type and concentration of metal in the soil, the nutrient biochemistry of the plant, and the immediate environment of the root. Uptake of gold (Au) is known to be sensitive to soil pH for many species. Soil acidification due to acid precipitation following volcanic eruptions can dramatically increase uptake by trees. Identification of high content in tree rings in dendrochronologically-dated, overlapping sequences of trees allows the identification of temporallyconscribed, volcanically-influenced periods of environmental change. Ion uptake, specifically determination of trace amounts of Au using neutron activation analysis (NAA) is performed for dendrochronologicallydated wood samples. The concentration of Au will be correlated with known environmental changes, e.g. volcanic activities, during historic periods. Several thousand wood samples will be scanned initially for Au. After this initial measurement, samples containing elevated levels of Au will be analyzed again for short and long half-life elements to investigate other elemental signatures of environmental change. The Malcolm and Carolyn Wiener Laboratory for Aegean and Near Eastern Dendrochronology in Cornell’s Department of the History of Art and Archaeology has archived more than 30,000 individually dated wood samples with 4.5 millions rings from forests in the eastern Mediterranean and former Soviet Union countries. The dates of these samples range from 7000 BC up to present. Initial data presented in this paper are from a single tree that grew in Turkey from 1411 until 1988. Using NAA, trace amounts of Au were measured with ppb level sensitivity in this tree's individual rings for this period. 345 SURVEY OF THE TEACHING AND APPLICATIONS IN RADIOCHEMISTRY IN LATIN AMERICAN COUNTRIES. M.B.A. Vasconcellos*, M. Saiki. IPEN/CNEN-SP-Brazilian Nuclear Energy Commission, Caixa Postal 11049, CEP 05422-970, São Paulo/SP BRAZIL.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI By initiative of the International Atomic Energy Agency, a Technical Meeting was held in Antalya, Turkey, (10-14 June 2002), in order to discuss the situation of the teaching and applications in Radiochemistry in Africa, Asia, Europe, Latin America and in the United States. The concern of the IAEA is due to the fact that previous studies have shown that a gradual decrease of teaching and training opportunities in Radiochemistry has been occurring in Europe and in the United States since more than two decades. In this paper, a description is made of the survey that was undertaken, for the first time, about the situation of Radiochemistry activities in the Region of Latin America, comprising twenty countries from South America, Central America and the Caribbean. It became clear from this study that very strong differences exist between the countries and that most of the nuclear facilities in operation, such as nuclear reactors, hot cells, radiochemical laboratories and cyclotrons are concentrated in six countries, accompanied by research and educational activities. A detailed study of the situation and trends in the Latin American countries is presented, as regards teaching and other activities related to Radiochemistry, as well as a series of suggestions for preservation of knowledge in the field. 346 RECENT DEVELOPMENTS IN SEMICONDUCTOR GAMMA-RAY DETECTORS. P. N. Luke1, M. Amman1, C. S. Tindall1. 1Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. The successful development of lithium-drifted Ge detectors in the 1960's has revolutionized the field of gamma-ray spectroscopy. In the 1970's, high-purity Ge became available, which eased detector fabrication and enabled the production of complex detectors and multi-detector systems. In the following decades, the technology of semiconductor gamma-ray detectors continued to advance, with significant developments not only in Ge detectors but also in Si detectors and room-temperature compound-semiconductor detectors. Our group at Lawrence Berkeley National Laboratory has been actively engaged in the development of semiconductor radiation detectors since the early days of lithium-drifted Ge detectors, and has developed technologies to ease the fabrication of complex detectors and to improve detector performance. In recent years, we have worked on a variety of gamma ray detectors based on different materials. Examples include fine-pitched Ge strip and pixel detectors, coplanar-grid CdZnTe detectors, and orthogonal-strip lithiumdrifted Si detectors. These advances provide new capabilities in the measurement of gamma rays, such as the ability to perform imaging and the realization of highly portable spectroscopic systems. An overview of these developments is presented. 347 ATMOSPHERIC MONITORING OF ANTHROPOGENIC NUCLIDES IN MELBOURNE, AUSTRALIA. R.A. Tinker1, R. O’Brien1, M. B. Cooper*2 ,1Australian Radiation Protection and Nuclear Safety Agency (ARPANSA), Environmental & Radiation Health Branch, Yallambie, Victoria, AUSTRALIA, 2Envirorad Services Pty Ltd, Beaumaris, Victoria, AUSTRALIA. The atmospheric radionuclide monitoring station has been continuously sampling at ARPANSA in Melbourne, Australia, since September 2000 as part of the verification system of the Comprehensive Nuclear-Test-Ban Treaty (CTBT). The monitoring station consists of a high volume sampler capable of sampling approximately 20,000 cubic metres of air in 24 hours. The air filters are analysed by highresolution gamma-ray spectroscopy with the resulting gamma-ray spectra enabling quantitative determination of atmospheric radionuclides. The station has proved to be capable of detecting anthropogenic radionuclides with a very high degree of sensitivity, for example, I-131 concentrations down to 1-2 µBq.m-3. Although in the two years of operation, the station normally measures only naturally-occurring airborne radionuclides, there has been the occasional detection of fission products attributable to the use of medical isotopes in Melbourne. In a recent occurrence, several anthropogenic nuclides, namely, I-131, Tc-99m, Au198 and I-124, were detected in one daily sample. It is likely that these radionuclides do not originate from the same source and the process to determine their likely origins is described in this paper. Also discussed are the implications of the presence of these types of fission products and other anthropogenic radionuclides on

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI the potential to interfere with the nuclear weapons test signals that are the target for monitoring compliance with the CTBT. 348 CORRELATION BETWEEN LIMESTONE DOSIS AND MINERAL CONTENTS IN TROPICAL GRASS FORAGE. M. J. A. Armelin1, O. Primavesi2, A. C. Primavesi2, M. Saiki1. 1 Radiochemistry Division, Instituto de Pesquisas Energéticas e Nucleares, IPEN/CNEN-SP, SP, Brazil. 2 Southeast Embrapa Cattle, São Carlos-SP, BRAZIL The field trial was performed at the experimental farm of Southeast Embrapa Cattle, São Carlos-SP, Brazil, on a 16 year old Brachiaria decumbens pasture, grown on a distrophic Hapludox, being recovered by limestone and fertilizer use. The experimental design was a randomized block, with 6 replications and 5 treatments. The 100 m2 blocks were established in the pasture. Each block received a sequence of limestone dosis (0, 1, 2, 4 and 8 t/ha). The forages samples were taken one year after limestone broadcast on soil surface application. Instrumental neutron activation analysis (INAA) followed by gamma-ray spectrometry was the analytical method used to determine mineral contents. The statistical analysis showed a negative linear correlation of Br, Co, Cr, Mn and Zn contents in forage with the limestone dosis, while Mg was affected in a positive linear. 349 PUBLIC AWARENESS OF NUCLEAR SCIENCE IN EUROPE. A.Kugler, Chairmen of Nuclear Physics Board of European Physical Society, Nuclear Physics Institute, CZ 250 68 Rez, Czech Republic PANS originated from the idea that it is important to convey to the general public important issues associated with Nuclear Science. The assumption is that an informed public is better able to come to sensible judgements based on knowledge instead of prejudice. The image of anything "nuclear" is presently viewed in Europe with suspicion mainly due to the public perception being influenced by sensational negative media coverage rather than a balance view across the whole field. If nuclear science is to have a healthy future, then it is important that we initiate activities that can start to bring about a more balanced view. This is the basic remit of PANS. It is an activity that was started several years ago by two bodies, which represent Nuclear Physics community in Europe, i.e. by the NPB of EPS and NuPECC of ESF. In the framework of PANS projects like BOOK and EXHIBITION were successfully carried out, while others are still in preparation, like CD-ROM, PANS-WEB etc. 351 SELENIUM AND NUTRITION: THE ACCURACY AND VARIABILITY OF THE SELENIUM CONTENT IN COMMERCIAL SUPPLEMENTS. A.E. Veatch1,2, J.D. Brockman3, V.L. Spate2, J.D. Robertson*2,3 and J.S. Morris2,4. 1School of Veterinary Medicine, University of Missouri, Columbia, MO 65211, USA. 2 Research Reactor Center, University of Missouri (MURR), Columbia, MO 65211, USA. 3 Department of Chemistry, University of Missouri, Columbia, MO 65211, USA. 4Harry S Truman Memorial Veterans Administration Hospital, Columbia, MO 65201, USA Selenium is a required trace-element that has been found to be protective against serious chronic diseases such as cancer and cardiovascular disease in some, but not all, epidemiological studies using both casecontrol and intervention designs. As a result, the fraction of the adult U.S. population now taking a daily selenium supplement is steadily increasing. In this study we analyzed 10 or more replicate Se supplement tablets, from each of 15 different products representing 12 different brand names and sampled at two different times separated by approximately 28 months. Two chemical forms, seleno-yeast and selenate were tested in 50, 100 and 200 mcg/tablet dosages (seleno-yeast) and 25 and 200 mcg/tablet dosages (selenate). Variations in contemporary lots were evaluated for 2 seleno-yeast supplements and one selenate-containing multi-vitamin for both sampling periods. The Se content provided on the product label is generally understated. One tablet contained 2.5 times more selenium than the stated dose. Selenate supplements are less accurately labeled and more highly variable compared to yeast supplements. One popular multivitamin,

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI labeled at 200 mcg/tablet, contained tablets in excess of 300 mcg. Many subjects using this supplement will exceed the 400 mcg /day tolerable upper limit of intake recently established for Se by the Institute of Medicine’s Food and Nutrition Board. 352 RADIOCHEMISTRY AT MU – A JOINT VENTURE WITH CHEMISTRY, NUCLEAR ENGINEERING, MOLECULAR BIOLOGY, BIOCHEMISTRY AND THE MURR. W. H. Miller, P. Duval, S. S. Jurisson, J. D. Robertson, J. D. Wall, T. P. Quinn and G. M. Neumeyer, Missouri University, Columbia, MO 65211, USA Missouri University, a recipient of a Department of Energy Radiochemistry Education Award Program grant in 1999, has significantly expanded its education and research mission in radiochemistry. MU has had a viable radiochemistry program through existing faculty expertise and the utilization of the Missouri University Research Reactor. The REAP award expanded upon this foundation by allowing the 1) hire of a new faculty member in radiochemistry (Dr. Paul Duval); 2) support of six graduate students in radiochemistry; 3) purchase of new laboratory equipment; 4) additional collaboration with DOE personnel; and 5) revised radiochemical curriculum (joint courses across disciplines and new courses in actinide chemistry). The most significant impact of this award has been in encouraging interdisciplinary education and research. The proposal was initiated by a joint effort between Nuclear Engineering and Chemistry, but has expanded to include: 1) actinide chemistry; 2) biochemistry (radiochemical analysis of uranium speciation in biological systems); 3) molecular biology (alpha emitters for treating cancer); 4) utilization of national laboratory facilities (analytical measurements at the Advanced Photon Source); 5) national laboratory personnel interactions, 6) three student internships at national laboratories and 7) new research funding. 353 PORTABLE PLUTONIUM MASS VERIFICATION SYSTEM. J. C. Swanson*, B. Buckley, Y.X. Dardenne, D.L. Johnson, and T.F. Wang , Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, Ca., 94551 USA Special Nuclear Material (SNM) accounting at some DOE facilities requires removal of samples from storage, transport to a counting facility, removal of the sample from its storage container, counting, repackaging, and transport back to the storage facility until selected in the next physical inventory. The procedure takes time, and results in both radiation exposure and increased potential for diversion. If a verification can be performed within the storage vault, and not require removal of the SNM from the container, personnel time and radiation exposure could be reduced, the sample would not have to leave the security of the storage vault, and costs for performing inventories could be reduced. Lawrence Livermore National Laboratory (LLNL) has developed an instrument, based on established coincidence counting techniques, to yield a semi-portable Pu mass verification solution to the problem of in-vault verification. Commercially available instrumentation is being used to enable in-situ verification of Pu masses in sealed containers. The detector assembly includes both neutron and gamma detectors. The device will operate on battery power, and will be mounted on a cart for portability. For mass verification of plutonium, two types of signal are analyzed. A gamma spectrum is analyzed for isotopic ratios using LLNL's MGAHI code. Neutron count rates and coincidence rates are measured to quantify the spontaneous fission rate within the Pu. Corrections for neutron scattering, alpha-neutron reaction sources, and neutron multiplication must be made to establish the necessary accuracy for this analysis. The system is intended to be easy to set-up and operate 354 DO WE NEED RADIOCHEMISTRY IN ACTIVATION ANALYSIS? J. Kucera1 and R. Zeisler2. 1 Nuclear Physics Institute, CZ-250 68 Rez near Prague, Czech Republic. 2National Institute of Standards and Technology, Gaithersburg, MD 20899, USA.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI It follows from the basic activation analysis equation that its procedures can be optimized towards achieving low-uncertainty results using both physical, nondestructive and chemical approaches. The former approach involves considerations about the nuclear constants σ, θ and λ (especially for polyisotopic elements), fluence of activation particles, sample mass, irradiation, decay and counting times (especially for short lived radionuclides), selectivity of activation (energy of activation particles), and selectivity and efficiency of radioactivity measurement. The chemical approach entails pre-irradiation or post-irradiation (radiochemical) separation of the analyte (radionuclide) of interest from interfering matrices or components. Examples of determination of arsenic, iodine, silicon, and vanadium by radiochemical neutron activation analysis (RNAA) and determination of fluorine by radiochemical photon activation analysis (RPAA) in biological materials show that in spite of methodological and instrumental developments in the physical approach, radiochemical procedures are indispensable for achieving the lowest detection limits and uncertainty. Other elements occuring at extremely low levels, such as Cr, Mn, or Pt in human blood or serum must be done by RNAA to obtain results. 355 FISSION PROCESS AND ITS APPLICATION IN CHARACTERIZATION OF TRU WASTE AND SPENT NUCLEAR FUEL*. R. Aryaeinejad, E.L. Reber, J.K. Jewell, J.D. Cole, and M.W. Drigert, Idaho National Engineering & Environmental Laboratory, Idaho Falls, ID 83415-2114, USA During the last ten years, we have been collaborating with several universities and national and international laboratories to study the prompt fission process using multi-detector arrays. Historically, this process was investigated by examining the fission fragments that were produced via beta decay. While these studies have provided much of the existing fission knowledge, they offer little insight into the prompt fission process itself. In this work, prompt X-rays and gamma rays emitted by spontaneous and thermal neutron-induced fission decay using fast coincidence techniques are used to identify both light and heavy fragments, obtain gamma-ray signatures and radiation multiplicity. The spontaneous fission experiments were performed with Cf-252 and Pu-242 sources using the Compact Ball at ORNL (20 Compton-Suppressed Ge detectors, CSGe), the Gammasphere at LBNL (75 CSGe detectors), and X-ray/Gamma-ray Spectrometer at the INEEL (2 LEPS X-ray and 3 Ge detectors). In the latter, the X-ray detectors operating in coincidence with gamma-ray detectors provided additional data (Z identification) that was used in identifying fission fragments. The thermal neutron-induced fission measurements were carried out with U-235 and Pu-239 targets using the Intense Pulsed Neutron Source (IPNS) at Argonne National Laboratory. The experimental techniques, comparison between spontaneous and induced fission, the results of the analysis and their applications in characterizing TRU waste and spent nuclear fuel will be presented. * Work performed under the auspices of the U.S. Department of Energy, DOE Contract No. DE-AC0799ID13727BBWI. 356 MEASUREMENT OF THE FISSION YIELDS OF SELECTED γ RAYS AND ASSOCIATED MASSES OF SPONTANEOUSLY FISSIONING 252Cf, 244Cm, 240Pu, and 242Pu.1E.L. Reber*, R.J. Gehrke, R. Aryaeinejad, and J.K. Hartwell, Idaho National Engineering & Environmental Laboratory, Idaho Falls, ID 83415, USA Singles γ-ray spectrometry measurements have been made of the fission yields of selected γ rays emitted by the spontaneously fissioning isotopes 252Cf, 244Cm, 240Pu and 242Pu. The measured γ rays were selected based on their relative abundance in the spectrum and their being either interference free or the interfering γ ray can be subtracted from the γ-ray peak of interest. From these data and the cumulative and independent yield data of T.R. England and B.F. Rider2 those γ rays that are primarily produced by radioactive decay (i.e., cumulative yield dominates) are converted into a mass yield and compared to the values of England and Rider2. For those γ rays whose production is dominated by direct (independent) yield, their γ-ray yield is reported and compared to the independent yield values of England and Rider2. In those cases where both

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI cumulative and independent yields are observed an effort will be made to separate out the contribution of each as in the 1279-keV γ ray resulting from direct fission yield to the 1279-keV excited state of 134*Te. The ability to distinguish the spontaneously fissioning radionuclides studied from the measured fission yields of the selected γ rays will be reported. 1. Work performed under the auspices of the U.S. Department of Energy, DOE Contract No. DE-AC0799ID13727BBWI. 2. “Evaluation and Compilation of Fission Yields”, T.R. England and B.F. Rider, ENDF-349, LA-UR-943106. 357 UTILIZATION OF PHOSWICH DETECTORS FOR MULTIPLE RADIATION DETECTION, William H. Miller and Manuel Diaz de Leon, Nuclear Science and Engineering Institute, University of Missouri-Columbia, Columbia, MO 65211, USA A phoswich radiation detector is comprised of a phosphor sandwich in which several different phosphors are viewed by a common photomultiplier. By selecting the appropriate phosphors, this system can be used to simultaneously measure multiple radiation types (alpha, beta, gamma and/or neutron) with a single detector. Differentiation between the signals from the different phosphors is accomplished using digital pulse shape discrimination techniques. This method has been shown to result in accurate discrimination with highly reliable and versatile digital systems. This system also requires minimal component count (i.e. only the detector and a computer for signal processing). A variety of detectors of this type have been built and tested including: 1) a triple phoswich system for alpha/beta/gamma swipe counting, 2) two well-type detectors for measuring low levels of low energy photons in the presence of a high energy background, 3) a large area detector for measuring beta contamination in the presence of a photon background, 4) another large area detector for measuring low energy photons from radioactive elements such as uranium in the presence of a photon background, and 5) an annular geometry, triple phoswich system optimized for measuring alpha/beta/gamma radiation in liquid waste processing streams. 358 AUTOMATED RADIOCHEMICAL ANALYSIS OF TOTAL TC-99 IN AGED NUCLEAR WASTE PROCESSING STREAMS. O. Egorov*, M. O’Hara, J. Grate, Pacific Northwest National Laboratory, Richland, WA 99352, USA Determination of Tc-99 in nuclear waste processing streams will be required during waste processing operations at the Hanford Site. Currently, there is a lack of analytical methodologies suitable for reliable, rapid, and selective determination of this radionuclide in chemically and radiologically complex matrixes. The research in our laboratory has been directed at the development of a fully automated Tc-99 analyzer instrument based on the radiochemical measurement approach. Technetium-99 quantification is carried out using flow-through solid scintillation detection, after the pertechnetate species are separated from interfering radionuclides. Microwave-assisted sample oxidation is carried prior to chemical separation in order to oxidize all non-pertechnetate species to pertechnetate. Advanced digital fluid handling techniques are used for sample/solutions manipulation and system integration. Performance characteristics of the monitor instrument and analysis of the caustic waste samples from the Hanford site will be discussed. 359 RADIOCHEMICAL SENSOR SYSTEM FOR THE ANALYSIS OF 99TC(VII) IN GROUNDWATER. O. Egorov*, M. O’Hara, J. Grate, M. Knopf, G. Anderson, John Hartman. Pacific Northwest National Laboratory, Richland, WA 99352, USA Monitoring of the radionuclide contaminants such as 99Tc in groundwater represents an important element in support of the Hanford site remediation activities. Direct determination (sensing) of the pure beta-emitter 99 Tc represents a substantial challenge due to short radiation range and energy overlap or interference problems. As the result, expensive and time measurements are used for determination of 99Tc in groundwater samples. Research in our laboratories has been directed at addressing the fundamental challenges of

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI monitoring of low levels of non-gamma-emitting radionuclides (such as 99Tc) in groundwater. We will present results on the development and testing of the reagentless radiometric sensor for in-situ 99Tc detection in groundwater. The sensing approach is based on the use of a dual-function composite sensor column that combines both radionuclide selective sorption and scintillating properties. This presentation will describe the principles of the equilibrium radiochemical sensing. In addition we will discuss design and testing of a probe that integrates sensor element, scintillation detection, data acquisition and instrument control components in a single functional sensor unit compatible with a 3.5-inch well geometry. 360 GAS CHEMICAL METHODS OF SEPARATION OF ELEMENTS IN RADIOISOTOPE PRODUCTION AND ACTIVATION ANALYSIS. Boris L. Zhuikov, Institute for Nuclear Research of Russian Academy of Sciences, 60th October Anniversary Prospect, 7A, Moscow, 117312, RUSSIA An analytical system is considered separate a number of elements of Periodic Table in the form of volatile elements and oxides at temperatures up to 14000C. Thermo-chromatography method as well as high temperature chemical filters are used. Separation in hydrogen or oxygen (air) stream is considered. The successive use of these gas carriers allows changing the chemical state for the required separation. Several advantages of the chemical filters made of various oxides or metal has been demonstrated. These are: selectivity and simplicity of processing, a possibility to separate both macro- and micro-quantities of different elements in one experiment. The approach has demonstrated its efficiency in a number of examples of carrier-free isotope production from the targets irradiated at accelerator as well in other applications: 109Cd from In, 22Na from Al, 72Se from GaAs, 188Pt, 183Re, 185Os and 201Tl from Pb or Bi, separation of Po from Pb and Bi, etc. Another application of high temperature chemical sublimation of elements and oxides was realized in activation analysis of noble metals in various ores and samples. Thus neutron activation following by the separation provided determination of Pt – up to 10 ng, Ir – 0.1 ng, Au – 0.01 ng, Ru – 2 ng, Ag – 20 ng in natural samples of several grams mass. 361 CROSS-SECTION STUDIES ON COPPER-64 WITH ZINC TARGET IN THE PROTON ENERGY RANGE 40 - 140 MeV. Mauro L. Bonardi1, Flavia Groppi1, Vladimir M. Kokhanyuk2, Elena V. Lapshina2, Michail V. Mebel2, Boris L. Zhuikov2. 1Università degli Studi and INFN-Milano, LASA, Via F.lli Cervi 201, I-20090 Segrate, Milano, ITALY. 2Institite for Nuclear Research of Russian Academy of Sciences, 60-th October Anniversary Prospect, 7A, Moscow, 117312, RUSSIA. The cross-sections for production of NCA Cu-64 from Zn target in proton energy range from 40 up to 140 MeV were measured. Stack foil technique was used at 160 MeV proton beam of INR LINAC in Troitsk, Russia. The stack of 12 thin Zn targets, with Al catchers, graphite energy degraders and Cu monitor foils were inserted into the water-cooled irradiation facility. Several Ga, Zn, Cu, Ni, Co and Mn radionuclides were detected in Zn targets at EOB. The activity of Cu-64 was measured through its only gamma emission of 1346 keV (0.47 % intensity). It was necessary in this case to carry out a radiochemical separation of Ga radionuclides from the bulk of irradiated Zn target and other radionuclides. All Zn targets were dissolved in 7 M HCl. Ga radionuclides produced in the targets with high yields (i.e. Ga-67 and Ga-66) were separated quantitatively and selectively as Ga(III) chlorocomplexes by L/L extraction in iso-propylether from the above solution. No other radionuclides were present in the organic phase. The 1346 keV emission of Cu-64 was detected in the aqueous phase with a good statistics. Theoretical calculations of cross-sections will be also presented. 362 DEVELOPMENT OF A NEW TECHNIQUE TO TRACE 15O-WATER UPTAKE IN A LIVING PLANT WITH AN IMAGING PLATE AND BGO DETECTORS. K. Tanoi*1, T. M. Nakanishi1, J. Hojo2, K.Suzuki2, 1Graduate School of Agricultural and Life Sciences, The University of Tokyo, 2National Institute of Radiological Sciences, Tokyo, JAPAN

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI Though water plays an important role in plant physiology, water behavior in a living plant has not been known well due to lacking tools for the research. Here, we present a new trial to measure real time water movement using a positron emitting nuclide, 15O. 15O was prepared by 14N(d, n)15O reaction and 10 ml of 15 O labeled water (1 to 2 GBq) was supplied from the root of a soybean plant. To detect radioactivity, an imaging plate (IP) as well as a pair of BGO detectors were used. Since the half-life of 15O is extremely short, 2.0 min, water uptake measurement was performed only for 20 min. The BGO detectors were set at the lowest stem and the gamma-rays (0.511 MeV) emitted from the nuclide were measured through coincidence counting. The performance of the BGO detectors, such as counting efficiency or detection limit is now studying and we will show the results at the conference. Since the positron energy of 15O is rather high, 1.73 MeV, some positrons are estimated to escape from the plant tissue before annihilation occurs. Therefore, we used an IP to get autoradiograph and compared the activity with that of BGO detector. The IP was exposed to the plant for 1 min, every 10 min during the measurement. We found that the water uptake activity of the plant was drastically reduced under high humidity (99%) and dark condition and there was a correlation between the uptake amount of water and light intensity. 363 EPAA3: JOB-DRIVEN NAA SOFTWARE. R. Kada1, P. Bouffard 2, G. Kennedy*1, L.G.I. Bennett2, J. St. Pierre1, and K.S. Nielsen2. 1Ecole Polytechnique, Montreal, Quebec, Canada. 2Royal Military College, Kingston, Ontario, CANADA Neutron Activation Analysis (NAA) benefits from many advantages over other chemical analysis techniques, but is handicapped by the lack of software developed specifically for this purpose. Most NAA software in use today relies on the results of peak search and peak area calculation routines developed for other spectrometry applications. The output of these routines must be fed into the NAA software to derive the relevant NAA quantities: the concentrations of the chosen elements. Difficulties arise because the NAA software must weed through large quantities of useless data. Furthermore, it is often difficult to direct the peak search software to the important peaks and the known interferences. We therefore developed job-driven NAA software; the original version was a DOS program, EPAA, written at Ecole Polytechnique. From the first step, the knowledge of the desired elements is used to direct the interactive treatment of the gamma-ray spectra. As a final step, a spreadsheet uses the EPAA output file to produce the analysis report. The original EPAA code was completely rewritten at Royal Military College to run under Windows, and was renamed NAA99. The latest version, EPAA3, is now being modified for improved peak fitting, expanded output files and to read the spectrum files of all gamma-ray spectrometers. 364 PORTABLE SYSTEM FOR NUCLEAR, CHEMICAL AGENT AND EXPLOSIVES IDENTIFICATION. W.M. Buckley1, W.E. Parker1, S.A. Kreek1, G.J. Mauger1, A.D. Lavietes1, A.D. Dougan1, A.J. Caffrey2. 1Lawrence Livermore National Laboratory, P.O. 808, Livermore, CA 94551 USA, , 2 Idaho National Engineering & Environmental Laboratory, Idaho Falls, ID 83415 USA The FRIS/PINS hybrid integrates the LLNL-developed Field Radionuclide Identification System (FRIS) with the INEEL-developed Portable Isotopic Neutron Spectroscopy (PINS) chemical assay system to yield a combined general radioisotope, special nuclear material (SNM), and chemical weapons/explosives (CWE) detection and identification system. The PINS system uses a shuttered neutron source and a high-purity germanium gamma-ray detector. CWE are detected via interrogation with neutrons and detection/analysis of the high-energy capture gamma rays associated with CWE. This system employs high-resolution gamma-ray spectroscopy for its radiation detection technology. The FRIS system uses the same radiation detection technology and its own analysis software to detect and identify SNM and other radioisotopes. The FRIS/PINS system uses the electromechanically-cooled germanium detector which makes the system completely portable for long periods and significantly easier to deploy than systems employing liquid nitrogen cooled germanium detector technology. The system is compact and truly portable, capable of battery operation. High-resolution gamma-ray spectrometry provides improved discrimination from

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI materials with similar composition to CWE or SNM that are shipped legitimately throughout the world. There is no other currently available integrated technology that can combine an active neutron interrogation and analysis capability for CWE with a passive radioisotope measurement and identification capability for SNM. 365 DEVELOPMENT OF AN “ISOTOPICS” PULSER. S. J. Luke*, G. Schmid, D. Beckedahl, B. Pohl and G. White, Lawrence Livermore National Laboratory, Livermore, CA94551, USA We have developed a pulser that is able to output a simulated signal from an HPGe detector for various plutonium and uranium isotopes. A pulser of this sort could be used for training or instrument authentication when it is not possible to have the presence of Special Nuclear Material (SNM). In this paper we describe the development of an “isotopics” pulser for the simulation of signals that are produced in an HPGe detector. We will discuss the several types of pulsers that have been developed. The present incarnations of the pulser generates the waveforms that are produced by an HPGe detector both before and after the preamplifier. These signals have been input into a normal MCA and the result is a standard pulse height distribution. We will describe the methods, which we used to generate the waveforms and demonstrate the pulser as well. This work was performed under the auspices of the U.S. Department of Energy by University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48. 366 INCREASED DETECTOR SENSITIVITY THROUGH EVENT-MODE DATA COLLECTION. D. Archer*, S.J. Luke, and W. Current, Lawrence Livermore National Laboratory, Livermore, CA94551, USA Increasing the sensitivity of radiation detectors is one characteristic that is desirable in detectors being built today. Sensitivity can be thought of in several different ways. Two of these include energy resolution and/ signal-to-background ratio. Increasing the energy resolution within current technologies is problematic for “real-world” applications because it compels the detector to take advantage of semiconductor technology, which necessarily causes the detector to have a small cross-sectional area and therefore have a limited acceptance. Improving the signal-to-noise ratio is usually accomplished by limiting the background. This is most conveniently accomplished by collimating the detector in some fashion, which reduces the effective active solid angle of the detector. These two approaches to increase the sensitivity of radiation detectors are not optimal for the detection of a source over a short time period. In order to increase the detector sensitivity for data obtained in a signal starved environment, we are developing an event-mode spectral-quality data acquisition system. This data acquisition system allows the user to manipulate the data with maximum flexibility achieving maximum signal-to-background for any single event. We will discuss the data acquisition system and present results from the system, including comparisons from typical MCA dwell times. This work was performed under the auspices of the U.S. Department of Energy by University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48. 367 A NEW APPROACH FOR THE MINIATURIZATION OF MULTIPLE FARADAY CUP COLLECTORS. J.C. Banar *1, E.P. Chamberlin 1, J. Poths 2, R.E. Perrin 1, P. Chastagner 3, 1 Los Alamos 2 National Laboratory, C-INC, Los Alamos, NM, 87545, USA Los Alamos National Laboratory, ESA-TSE, 3 Los Alamos, NM, 87545, USA Private Consultant, Savanna, Ga, 31410, USA The mass spectrometry section in C-INC at Los Alamos National Laboratory has been working for several years on a novel solution to overcome the size and placement restrictions of multiple Faraday cup collectors. Use of simultaneous collection of multiple isotope ion beams both increases precision in the isotopic measurements and shortens the data collection time. Our application is for the measurement of the isotopic

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI composition of Xe, ionized in a source that produces a large (10-11 amp) but variable ion beam. We chose a Mattauch-Herzog geometry mass spectrometer with a 25 cm radius for these measurements. This mass spectrometer has the advantage that excellent electron suppression at the collector cups is achieved by placement of the Faraday cups at the focal plane within the gap of the analyzer magnet. However, it has the disadvantage of low dispersion -- the Xe ion beams are separated by less than 1mm per mass unit. The standard method of fabricating metal cups, supported and insulated with an intricate mounting system, could not meet the requirements for size and fabrication tolerances for this instrument. We therefore opted to construct a multiple cup assembly from an insulating substrate with a metal film applied to the ion-impact and current carrying surfaces. Thus, the insulating and support functions could be fabricated to very tight tolerances. This considerably simplified design allowed Faraday cups to fabricated for ion beams separated by only 0.94mm. Testing of this prototype collector assembly with Xe ion beam shows encouraging results. 368 SORPTION/DESORPTION OF CESIUM IN SULFATE-RESISTANT PORTLAND CEMENTS. M.J. Rudin*1, W.H. Johnson1, and S.M. Steinberg2. 1Department of Health Physics, University of Nevada, Las Vegas, Las Vegas, NV 89154-3037, USA. 2Department of Chemistry, University of Nevada, Las Vegas, Las Vegas, NV 89154-4003, USA. Relatively high levels of sulfate found in the desert soils of the southwest U.S. preclude the use of ordinary Portland cements in many underground applications. Typically, sulfate-resistant cements, such as a Type V or a Type II/V, are used to minimize sulfate attack and maintain cement integrity in these harsh environments. The sorption and desorption properties of cesium on three sulfate-resistant Portland cements, and one Type III Portland cement, with water-to-cement ratios of 0.33, 0.43, and 0.53 was evaluated. A batch sorption procedure was utilized to determine distribution coefficients (Kd) for cesium. Initial results indicated that maximum cesium sorption occurs at 1 d and tends to decrease as the time of contact between the cement and the cesium solution is increased. Experimental Kd values obtained at 1 d ranged from 0.9237.1 L kg-1 with the smallest values observed for the Type V cements, and the greatest amount of cesium sorption occurring in the Type III cement. The effect of varying the water-to-cement ratios of the mixes on cesium sorption was negligible. A number of washes were then performed on each of the cements using a 0.01M CaCl2 solution to examine the kinetics of cesium desorption. Results indicated that cesium sorption was reversible on all cement types with the greatest rate of desorption occurring in the Type V cements. 369 COMPARISON OF DIRECT KINETIC PHOSPHORESCENCE ANALYSIS AND RECOVERY CORRECTED KINETIC PHOSPHORESCENCE ANALYSIS FOR THE DETERMINATION OF NATURAL URANIUM IN HUMAN TISSUES. J. T. Elliston,*1 S. E. Glover,2 R. H. Filby3. 1United States Transuranium and Uranium Registries, Nuclear Radiation Center, Washington State University, P.O. Box 641300, Pullman, WA 99164-1300, USA. 2Isotope & Nuclear Chemistry, Los Alamos National Laboratory, Mailstop J514, Los Alamos, NM 87545, USA, 3Department of Chemistry, Washington State University, P.O. Box 644630, Pullman, WA 99164-4630, USA In the analysis of biological samples with sub ng/g uranium concentrations, pre-concentration has been shown to improve the detection limit for the determination of uranium. Recovery corrected kinetic phosphorescence analysis (KPA) combines pre-concentration and separation of uranium by anion exchange from human tissues dissolved in 6 M HCl, with the radiochemical yield determined by alpha spectrometry, using 232U as a tracer. Total uranium is determined by KPA after correction for chemical recovery. Twentyone randomly selected dissolved tissue samples from the United States Transuranium and Uranium Registries (USTUR) Case 0242 were chosen for comparative analyses. The set of samples included dissolved bone and soft tissues. Uranium concentrations for seven of the samples had not been previously reported. Direct KPA could not be used to determine uranium concentrations of five unreported tissues. Three of these tissues had uranium concentrations at or below the KPA LQ value of 0.028 ng/mL and two tissues had known matrix interferences. All seven of the unreported tissues were successfully analyzed by recovery corrected KPA; concentrations ranged from 9 ng to 1380 ng per tissue, including those that could

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI not be analyzed by direct KPA due to matrix problems. Recovery corrected KPA gives results similar to direct KPA where matrix interferences and low detection limits are not encountered. A comparison of the direct method of KPA versus recovery corrected KPA shows marked improvement for the determination of uranium in samples that heretofore either uranium was not detected or the sample had to be drastically diluted to minimize matrix effects in order to measure uranium. 370 SIGNAL PROCESSING AND METROLOGICAL QUALITY IN INAA. R. Zeisler, Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-8395, U.S.A. Gamma-ray spectrometry losses through pulse processing dead time, pile-up and coincidence events can become a significant source of measurement bias if not properly accounted for. These effects are more consequential in experiments that attempt to minimize counting uncertainties through the acquisition of high numbers of counts, in many instances in conjunction with the use of high count rates. External pulse, livetime clock extension, loss-free counting (LFC), and digital dead time compensation (“zero dead-time” ZDT) methods are available for correction. In this work, basic performances of LFC and ZDT were tested through dual source calibration and decaying source techniques. Results demonstrate the reliability of the LFC and ZDT methods for the accurate correction of dead-time losses during high rate counting, including during rapid changes in the dead time as encountered with the decay of short-lived activities. Applications of INAA in “metrological quality” determinations of major constituents as well as of trace elements illustrate the applicability of the correction methods, however a full assessment of uncertainties is difficult. 371 RADIOCHEMICAL SEPARATION ADVANCEMENTS USING EXTRACTION CHROMATOGRAPHY: A SYNOPSIS OF RECENT EICHROM USERS’ GROUP WORKSHOP PRESENTATIONS WITH A FOCUS ON MATRIX INTERFERENCES. L.E.Jassin*1, M. Fern1, M. Langer2, P. Letessier2 and A Thakkar1. 1Eichrom Technologies, Inc., Darien, IL 60561, USA, 2Eichrom Europe S.A.R.L., Paris France 75010. Starting with some basic tools, Eichrom Technologies has endeavored to advance the efficiency with which a myriad of radiochemical separations are performed. These tools fall under the broad classification of Extraction Chromatography, ‘EXC’. By combining the selectivity of chemical extractants with the ease of use of a chromatographic resin column, Eichrom offers radiochemistry laboratories a powerful approach to preparing samples for analysis. But how powerful are these materials? Certainly they perform well for many sample types, but what about actinides in large soil sample, Sr-90 in bone, U from an air filter with significant Po-210 and Tc-99 in a sample high in Th-234? Can EXC be considered as a tool for handling these samples. Recent presentations made during Eichrom Users’ workshops answer with a resounding yes! Certainly, standard water methods require modification to handle these types of matrix interferences, but in all cases, EXC can be used to perform these separations. This paper will provide data and the method details required to handle these real world samples. 372 GROSS ALPHA DETERMINATION IN DRINKING WATER USING A HIGHLY SPECIFIC RESIN AND LSC. P.R. Letessier*1, A.H. Thakkar2, P.J.M. Kwakman3, J.H.R. Eikenberg4, E.P. Horwitz2., 1 Eichrom Europe - 50 Rue de Paradis - 75010 Paris – France / 2Eichrom Technologies, Inc., Darien, IL 60561, USA / 3RIVM - P.O. Box 1 - 3720 BA Bilthoven - The Netherlands / 4Paul Scherrer Institute Villigan PSI - 5232 – SWITZERLAND. Currently the most popular protocol for the gross alpha measurements is the evaporation of water samples on a planchet and counting of the residue by a Gas flow Proportional Counter. Due to self absorption, the counting efficiency of alpha particles using GPC can decline to less than 10% when 100mg of solids are left on the planchet. Moreover, in order to reach good detetction limit (0.04 Bq/L), the planchet evaporation technique requires long counting time (routinely 18 or 24 hours). Eichrom Technologies has developed the

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI PSM-111 resin which consists of a combination of several extractants supported on an inert polymeric substrate. It shows a strong affinity for actinides in the tri-, tetra- and hexavalent oxidation state as well as for radium out of aqueous solutions. Results obtained show that radium retention is still about 100% even when large amount of calcium is present, i.e., above 300 ppm. The protocol is very simple, quick, and does not require any specific knowledge or skills. The PSM-111 resin in combination with Liquid Scintillation Counting, using α/β discrimination, allow to obtain a detection limit of 0.03 Bq/L within 6 to 8 hours for a sample volume of 100 ml. 373 ALPHA-SPECTROMETRIC THIN SOURCE PREPARATION WITH EMPHASIS ON HOMOGENEITY. H. Klemenčič, L. Benedik* and U. Repinc. Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, SLOVENIA Alpha spectrometry of low-level environmental samples is performed after a radiochemical separation and deposition of the alpha emitting radioisotopes on to a counting surface. The critical stages of such procedures are chemical and radiochemical isolation of the analyte radionuclide from the sample and its components, preparation of a thin, virtually weightless source for high resolution alpha spectroscopy and measurement of the activity in a vacuum chamber with associated electronics as an alpha spectrum. Accurate determination of alpha-emitting nuclide concentrations in environmental samples is heavily dependent on the analyst's ability to prepare and mount the analyte in as pure a form as possible, free of any gravimetric or radiometric interferences which could lead to complications in the interpretation of the measured spectra and reduced overall sensitivity. In the present work the preparation of alpha sources of thorium isotopes by electrodeposition and the microprecipitation technique was studied. Electrodepositions were carried out in home-made electrolytic cells. Differently shaped Pt anodes were used and their influence on the quality of the thin layer of deposited radioisotope was studied. A comparison between the electrodeposition technique and the microprecipitation technique is also described. The quality of homogeneity of thin sources we checked by autoradiography using FUJI TR 8 imaging plates. 374 DETERMINATION OF VANADIUM IN BIOLOGICAL AND ENVIRONMENTAL SAMPLES BY RNAA WITH EMPHASIS ON QUALITY CONTROL, U.Repinc*, L.Benedik, V.Stibilj. Department of Environmental Sciences, Jožef Stefan Institute, Ljubljana-1000, SLOVENIA Vanadium is released in large quantities to the atmosphere by burning fossil fuels, especially oil. Various processes in ferrous metallurgy involve the production of vanadium-containing vapours, which condense to form respirable aerosols and cause adverse effects on organisms and human health. The production of vanadium steel alloys and other compounds causes the pollution of soil and water with consequent contamination of food. Data on the low levels vanadium in biological and environmental samples are scarce, variable or in some cases practically non- existent. In the present work the improvement of radiochemical neutron activation analysis for determination of nanogram levels of vanadium in foodstuffs is described. The procedure was adopted from Byrne1. After irradiation and rapid dissolution of the irradiated sample, solvent extraction was used for separation of vanadium. BPHA reagent (N-benzoyl-N-phenyl hydroxylamine) used for extraction, gives a violet chelate with vanadium(V) in strongly acidic medium. The chemical yield of radiochemical procedure of each sample aliquot was determined by using spectrophotometry and compared with a re-irradiation procedure of the vanadium carrier and measurement by instrumental nevtron activation. The yield was in the range 90 - 95 %. The agreement between the two procedures for the chemical yield was excellent. The vanadium contents in various foodstuffs (eggs, meat, honey, potatoes, cabbage) is in the range from 1 -90 ng/g dry weight. _________ 1 Byrne, A.R., Kosta, L., J. Radioanal. Chem., 44, 247-264 (1978)

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 375 DETERMINATION OF POLONIUM-210 AND LEAD-210 IN HYDROMETALLURGICAL SAMPLES USING LIQUID SCINTILLATION COUNTING S. A. Brown and B. J. Robinson. ANSTO Environment, Australian Nuclear Science and Technology Organisation, New Illawarra Road, Lucas Heights, NSW, 2234, AUSTRALIA Polonium-210 and lead-210 are produced from the radioactive decay of uranium-238. Mining and subsequent refining of uranium-bearing ores and minerals results in partitioning of these radionuclides into process streams according to their chemistry. Measurement of polonium-210 by alpha spectrometry and lead210 by beta spectrometry provide accurate methods of determination at low levels, however, both techniques are time consuming and provide no scope for “on-line” evaluation. Liquid scintillation counting is a sensitive and widely used technique for the detection and quantification of radioactivity. Use of the technique provides high counting efficiencies with minimal sample preparation. Although the technique suffers from interferences, for example quenching, the effects on detection efficiency have been minimised by advances in both instrumentation and scintillation cocktails. An experimental program has recently commenced to assess the viability of using the liquid scintillation technique as a fast and accurate counting procedure for the determination of polonium-210 and lead-210 in hydrometallurgical samples. The study involves assessment of detection limits for alpha, beta, alpha/beta and Cerenkov counting for these radionuclides (and also bismuth-210) in typical hydrometallurgical matrices containing gram per litre levels of acids and cations. This paper describes the results of that research. 376 CESIUM ACCUMULATION BY MUSHROOM AND MICROORGANISM. H. Sugiyama*1, A. Fukumoto2, C. Kuwahara3, H. Shibata4, H. Terada1, and F. Kato2. 1National Institute of Public Health, Shirokanedai 4-6-1, Minato-ku, Tokyo, 108-8638, JAPAN. 2School of Pharmaceutical Sciences Toho University, Miyama 2-2-1, Funabashi-shi, Chiba, 247-0072, JAPAN. 3Kanagawa Prefectural Public Health Laboratory, Nakao 1-1-1, Asahi-ku, Yokohama-shi, Kanagawa, 241-0815, JAPAN. 4Yamanashi Forestry and Forest Products Research Institute, Saisyoji 2290-1, Masuho-cho, Minamikuma-gun, Yamanashi, 400-0515, JAPAN Mushrooms still show the higher radiocesium (137 Cs) concentrations in all of foodstuffs involving imported foods in Japan, though over sixteen years have passed since Chernobyl accident. In this study, to find the characteristics of cesium uptake and accumulation by mushrooms, we carried out tracer cultured experiments using one of popular edible mushrooms (Pleurotus otsreatus) and microorganisms isolated from mushroom substrata. The concentrations of radiocesium in wild mushrooms and surface soils collected from the several forests in Japan have been investigated by gamma-ray spectrometry. On the Cs feeding experiments, brilliant spots were observed both in the mushroom mycelia (P. ostreatus Y-1) and in the mycelia of actinomycetes isolated from mushroom substrata using a scanning electron microscopy (SEM). Elemental analysis of these spots by energy dispersive X-ray microanalyzer (EDX) showed distinctive higher peaks of Cs and P in comparison with the non-spots areas. We found higher peaks of Rb, Ca or Sr in the spots of the mushroom mycelia grown on the agar plate containing Rb, Ca and Sr by EDX. These peaks heights of Cs, Rb and P by EDX were obviously reduced in the case of rinsing the mycelia with water. To understand Cs accumulation by mushroom, radiocesium distribution in wild mushrooms and soils, relationship between alkali and alkaline earth elements, uptake of Cs by microorganisms will be discussed. 377 DEVELOPMENT OF IN-SITU RADIOACTIVITY MONITORING EQUIPMENTS IN MARINE ENVIRONMENT AND THEIR PERFORMANCE. S. SHIMA*1, K. ISEDA*1, S. GASA*1, T. NAKAYAMA*1, K. NISHIZAWA*1, T. KUJI*1, Y. KOBAYASHI*2, H. KAWAMURA*1. 1Mutsu Marine Laboratory, Japan Marine Science Foundation, Mutsu, 035-0064, JAPAN 2Ibaraki, 311-0105

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI Three types of in-situ gamma-ray monitoring system in marine environment have been developed in order to establish a technology of a radioactivity survey in the coastal zone around the Japanese spent fuel reprocessing plant under construction. One of them is remotely operated vehicle (ROV) equipped with an NaI(Tl) detector or a small mechanically cooled Ge detector. The ROV can dive into a water depth of 200m and has a CTD, a current meter, still camera, and TV cameras. The observed data can get on a mother vessel of ROV in real-time. The others are buoys equipped with NaI(Tl) detector, which are different in size and the purpose of usage. The larger one in size will be moored in coastal area (BUOY) and the smaller one will be used as drifter (FLOAT). The BUOY works by solar panel and lead batteries in a deployed point. The FLOAT drifts along seawater flow and will run by Li-battery within 10 days. The acquired data transmit to a land station through radio-communication every 5 min. The results of their performances and its unique phenomena of time series for gamma spectra above a seabed will be introduced and discussed in this presentation. 378 ENVIRONMENTAL RADIOACTIVITY AND RADIONUCLIDE ULTRA-SENSITIVE MEASUREMENT METHODS. Calmet D., CEA - Environment, Surveillance, Materials division – Bâtiment DAM, BP12 – 91680 Bruyères le Châtel, FRANCE. e-mail : [email protected] In most countries, environmental and human health risk assessment studies are legally required to determine the impact of any, even very low-level, radioactive substances discharged into the environment. The public credibility of such studies relies, both on the representativity of the exposure pathways selected and on the quality and reliability of measurement data used to validate the exposure computations. The radiological protection principle whereby exposure should be kept as low as reasonably achievable is soon to be completed with, on the one hand the use of the best available technology (BAT) and on the other hand the intention to limit the added “exposure” to a fraction of a µSv.a-1. As a result, authorized radioactive effluent discharges decrease with time and the environmental activity levels are now considered trace levels for most of the radionuclides that justified the use of ultra-sensitive measurement techniques to determine their presence in the environment. Radionuclides have to be measured in various environmental matrices and are identified and quantified following two approaches : by mass spectrometry or the detection of nuclear emissions during their radioactive decay. The presentation will cover the recent developments of the last ten years in the area of field sampling (including solid-phase microextraction fiber application), sample preparation and the various improvements in analysis methods (New HP detector for nuclear techniques and various injection modes for MS, laser ablation, HR MS, LA-ICPMS, TIMS, etc). Exemples will be given of different applications in the field of environmental routine monitoring, impact assessment, research studies as well as monitoring of treaty compliance. 379 ULTRA-SENSITIVE RADIONUCLIDE SPECTROMETRY – RADIOMERTRICS AND MASS SPECTROMETRY SYNERGY. P. P. Povinec, International Atomic Energy Agency, Marine Environment Laboratory, MONACO Recent developments in radiometrics and mass spectrometry techniques for ultra-sensitive analysis of radionuclides in the marine environment are reviewed. In the radiometrics sector the dominant development has been utilisation of large volume HPGe detectors in underground laboratories with anti-cosmic or anticompton shielding for analysis of short and medium-lived radionuclides in the environment. In the mass spectrometry sector applications of Inductively Coupled Plasma Mass Spectrometry (ICPMS) and Accelerator Mass Spectrometry (AMS) for analysis of long-lived radionuclides in the environment represent the most important recent achievement. A comparison of radiometrics and mass spectrometry techniques for analysis of radionuclides in the marine environment will be made and illustrated on radionuclide analysis of different types of marine samples (seawater, sediment, biota). These recent developments do not only considerably decrease the detection limits for several radionuclides (up to several orders of magnitude), but

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI they also enable to decrease sample volumes so that sampling, e.g. of the water column can be much easier and more effective. 380 SEQUENTIAL SEPARATION METHODS FOR ANALYSIS OF ACTINIDES IN MARINE SAMPLES USING ANION EXCHANGE RESIN AND EXTRACTION CHROMATOGRAPHY. S.-H. Lee, J. Gastaud, J. La Rosa, P. P. Povinec*, E. Wyse, Marine Environment Laboratory, International Atomic Energy Agency, MONACO Existing analytical methods for the determination of actinides in marine samples include various processes such as precipitation, the use of ion exchange resins and solvent extraction. Radionuclide separation using ion exchange resins is effective for large samples, however, the process requires the use of several chemicals, is time consuming and produces large amounts of chemical wastes. Extraction chromatography reduces the number of chemicals needed, as well as the processing time. However, large samples still need preconcentration techniques such as co-precipitation to reduce the amount of matrix before chromatography can be applied. A new and quantitative method for the determination of actinides has been developed and applied for analysis of actinides in sediment (IAEA-385) and fish (IAEA-414) reference materials produced by IAEA-MEL. The anion exchange resin (Bio Rad AG1-X8 : 100-200 mesh) method can be used for large volume samples and gives an excellent selectivity of extraction chromatography (UTEVA and TRU), as well as high chemical recoveries. The procedure included total dissolution, separation by anion exchange resin, separation and purification by extraction chromatography with measurement of the radionuclides by Semiconductor Alpha Spectrometry (SAS), high resolution Inductively-Coupled Plasma Mass Spectrometry (ICP-MS) and Accelerator Mass Spectrometry (AMS). The results of analysis of uranium, thorium, plutonium and americium isotopes in marine samples obtained using the different techniques were in good agreement. 381 RECENT DEVELOPMENTS IN ANALYSIS OF TRANSURANICS (Np, Pu AND Am) IN SEAWATER. J. La Rosa, J. Gastaud, S.-H. Lee, I. Levy, P. P. Povinec*, E. Wyse, International Atomic Energy Agency, Marine Environment Laboratory, MONACO The study of the transuranics is very useful as a key to understanding their chemical behaviour in the marine environment, as a way of assessing the radiological situation, and as a tracer for following water movements, sedimentation and uptake by biological systems. A successful approach to the quantitative determination of transuranics incorporates a combined Np, Pu, Am radiochemical separation procedure from 50 liters of seawater. Tracers 239Np (milked from 243Am), 236Pu or 242Pu, and 243Am are added to acidified seawater followed by potassium permanganate. A primary pre-concentration of the actinides is made by coprecipitation with MnO2 precipitated from this solution. After dissolution of the primary MnO2, a secondary MnO2 precipitation of considerably smaller mass is made. The secondary MnO2 containing the actinides is dissolved with reduction in dilute nitric acid. The oxidation states of neptunium and plutonium are adjusted to Np(IV) and Pu(IV), and they are separated from Am(III) in 8M HNO3 as anionic nitrate complexes using anion exchange column chromatography. On the same column, plutonium is separated from neptunium by reduction to Pu(III) and elution, while Np(IV) remains on the column. Neptunium is subsequently eluted from the column by dilute HF – HNO3 solution. Rigorous radiochemical purification of the individual Np, Pu and Am fractions is carried out with care to maximize chemical recoveries. Purified Np fraction is analyzed by Inductively Coupled Plasma Mass Spectrometry (ICPMS) to measure 237Np. Plutonium can be measured for 238Pu and combined [239Pu+240Pu] by alpha spectrometry from an electrodeposited source. 241Pu can be measured by Liquid Scintillation Counting (LSC) using the same source. Subsequently, the plutonium can be dissolved off the disk source, chemically purified, and 239Pu and 240Pu measured by ICPMS or Accelerator Mass Spectrometry (AMS). The americium fraction is prepared as an electrodeposited source for alpha spectrometry measurement of 241Am (and 244Cm, if present). Results of the measurements show the concentration variation with depth. Atom ratios of 240Pu/239Pu give information on the origin of the Pu. Comparison of the Np, Pu and Am activity concentrations at each depth can provide information on chemical

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI fractionation when compared with the original source term ratios. The results will be illustrated on the NorthWest Pacific and Mediterranean seawater profiles. 382 IN SITU STATIONARY MONITORING OF Cs-137 IN SEAWATER OF THE NW IRISH SEA. I. Osvath1, P. P. Povinec1*, T. P. Ryan2. 1Marine Environment Laboratory, International Atomic Energy Agency, MONACO. 2Radiological Protection Institute of Ireland, Dublin, IRELAND Gamma-ray spectrometers operating underwater can be effectively used for short term as well as long term monitoring of marine radioactivity, but also for monitoring rivers and lakes. They can, in specific cases, replace sporadic sampling campaigns and laborious analytical measurements in the laboratory. Stationary monitoring systems have several advantages when compared to traditional sampling systems, e.g. (a) real time reporting of data, (b) searching for temporal changes, (c) development of time series. As released radionuclides are usually accompanied by gamma-emitters (e.g. in discharges from reprocessing plants and nuclear power stations, from dumped radioactive wastes) a gamma-monitoring system would provide an excellent solution for the monitoring of radionuclides in the aquatic environment. An in situ monitoring system called the "NEMO Observatory" (Nautique-Environnement Marin-Observatoire) capable of stationary measurements of gamma-activity in seawater (equipped with a 75 mm dia x 75 mm long NaI(Tl) detector, as well as current, temperature and salinity meters and satellite data transmission capability was recently put into operation by the IAEA's Marine Environment Laboratory in Monaco and successfully tested in the Bay of Monaco. Jointly, with the Radiological Protection Institute of Ireland, the NEMO Observatory was deployed in the North-west Irish Sea for 6 months of continuous investigations of 137Cs transport in surface water and its possible resuspension from sediment. The data were transported via satellite to IAEAMEL, Monaco twice weekly. The parameters of the monitor, the NaI(Tl) detector's response to 137Cs and other gamma-emitters in seawater (40K, 214Bi, etc.) and measured oceanographic parameters will be discussed in detail. 383 IAEA-MEL UNDERGROUND LABORATORY FOR THE ANALYSIS OF RADIONUCLIDES IN THE ENVIRONMENT AT VERY LOW LEVELS. P.P. Povinec, J-F. Comanducci, I. Levy-Palombo. International Atomic Energy Agency, Marine Environment Laboratory, MONACO An underground laboratory for low-level gamma- and beta- spectrometry has been constructed in Monaco by IAEA-MEL for the analysis of environmental radionuclides. The laboratory is situated a depth of 40 m w.e. and equipped with 4 large volume HPGe detectors placed in a common lead shield with anti-cosmic plastic scintillator shielding. There is also an anti-Compton gamma-spectrometer, comprised of an HPGe detector and NaI(Tl) shielding, and finally, a liquid scintillation spectrometer Quantulus. Monte Carlo simulations of background characteristics of the individual HPGe spectrometers, as well as of the anti-Compton spectrometer, have been carried out in order to optimise the performance of the spectrometers under different shielding conditions. It was found that 15 cm of lead shielding plus anti-cosmic shielding made of plastic scintillators gives the best counting parameters. The internal lining of the lead shield has also been studied, showing that the lowest background can be achieved without any additional layers. The performance of the gamma-spectrometers under different shielding conditions will be discussed in more detail, as well as the impact of their parameters on further analysis of radionuclides in the marine environment (e.g. a reduction in sample size and counting time). 384 RADIOCHEMICAL SEPARATIONS FOR ANALYSIS OF PRODUCTS RELEASED IN EXPERIMENTS ON SEVERE REACTOR ACCIDENTS. G. Skarnemark*, A. Ødegaard-Jensen, Nuclear Chemistry, Department of Materials and Surface Chemistry, Chalmers University of Technology, S-412 96 Göteborg, SWEDEN

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI In the European Phebus project severe reactor accidents are studied in pilot scale. The products released during the melting of the fuel are collected in filters which are then leached with acid. The contents of the acid are then fractionated using solvent extraction and the nuclide concentrations determined by radiometrical methods (α- and γ-spectrometry, and liquid scintillation counting) and ICP-MS. The contribution will describe the used analysis scheme in detail. Experimental errors and uncertainties will also be discussed. 385 LIQUID-LIQUID EXTRACTION APPLIED TO ONE-ATOM-AT-A-TIME STUDIES OF TRANSACTINIDE ELEMENTS. G. Skarnemark*, C. Ekberg, Nuclear Chemistry, Department of Materials and Surface Chemistry, Chalmers University of Technology, S412 96 Göteborg, SWEDEN Liquid-liquid extraction is one of the methods that is used for one-atom-at-a-time separations of transactinide elements from heavy-ion reaction product mixtures. It is suitable for this purpose because it is fast, provided that a chemical system with negligible kinetics is used, and it can be used for continuous separations. It is, however, not quite easy to determine the uncertainties of the measured distribution coefficients or complex formation constants. In this paper methods for such estimates will be discussed. 388 IODINE DAILY DIETARY INTAKE IN A GROUP OF BRAZILIAN WORKERS. , V.A. Maihara1, P.L.C. Moura1, D.I.T.Fávaro1, M.B.A.Vasconcellos1 1Radiochemistry Division, Instituto de Pesquisas Energéticas e Nucleares, IPEN/CNEN-SP, SP, BRAZIL Iodine is an essential constituent of the thyroid hormones thyroxine (T4 and T3). The main role of iodine in nutrition arises from the important part played by the thyroid hormones in the growth and development of humans and animals. The recommended dietary allowance (RDA) for adult men and women is 150 µg/day and the tolerable upper intake level (UL) for adults is 1,100 µg/day. Low iodine levels in the diet lead to iodine deficiency disorders. Iodine deficiencies can be prevented or reduced by increasing of its dietary intake through fortification of food. There is an intensive international effort to fortify the cooking salt with iodine in several countries, including Brazil. In this study, iodine dietary intake was evaluated through determination of iodine in duplicate portion diet samples by epithermal neutron activation. The collection of samples was carried out in a group of twenty-six workers from a steel industry of São Paulo city. The 3 daydiet samples were prepared by freeze-drying process in an industrial freeze dryer and mixed and homogeneized in a domestic blender. Epithermal neutron activation analysis (ENAA) was employed to reduce the main interferentes present in the diet samples, such as Na and Cl. Three NIST reference materials: RM 8435 Whole Milk Powder, SRM 1549 Non Fat Milk Powder and SRM 1548a Typical Diet were analyzed for validation of the methodology. The average daily dietary intake found for worker’s group was 840 µg/day, ranging from 400 to 1540 µg /day. Some of the daily iodine intakes were about 10 times higher than the RDA value. 389 INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS APPLIED TO THE CHEMICAL COMPOSITION OF METALLIC MATERIALS WITH STUDY OF INTERFERENCES. E. G. Moreira*1, M. B. A. Vasconcellos1, M. Saiki1. 1 Centro do Reator de Pesquisas, Instituto de Pesquisas Energéticas e Nucleares, São Paulo, SP 05508-000, BRAZIL. Instrumental Neutron Activation Analysis was used to evaluate the chemical composition of iron, steel, silicon and ferrosilicon reference materials. Samples were irradiated at 1012 n cm-2 s-1 flux at IEA-R1 Research Nuclear Reactor at IPEN for 30 min for long lived radionuclides and 30 s for short lived ones. Induced radioactivity was measured in a CANBERRA gamma ray spectrometer for suitable periods of time after appropriate sample decay. The concentration of As, Co, Cr, Mn, Mo, Ni, V and W were analyzed in the iron and steel samples whereas As, Br, Co, Cr, K, Eu, Fe, La, Mn, Mo, Na, Nd, Sb, Sc, Sm, Tb Th, U, V, W and Yb were determined in silicon and ferrosilicon samples. Method validation was

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI assessed by comparison of the obtained results to reference material certified values. As relative element concentration may be large in metallic matrices, interferences in neutron activation analysis are possible to occur. Interference of Cr and Mn in V, Fe and Co in Mn, Co in Fe and Cr in Ti were quantified and only the last one was critical to the analysis of the materials employed in this work. 390 THE SUM-OF-SQUARES SPECTRUM WITH ZERO DEAD TIME COUNTING AND ITS RELATION TO STATISTICAL UNCERTAINTY. S. Pommé. EC-JRC-IRMM, Institute for Reference Materials and Measurements, Retieseweg, B-2440 Geel, BELGIUM Important novelties implemented in the DSPECplus TM digital spectrometer are the ‘Zero Dead Time’ (ZDT) pulse loss correction system, in combination with the ‘sum-of-squares’ spectrum. The latter consists of the squares of the number of counts registered per event in the corresponding channels of the ZDT-spectrum. The constructor calls it the ‘variance’ spectrum, claiming that the statistical variance of the ZDT-counts corresponds to the number of counts in the ‘sum-of-squares’ spectrum. In this work, the validity of this statement is scrutinised on the basis of mathematical and experimental evidence. 391 PIXE ANALYSIS FOR THE BIOACCUMULATION OF SEVERAL TRACE METALS BY MARINE MICRO-ALGA. Y. IWATA*, A. SATOH, Y. SASAKI, R. ITO and K. KURAMACHI. Department of Chemistry, Faculty of Education and Human Studies, Akita University, Akita 010-850, JAPAN The bioaccumulation by micro-alga in the ocean was simulated in the nutritive seawater containing known amount of trace metals and concentration factors for Fe, Zn, Cd and Pb were measured by PIXE. Trace metals in nearshore seawater obtained from Kamaishi Bay were removed by Celex-100 . Trace metals and nutritive salts were added to the purified seawater. Marine micro-algae (Nannochloropsis sp., and Phaeodactylum sp.,) were purely cultured in the nutritive seawater. An interested metal ion was added to the nutritive seawater (0.025 - 5.0 mg / l). The alga in 10 ml of the nutritive seawater was collected on a polycarbonate filter (pore size : 1.0 µm) by a suction filtration and subjected to the 2.9 MeV proton bombardment. Na, Mg, Si, P, S, Cl, K, Ca, Cr, Mn, Fe, Cu, Zn, Cd and Pb were simultaneously determined. PIXE could do multi-element analysis by less than 1 mg of analytical sample. The quantity of the metal in alga was increased in proportion to the concentration in the nutritive seawater. For example, the concentration factor for zinc was given as 10200 ± 300 ml / g (dry weight base) for Phaeodactylum sp.. It is shown that PIXE is a powerful tool for the measurement of the bioaccumulation of trace elements. 392 PREPARATION OF PROFICIENCY TEST SAMPLES CONTAINING ‘FRESH’ FISSION PRODUCTS. Arend V. Harms†, Satwant K. Johal and Simon M. Jerome‡, National Physical Laboratory, Teddington, UK NPL was recently asked to provide sources for two proficiency test exercises. The aim of these exercises was to measure fission product radionuclides arising from the neutron irradiation of highly (>99%) enriched 235U, within 50 days (preferably less) of the irradiation taking place. Furthermore, the samples were to contain fission products, but no fissile material. The samples in the first exercise were to contain a mixture of fission products with (as far as possible) only the 235U removed, leaving the fission products as ‘undisturbed’ as possible. A number of radionuclides were reported in this sample and included; 91Y, 95Zr, 95mNb, 95gNb, 99Mo, 99m Tc, 103Ru, 106Ru, 127Sb, 129mTe, 129gTe, 131I, 132Te, 132I, 137Cs, 140Ba, 140La, 141Ce, 144Ce, and 147Nd. Of these nuclides, NPL provided certified values for 91Y, 95Zr, 95mNb, 95gNb, 99Mo, 99mTc, 103Ru, 106Ru, 132Te, 132I, 137 Cs, 140Ba, 140La, 141Ce, 144Ce, and 147Nd. The second exercise focused on a smaller subset of radionulides; 95 Zr, 99Mo, 103Ru, 106Ru, 140Ba, and 155Eu, although 95gNb, 99mTc, 132I and 140La were present as daughter radionuclides and 91Y, 127Sb, 129mTe, 129gTe, 131I, 132Te, 137Cs, 152Eu, 154Eu and 155Eu were present as impurities.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI This paper describes the development of suitable separation techniques, based on a combination of extraction chromatography, ion exchange chromatography and selective precipitation, used to (i) produce the ‘fresh’ fission product mixture from irradiated 235U, and (ii) isolate the specific set of radionuclides in the second exercise from mixtures containing irradiated 235U and fission products. The irradiation conditions and separation schemes used in the preparation of the proficiency test samples is detailed with comments on the selectivity of the process and the purity of the final materials. 393 WWW-BASED REMOTE ANALYSIS FRAMEWORK FOR UNISAMPO AND SHAMAN ANALYSIS SOFTWARE. P.A. Aarnio1, J.J. Ala-Heikkilä1, T.T. Hakulinen*2, M.T. Nikkinen3, J.T. Routti1, 1 Helsinki University of Technology, Department of Engineering Physics and Mathematics, FIN-02015 HUT, FINLAND, 2CERN, CH-1211 Geneva 23, SWITZERLAND, 3STUK, Radiation and Nuclear Safety Authority, FIN-00881 Helsinki, FINLAND UniSAMPO and SHAMAN are well established analysis tools for gamma spectrum analysis and the subsequent radionuclide identification. These tools are normally run locally on a Unix or Linux workstation in an interactive mode. However, it is also possible to run them in batch/non-interactive mode by starting them with the correct parameters. This is how they are used in the standard analysis pipeline operation. This functionality also makes it possible to apply them for remote operation over the network. We have developed a framework for running UniSAMPO and SHAMAN analysis using the standard WWW-protocol. A WWWserver receives requests from the client WWW-browser and runs the analysis software via a set of CGIscripts. Authentication, input data transfer, and output and visualization of the final analysis results is all carried out using standard WWW-mechanisms. This WWW-framework can be utilized, for example, by organizations that have radioactivity surveillance stations in a wide area. A computer with a standard internet/intranet connection suffices for on-site analyses. 394 HIGH-ENERGY PROTON IRRADIATION AND INDUCED RADIOACTIVITY ANALYSIS OF SOME CONSTRUCTION MATERIALS FOR THE CERN LHC. P.A. Aarnio1, J.J. Ala-Heikkilä1, T.T. Hakulinen*2, M.P. Huhtinen2, 1Helsinki University of Technology, Department of Engineering Physics and Mathematics, FIN-02015 HUT, FINLAND, 2CERN, CH-1211 Geneva 23, SWITZERLAND The dose rate to personnel due to remnant radioactivity during maintenance periods will be an important issue at the forthcoming Large Hadron Collider (LHC). Among the most abundant construction materials are aluminium, steel, copper and lead. In order to obtain more reliable estimates on the radioisotope production in a high-energy hadron environment, we irradiated small samples of these materials behind the beam-stop of the CERN 24 GeV/c proton synchrotron. This environment is characterised by a high spallation neutron fluence and a non-negligible contribution of protons and pions up to the total beam momentum. Gamma-ray spectra of the samples were measured and analyzed with the SAMPO software package and a detailed nuclide identification was carried out with the SHAMAN software package. The total energy emission and results of the spectrum analysis were compared to predictions of the FLUKA hadron cascade simulation package. 395 ACTINIDE AND LANTHANIDE METALLOFULLERENES STUDIED BY RADIOCHROMATOGRAPHY. K. Akiyama*1, K. Sueki2, K. Tsukada1, H. Haba3, M. Asai1, S. Ichikawa1, Y. Nagame1, K. Kikuchi4, M. Katada4, and H. Nakahara4. 1Advanced Science Research Center, Japan Atomic Energy Research Institute (JAERI), Tokai, Ibaraki 319-1195, Japan. 2Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan. 3Cycrotron Center, RIKEN, Wako, Saitama 351-0198, Japan. 4 Department of Chemistry, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, JAPAN. We report radio-chromatographic behavior of metallofullerenes of the light actinide elements, from Ac to Am, and of those of lanthanide elements. The metallofullerenes in crude fullerene soot synthesized by the DC arc-discharge method were injected into HPLC columns filled with the propylpyrenyl and

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI pentabromobenzyl stationary phases. HPLC elution behavior of Ac, U, Np, Pu, and Am metallofullerenes is similar to each other on both columns, and also similar to that of the metallofullerenes of the trivalent lanthanide elements, such as La3+@C82. As for the metallofullerenes of Th and Pa, the elution behavior is quite different from that of the other actinide elements. Macroscopic quantities of U and Th metallofullerenes were prepared for spectroscopic studies with TOF/MS, UV/vis/NIR, XANES, and NMR. The main species of these metallofullerenes were identified as U@C82 and Th@C84, and the charge states of encapsulated metal atoms were 3+ for U and 4+ for Th. Similarity of the HPLC retention times for the Ac, Np, Pu, Am metallofullerenes suggests that the products for these metallofullerenes are in the form of M@C82 with the metal atoms in the 3+ state, while that for Pa metallofullerene is of M@C84 with 4+. In the presentation, we will discuss detailed characteristic properties of actinides and lanthanides metallofullerenes studied by the radio-chromatographic method. 397 A SOLUTION IN-LINE ALPHA COUNTER FOR ACTINIDE PROCESS CONTROL APPLICATIONS. L. D. Schulte*1, R. R. Salazar1, J. E. Farnham2, M. M. Fowler3, R. E. Gritzo3. 1 Nuclear Materials Technology Division, NMT-2, Los Alamos National Laboratory, Los Alamos, NM 87545, USA. 2 Nonproliferation and International Security Division, NIS-10, Los Alamos National Laboratory, Los Alamos, NM 87545, USA. 3 Chemistry Division, C-INC, Los Alamos National Laboratory, Los Alamos, NM 87545, USA A Solution In-Line Alpha Counter (SILAC) has been developed to provide real-time data useful for actinide R&D and process control needs. The hazard and regulatory control of liquid effluent streams associated with plutonium processing is primarily associated with the alpha content of the solution. Significant effort has been expended to improve separations chemistry schemes to remove small quantities alpha-emitting elements from plutonium process effluent streams throughout the DOE complex. Real-time data that can be directly related to alpha content of a solution is useful for process control of waste minimization efforts. The detection system described here allows the monitored stream to come in contact with a small fiber-optic rod of scintillating material in a light-tight enclosure. Light is produced through scintillation events, measured with a photomultiplier tube, and is proportional to the alpha content of the solution. SILAC detectors have been constructed to provide an alpha monitor with a wide dynamic range, compact installation, and high chemical resistance to hydrochloric acid vapors/solutions. The performance of the detector as a process control monitor on operations to remove alpha activity from solutions in a TA-55 glovebox will be presented. 398 Pb ISTOPIC RATIOS IN ENVIRONMENTAL SAMPLES IN THE METROPOLITAN ZONE OF MÉXICO VALLEY. T. Martinez1*, J. Lartigue1, F. Juarez2, P. Avila-Perez3, G. Zarazua3, C. Marquez1, M.P. Orta4. V. Alvarez1. 1National University of Mexico, Faculty of Chemistry, Building D,. CU (O4510) México, D.F. (Mexico). 2Institute of Geophysics, Circuito Institutos, CU (04510) México, D.F. 3National Institute of Nuclear Research., Carr. México-Toluca Km 36.5, (52045) Salazar, Ocoyoacac, Edo. de México (Mexico). 4Environmental Laboratory, Federal District Government, Av. Sur de los Cien Metros s/n (07750) México, D.F. MEXICO. Application of the Pb isotopic composition in environmental studies has increased in the last decade, due to its potential to differentiate sources of pollution. In the environment, Pb isotopic ratios reflect the mixing of local/natural Pb with anthropogenic inputs, and a mixing process can be showed if each source has a characteristic isotopic ratio. In this study, recently acquired isotopic data from environmental samples are presented. Environmental samples were collected in different monitoring stations covering the Metropolitan zone of Mexico. Samples are leached or dissolved using ultra pure reagents. Lead concentration was measured by TXRF and Lead isotopic ratios were determined by inductively coupled plasma mass spectrometry (ICP-MS). NIST standards were employed for quality control. 399 INDOOR RADON, RADON PROGENY AND THORON CONCENTRATIONS IN THE PYRAMIDES OF TEOTIHUACAN. T. Martinez1*, G. Martinez2, F. Juarez3, M. Navarrete1, L. Cabrera1, P.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI Gonzalez3. A. Ramirez1. 1National University of Mexico. Faculty of Chemistry, Building D,. CU (O4510) México, D.F. (Mexico). 2Coordinación Nacional de Conservación del Patrimonio Cultural. Xicontencatl y General Anaya s/n. (04120) México, D.F. México. 3Institute of Geophysics. Circuito Institutos, CU (04510) México, D.F. Mexico. 4National Institute of Nuclear Research.. Carr. México-Toluca Km 36.5, (52045) Salazar, Ocoyoacac, Edo. de México MEXICO. Teotihuacan (50 Km from Mexico City) was the most important City in Mesoamerica in the Classic period. In the archeological site are the Sun and Moon pyramids and some temples as that for Quetzatcoatl. Below these, it had been built several tunnels and chambers, some of them before Christ. Since radon, radon progeny and thoron concentrations in tunnels vary widely, due to different ventilation conditions and building materials and as long as for a given radon concentration the effective dose is mainly dependent on the equilibrium factor between radon and its progeny, the aim of this work is to provide data to support the monitoring of dose received by people occasionally working indoor pyramid and temples. Radon and thoron concentrations were measured with the electret passive environmental radon monitor (E-PERM) system, in different configurations such as LLT, HST and SST, with lectures at different times during a three months period. Radon progeny concentration was measured by means of continuous working monitors and the Equilibrium Factor and dose were calculated. Gamma radiation was measured by means of TLD dosimeters. A quality control program was also improved. 400 EFFICIENCY OF GERMANIUM DETECTORS AS A FUNCTION OF ENERGY AND INCIDENT GEOMETRY: COMPARISON OF MEASUREMENTS AND CALCULATIONS. R. M. Keyser*1 and W. K. Hensley2, 1ORTEC, 801 South Illinois Avenue, Oak Ridge, TN 37831 2Pacific Northwest National Laboratory, Richland, WA 99352, USA The use of HPGe detectors in counting situations where the sample is large or not easily reproduced has increased the interest in the use of calculations or models to determine the counting efficiency for the specific geometry. Much work has been done on modeling programs such as MCNP to generate the response of HPGe detectors in a wide variety of detector-source geometries. The accuracy of these simulations of the germanium detector response relies on detailed knowledge of the performance of the detector. The detector construction materials and surface dead layers must be well specified. The dead layer is especially important at energies below a few hundred kilovolts. Other investigators [1,2] have shown that the efficiency changes with position of the incident gamma ray on the detector. The efficiency as a function of incident pencil beam gamma rays has been measured for several different types of detectors at different energies [3]. These measurements showed that the dead layer was not uniform on the surface of a crystal and differed from detector to detector. Based on these measurements, the dead layer on the sides (cylindrical surface and closed end) of the detector was estimated. These estimates and the construction details were used in the MCNP program to calculate the efficiency in the same geometry for several detectors. Using the detailed measurements in the model, some agreement between experimental data and calculations was obtained, however, the calculations differ significantly in some areas. [1] R. J. Gehrke, R. P. Keegan, and P. J. Taylor, “Specifications for Today’sCoaxial HPGe Detectors,” 2001 ANS Annual Meeting, Milwaukee, WI. [2] R. L. Metzger, private communication, see also: R. L. Metzger, K. A. Van Riper, and K. J. Kearfott, “Radionuclide Depth Distribution by Collimated Spectroscopy,” 2002 ANS Topical Meeting, Santa Fe, NM. [3] R. M. Keyser, “Resolution and Sensitivity as a Function of Energy and Incident Geometry for Germanium Detectors”, 2002 IRRMA Meeting, June 2002, Bologna, Italy. 401 THAT’S GOOD, BUT YOU CAN DO BETTER. Kenneth G.W. Inn*1, Iisa Outola1, Linda Selvig1, Cari Bershell2, Hiromu Kurosaki1, Svetlana Nour1. 1Ionizing Radiation Division, NIST, Gaithersburg, MD

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 20899-8462, USA. 2Physics Department, Southern University and A&M College, Baton Rouge, LA 70813, USA Many radioactivity measurements are made on an annual basis within the United States to support environmental monitoring, nuclear waste remediation and occupational health. The reliability of these measurements is assessed for the laboratories participating in inter-laboratory comparisons by testing them with samples of known but undisclosed massic activity. Over the years, the NIST Radiochemistry Intercomparison Program used relevant in vitro radiobioassay and environmental matrices (synthetic urine, synthetic feces, air filters, acidified water, and soil to test the participating laboratory’s measurement traceability for Am241, Pu238, U238 and Sr90. However, we ask the following question: are these laboratories improving with time? We have evaluated the results of NRIP participants and have found them to be in general agreement with NIST values and some that indicate improvement over time. There are instances however, where the results may indicate: 1) matrix dependent differences in measurement capability; 2) constant positive or negative measurement differences from the NIST values; 3) systematically changing differences from the NIST values; 4) poor analytical reproducibility; and 5) poor estimation of measurement uncertainty. The participating laboratories, should evaluate potential problems in their measurement system that may include, but are not limited to: 1) unstable isotope dilution standards; 2) incorrect calibration of the isotope dilution standards; 3) incomplete uncertainty evaluation; and 4) incomplete operator training. 402 THIN FILM TO PREVENT RECOIL CONTAMINATION OF SOLID-STATE ALPHA DETECTORS. Kenneth G.W. Inn*1, Iisa Outola1, Linda Selvig1, Hiromu Kurosaki1, Svetlana Nour1. 1 Ionizing Radiation Division, NIST, Gaithersburg, MD 20899-8462, USA Over the past decade, NIST has used an easily prepared thin film technique to minimize recoil contamination of solid-state alpha detectors. Sill and Olson (Analytical Chemistry, 42, 1596 (1970)) published an elegant paper advocating the use of 12 µg/cm2 air and a 6 volt negative bias on the source to control alpha recoil contamination of alpha detectors. As an alternative, NIST has used thin films (12 µg/cm2 thickness) and a 10 volt negative bias on the source to control alpha recoil contamination of it alpha detectors. A single drop of 1:1 isoamyl acetate:collodion is dropped on the surface of distilled water and allowed to dry for a few minutes. A vertical loop is then inserted into the water bath, and lifts the film off of the water vertically to form a double thickness of film. The film is then transferred to a metal ring that has a diameter larger than a counting source, and air dried. When used, the film is placed about 1 mm above the counting source. Although we have not determined the mechanism for trapping the recoil products, we have successfully used these disposable thin films for many years and have not suffered any noticeably detectable loss of spectral resolution. 403 COMPARISON OF ANALYTICAL METHODS FOR URANIUM. Kenneth G.W. Inn, Ionizing Radiation Division, NIST, Gaithersburg, MD 20899-8462, USA In 1978, the National Bureau of Standards (NBS) began a long-term program to develop a suite of environmental-level natural matrix radionuclide Standard Reference Materials (SRMs) for the evaluation of analytical methods. Occasionally, a customer would report a significant difference between their determined value for a certified analyte and the NBS value. One such report from a customer who determined uranium massic concentration in SRM 4353 (Rocky Flats Soil – I) by total acid dissolution and thermal ionization mass spectrometry but reported a value approximately 15% lower than the certified concentration value. This report indicated that we should investigate the cause for the discrepancy. Several independent methods were called upon to confirm the certified uranium value. Further investigation indicated the likely cause for the discrepancy to be a highly insoluble minor mineral fraction in the SRM that contained high concentration of uranium. The suspect mineral fraction, zircon, is widespread in soils and sediments that are derived from igneous and metamorphic rocks, and represents an analytical complication that deserves attention when planning dissolution treatments of soils and sediments.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 404 NATURAL 32Si AS ENVIRONMENTAL TRACER. U. Morgenstern*, Institute of Geological and Nuclear Sciences, Lower Hutt, New Zealand ([email protected]). There is a pressing need for an effective dating tool to cover the historical past. Cosmogenic 32Si, with a halflife of ca. 140 years, is ideally suited to provide time information in the range 30-1000 years. Detection of 32 Si is, however, very difficult due to extremely low natural concentrations and isotopic ratios. The difficulties of setting up extremely low background systems, and the need for large samples have previously deterred wider use of 32Si. At GNS we have developed improved methods for radiometric detection of natural 32 Si [Morgenstern et al., 2001] and, in collaboration with Australian National University, have succeeded in measuring natural 32Si by accelerator mass spectrometry (AMS) [Morgenstern et al., 2000]. For AMS the necessary sample size can be reduced by a factor of ca. 1000, making it suitable for analysing ice core samples of only ca. 1 kg . The problematic in 32Si analysis of natural samples will be demonstrated, together with some applications including the detection of 32Si in ground waters, sediment cores, glacier ice, and deep ocean glass sponges. References Morgenstern U., Fifield L.K., Zondervan A., (2000), Nucl. Inst. Meth. B 172:605-609. Morgenstern, U., Geyh M.A., Kudrass, H.R., Ditchburn R.G. and Graham I.J. (2001) RADIOCARBON, Vol 43, Nr 2B, 909-916 405 A STUDY OF 109Cd UPTAKE AND TRANSLOCATION MANNER IN A SOYBEAN PLANT UNDER DIFFERENT pH CONDITIONS. T. Ohya, H. Iikura and T. M. Nakanishi, Graduate School of Agricultural and Life Science, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657, JAPAN Though it has been reported that the accumulation of Cd in plant tissue increases with the decrease of the pH in soil, the mechanism of Cd accumulation in plant has not been clarified yet. Therefore, we investigated the effect of environmental pH condition on the Cd accumulation in soybean plant root, which is a gate for Cd uptake, using 109Cd as a tracer. Cadmium uptake by root tissue was found to be a fast reaction; the amount of Cd uptake reached the plateau within about 2 hours (its time constant is 30 minutes), and moreover, its dynamics did not depend on either the concentration of carrier Cd (0.1, 1uM) or an environmental pH condition (pH4.5, 6.5). However, it was found that the Cd absorbed at pH 4.5 bound stronger to the root than that at pH 6.5. It was also suggested that Cd uptake was hardly affected by cell wall and penetrated easily into apoplast. Based on these results, we are studying the translocation manner of Cd from apoplast to vessel under different pH conditions using high performance image analyzer (FLA-5000: FUJIFILM). Moreover we also examined the fluctuation of both interacellular and extracellular pH by Cd treatment through microscopic observation. 406 CADMIUM EFFECT ON AN ELEMENTAL PROFILE IN AN EDIBLE PART OF SOYBEAN PLANTS REVEALED BY INAA. *1H. Iikura, *2M. Katsu, *3S. Takase, *1T. Ohya and *1T. M. Nakanishi, *1 Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1, Yayoi, Bunkyo-ku, Tokyo113-8657, Japan, *2 Graduate School of Bioresource Sciences, Nihon University, 1866, Kameino, Fujisawa-shi, Kanagawa 252-8510, Japan, *3 Department of Life Sciences, Faculty of Life Sciences, Toyo University, 1-1-1 Izumino, Itakura-machi, Ora-gun, Gunma 374-0193, JAPAN Cadmium induces a serious damage for both animals and plants, but little study has been performed to know the mechanism of Cd toxicity. Since there is a recommendation by CODEX committee to regulate the Cd concentration less than 0.2 ppm in an environmental sample, the Cd accumulation in an edible part of the crop plant has bean gathering the attention. Therefore, we analyzed the Cd distribution manner within a soybean plant, as well as those of the other heavy metals, during the developmental stage. Soybean plants were grown in soil, which contained high amount of Cd, about 3 ppm. Before and after ripening process, pods, leaves and stems were harvested and the elemental concentrations were measured by INAA. The samples were dried and sealed with a double layer of ultra pure polyethylene vinyl bags and irradiated by a

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI research reactor, JRR-3M, installed at Japan Atomic Energy Inst. (JAERI). The total thermal neutron flax was 1.9×1013 n cm-2 and the elements were determined by gamma-ray spectroscopy. Though the elemental amount in leaves and seed shells changed by Cd treatments, concentrations in seeds were maintained in relatively constant values. We also carried out ICP analysis to compare the sensitivity of Cd determination with that of INAA. 407 WATER MOVEMENT AT BEAN PLANT ROOTS BY NEUTRON BEAM ANALYSIS. T. M. Nakanishi, Y.Okuni, Y.Hayashi and H.Nishiyama, Graduate School of Agricultural and Life Science, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657, JAPAN Though water plays an important role in plant activity, water uptake manner near the root has not been studied well, because of lacking tools for the research. We present water profile near the roots of bean plants by neutron beam analysis. Three kinds of bean plants were grown in cylindrical Al containers and were irradiated by thermal neutrons from a research reactor, JRR-3M, installed at Japan Atomic Energy Research Institute. After penetrating the sample, neutrons were converted to light by a fluorescent converter and was guided to a cooled CCD camera. Taking the projection images at different angles of the samples, CT images as well as spatial projection images were constructed. Through image analysis, it was shown for the first time that there was a minimum value in the water gradient toward the root surface in soil, at about 1mm far from the root surface, and then, water amount was drastically increased toward the surface. This tendency was observed in all three kinds of bean plants. When 10mM of Al was added to the soil, water content around the root was decreased. We also analyzed how the water content within a root or total area of the root surface change under Al stress through image analysis. 408 COLD AND VERY COLD NEUTRON RADIOGRAPHY FOR HIGH CONTRAST NEUTRON IMAGING IN KYOTO UNIVERSITY REACTOR Y.Kawabata*1, M.Hino1, U.Matsushima2, T.Horie3, T.Nakano3,1Research Reactor Institute, Kyoto Univ., Kumatori, Osaka 590-0494, Japan, 2Faculty of Agriculture,University of the Ryukyus, Nishihara, Okinawa 903-0213, Japan, 3Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan. Neutron radiography is a developed nondestructive research method. The neutron total cross-sections of light elements, especially hydrogen, make it quite unique as compared to X-ray radiography. The research field of the neutron radiography is very wide and the botany is one of the most promising ones because water plays an important role in plant activity. The cold neutron facility in Kyoto University Reactor (KUR) is used to estimate the water distribution in thin leaves. As the neutron spectrum and the effective total cross-section of water are evaluated, the difference of same plant images can be converted to the change of water distribution. Though the spatial resolution of a neutron imaging plate is very high, thermal neutrons can not show very small objects. As the attenuation factor of thermal neutrons is usually very low, it is hard to get a high contrast image. The only way is to use very low energy neutrons because the absorption cross-section is inversely proportional to neutron velocity. Very cold neutrons (VCN) are promising to show the details of objects and the VCN facility in KUR is one of few VCN ports in the world. 409 ESTIMATION OF VOLUMETRIC WATER CONTENT IN CHRYSANTHEMUM TISSUES USING COLD NEUTRON RADIOGRAPHY. U. Matsushima*1, Y. Kawabata2 , T. Horie3. 1 Department of Bioproduction, Faculty of Agriculture, University of the Ryukyus, Nishihara, Okinawa 903-0213, Japan. 2 Research Reactor Institute, Kyoto University, Kumatori, Osaka 590-0494, Japan. 3 Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, JAPAN. Radiographies using cold neutron beams are preferable than those by thermal neutron beams to detect slight amount of water in thin plant tissues, because low energy neutron beams make high contrast in neutron images. However, the beam spectrums of the cold neutron are not uniform. Therefore, the quantitative

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI analysis of water in a neutron image was developed for cold neutron radiography, where the scanning method was applied for the plant sample in front of beam ports. In this method, the spectrum of the cold neutron beam as well as the cross section of water were used to determine water thickness in chrysanthemum tissues without using standard materials. To check the accuracy of this method, stainless steal tubes, filled with water, were employed to compare the water amount obtained by image analysis with that of the actual water thickness. In addition to the 2-dimentional analysis, volumetric water content of chrysanthemum stems was estimated from the image. The values were slightly smaller than those of the actual sunflower stems. The difference seemed to be attributed to the actual water loss due to the cutting of the sample, suggesting that the water amount obtained by image analysis is in a good accordance with the real value. This method was shown to be an effective tool to trace water loss in chrysanthemum tissues. 410 RETENTION AND DISTRIBUTION OF IODINE IN MANGROVE SEDIMENTS. E.C. Machado1, W. Machado1, C.J. Sanders1, L.F. Bellido*2, S.R. Patchineelam1, A.V. Bellido Jr.3, 1Departamento de Geoquímica, Universidade Federal Fluminense, Niterói, RJ 24020-007, Brazil, 2Comissão Nacional de Energia Nuclear, Rio de Janeiro, RJ 22290-901, Brazil, 3Departamento de Físico-Química, Universidade Federal Fluminense, Niterói, RJ 24020-007, BRAZIL Laboratory experiments to investigate iodine ion removal by sediments from overlaying water, as well as its distribution in sediments, from a mangrove tidal creek in Sepetiba Bay were carried out. To provide information on time dependent interactions and distribution coefficients, 131IO3– and 123IO3– were used as radiotracers. Preliminary experiments, where local water was added to 6–7 cm sediment cores and spiked with 131IO3–, showed that 65−76% of initial 131IO3– activity in water was retained by sediments after one day. After 8 days, this retention was 84−90%, while 84−95% of the total activity in sediments was in the upper first cm layer. In another experiment, 600 mL of water was percolated (during about 15 h) through another core, 56% of the initial 123IO3– in water was retained in the sediment, and 85% of the activity in the sediment was within upper 2-cm layer. Since the creek studied is the main waterway draining responsible for water exchange between the mangrove ecosystem and Sepetiba Bay, results suggest that sediments trapping can substantially affect the iodine exchange. 411 MEASUREMENTS OF NATURAL LEVELS OF 14C IN HUMAN'S AND RAT'S TISSUES BY ACCELERATOR MASS SPECTROMETRY IN KOREA. Seung Y. Cho*1, Jeong Y. Lee2, Hyo. J. Ku3, Jin H. Kang3, Min Y. Yoon4 and Jong. C. Kim4, *1Dept. of Environmental Engineering of Yonsei Uinversity, Koea, 2NuEYES Inc., Korea, 3The Catholic University of Korea, 4Dept. of Physics of Seoul National Univsersity, KOREA Accelerator mass spectrometry(AMS) is the most sensitive, safe and precise analytical method for quantifying long-lived isotope in biomedical research with animal as well as human. In Korea, AMS lab has been operating successfully for years for measuring especially archeological samples for 14C dating. This year biological sample pretreatment facility was set-up and we have also started to work on biomedical applications. For preliminary study we measured the natural background levels of 14C in several tissues and blood of human and rat. The results were agreed with the other reported levels and gave stable and reproducible results within 1-2%. 412 DUPLICATE DIET STUDY OF KOREAN GERIATRIC POPULATION BY NEUTRON ACTIVATION ANALYSIS. Seung Y. Cho*1, Woo J. Hong1, Han S. Kim1, Jeong Y. Lee2 and Yong S. Chung3, 1Dept. of Environmental Engineering, Yonsei Uinversity, Korea, 2NuEYES Inc., Korea, 3Korea Atomic Energy Research Institute, KOREA One day duplicate diet samples of 30 Korean geriatric population over 60 years old were collected. Samples were analyzed by NAA(Neutron Activation Analysis) after sample preparation such as homogenization and

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI freeze-drying. SRM(Standards Reference Materials) from NIST were analyzed for quality control of the analytical method. Analytical results were classified into three groups such as macro elements(Ca, K, Mg, Na) and minor elements(Cr, Fe, Mn, Se, Zn) and toxic elements(Al, As, Hg). Analytical results for daily intake of geriatric population in Korea were showed that macro and minor elements were lower than RDA and IAEA study except Na and Cr. The results for distribution of macro and minor elements in hair were shown that Mg, Zn, Cr and K were similar to Korean reference values and Na, Fe, Mn and Se were lower than Korean reference values but Ca was very higher than Korean reference value. Toxic elements such as Al, As, Hg were higher than Korean reference values. In conclusion, NAA is proved to be a sensitive analytical method useful for performing both qualitative and quantitative multi-elemental analysis of macro and minor elements in diet and biological materials. 413 EMPIRICAL METHOD FOR THE CORRECTION OF PILE-UP LOSSES. C. Katzlberger*1, M. 1 Korner , M. Ditto2, 1Department of Radiation Protection and Radiochemistry, Austrian Agency for Health and Food Safety, Vienna, Austria. 2Federal Ministry of Social Security, Health and Generations, Vienna, Austria. A gamma quant entering a detector results in an impulse with an amplitude proportional to the absorbed energy. In case of full absorption, the impulse corresponds to the energy of the gamma quant (full-energypeak). However, the impulse amplitude can be varied by simultaneous impulses resulting in a different position in the energy spectrum. Count losses of these peaks are either due to true coincidence summing (independent from counting rate, photons of a single atomic nucleus) or random summing (pile up losses, dependent on counting-rate). Impulses within the time period τ (time resolution of the electronic system) are summed up. Assuming Poisson distribution, the following equation is valid for the probability (pc) of random coincidence within τ: pc = 1-e-2Rτ (counting rate R). pc is equivalent to the relative counting loss of the peak area. The true peak area can be determined from the measured peak area, R and τ. R can be calculated from the spectrum and τ can be determined experimentally with one fixed and one mobile source of noninterfering radionuclides measured at various distances from the detector. A detailed description of the experimental method and results for different detectors is presented in the paper. The correction factor of pile up losses is dependent on various parameters of the electronic system, especially the shaping time of the amplifier. 414 PRODUCTION OF HIGH SPECIFIC ACTIVITY GE-68 AT BROOKHAVEN NATIONAL LABORATORY. K.L. Kolsky*, L.F. Mausner, G.E. Meinken, S.O. Kurczak. Medical Department, Brookhaven National Laboratory, Upton, NY 11973, USA. Germanium-68 is widely used to calibrate PET systems. It decays (t1/2 = 271 d) by electron capture to 68 Ga(t1/2 = 68.1 m) which decays by positron emission (90.5%). Germanium-68 is produced at BNL using the natGa(p,xn) reactions by irradiating natGa metal targets (~ 140 g) with 45 MeV protons. Typical irradiation yields are ~ 16 GBq. For PET calibration applications, large amounts of no-carrier-added radioactivity with high activity concentration, > 1.85 GBq/mL, and solution pH ³2 are required. In the past, 68 Ge was recovered from the irradiated targets by dissolution in HCl/H2O2 followed by subsequent extraction from 10 N HCl into toluene to remove co-produced 65Zn. A back extraction into 2-4 mL 0.1 N HCl provided the final product with high activity concentration. This procedure had several challenges. Germanium tetrachloride is extremely volatile, making any volume reduction to meet the activity concentration specification difficult. However back extraction into small volumes result in erratic recoveries. Another difficulty involved adjusting the pH of the final solution while minimizing total volume. We report here on developments to improve the procedure. A distillation method was investigated to recover 68Ge directly from the target into a small volume of distillate. This method proved unsuccessful. Another approach was studied involving the creation of a nonvolatile germanium complex before final volume reduction. Results of these studies will be discussed.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI

415 COMPTON SUPPRESSION NEUTRON ACTIVATION ANALYSIS FOR CHEMICAL ELEMENT ASSESSMENT IN GRAINS OF THE BRAZILIAN DIET. M. A. Bacchi, L. G. C. Santos, E. A. De Nadai Fernandes*. CENA, University of São Paulo, 13416-903 Piracicaba, BRAZIL. Food supply for the increasing world population is a major challenge for humanity. Along with the efforts for a higher productivity, there has been a worldwide concern with food quality comprising both nutritional and safety aspects. Aiming at the understanding of the complex processes involved in nutrition and health, different items from human diet have been analyzed for organic compounds, inorganic substances and chemical elements. For plant products a special attention is addressed to the amount of pesticide residues and mineral elements, chiefly those classified as heavy metals. Several elements have well-known physiological behavior, being either essential or toxic depending on their contents, while others still have undefined effects for humans. In this study, beans and rice, basic components in the Brazilian dietary habit, as well as pea, lentil and chickpea were collected from the local market and directed to NAA for chemical characterization. Radioactivity was measured with a Compton suppression system, acquiring both suppressed and unsuppressed spectra for comparison. Data is discussed based on literature information and on limits imposed by international standards and laws for food safety. 416 EFFICIENCY SELF-CALLIBRATION OF THE HPGE DETECTOR FOR ON-LINE ASSAY OF PEBBLE BED REACTOR FUEL. A. I. Hawari*1, J. Chen2, B. Su2. 1Department of Nuclear Engineering, North Carolina State University, Raleigh, NC 27511, USA. 2Nuclear and Radiological Engineering Program, University of Cincinnati, Cincinnati, OH 45221, USA. Pebble bed reactors are characterized by multi-pass fuel systems in which spherical fuel pebbles are circulated through the core until they reach a proposed burnup limit (80,000 – 100,000 MWD/MTU). For such reactors, the fuel is assayed on-line to ensure that the burnup limit is not breached. We considered assaying the fuel using an HPGe detector to perform passive gamma-ray spectrometry of fission products. We studied the use of absolute burnup indicators such as Cs-137, which would require absolute efficiency calibration of the detector. Alternatively, we investigated the option of doping the fuel with Co-59 and constructing an indicator that is resistant to power history variations using the activity ratio of Co-60/Cs-134. A relative indicator requires knowledge of the relative efficiency of the HPGe detector. This allows the use of a self-calibrating approach for efficiency determination. In this work, we study the utilization of several fission products as built-in on-line relative calibration standards. In addition, we discuss the construction of the relative efficiency curve. To perform the analysis, we combined the capabilities of the computer codes ORIGEN2.1, MCNP4C, and SYNTH to produce simulated gamma-ray spectra of the fuel pebbles at various levels of burnup. This allowed us to visualize the spectra and consider issues of detectability and spectroscopic interference, which otherwise would be difficult to address due to the lack of experimental data. 417 WHAT HAS BEEN DONE AND WHAT HAS TO BE DONE IN BRAZIL TO PRODUCE AN ORGANIC COFFEE CERTIFIED REFERENCE MATERIAL. F. S. Tagliaferro1, E. A. De Nadai Fernandes*1, P. Bode2, 1Centro de Energia Nuclear na Agricultura, Universidade de São Paulo (CENA/USP), P.O. Box 96, 13400-970, Piracicaba, SP, BRAZIL, 2Interfaculty Reactor Institute, Delft University of Technology (IRI/TUDelft), 2629JB, Delft, THE NETHERLANDS Certified reference materials (CRMs) play a fundamental role in analytical chemistry to verify the accuracy and reliability of measurements results in the framework of the laboratories’ internal quality control. In spite of the vital importance of chemical measurements in the food sector, Brazil does not produce CRMs to supply its current demand. Since 1998 the CENA/USP and the IRI/TUDelft have dedicated efforts for the evaluation of elemental composition of coffee beans by neutron activation analysis (INAA). A series of

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI experiments was performed for the element content characterization of Brazilian coffee brands, for the evaluation of homogeneity of the coffee matrix and for the discrimination of coffees cultivated under conventional and organic systems. Such approach consisted on the first steps in developing a better understanding of the coffee matrix before going to the production of an Organic Coffee CRM. Feasibility studies are on the way in order to establish a design model for such a production, searching for the optimal conditions of material sampling and preparation, homogeneity and stability tests, analytical techniques for the certification and statistical data treatment. 418 A SUGGESTED GENERAL ROBUST GAMMA SPECTROMETRY ANALYSIS LIBRARY FOR ENVIRONMENTAL ANALYSIS. C. M. Johnson, Jr. *1 B. S. Crandall2,, and T. L.. Rucker1. 1Science Applications International Corporation, 301 Laboratory Road, Oak Ridge, TN 37830, USA. 2Savanah Rive Site, 13715 Rider Trail North, Earth City, MO 63045, USA. Gamma spectroscopy is utilized extensively for identification and quantification of gamma emitting radionuclides in the environmental radioanalytical industry. These analyses are frequently used to demonstrate compliance with local, state or national environmental regulations or programs. Additionally, gamma spectral analyses are frequently requested as part of the analysis suite for the closure of risk-based environmental remediation projects. Gamma spectroscopists remain in fear (rational or irrational) of lawsuits, fines, prosecution, or a loss of employment or occupational tranquillity which has made them adopt a conservative philosophy of maximizing false positives and minimizing false negatives. These fears have forced conservatism on our industry and that is unfortunate since false positives can actually drive remediation projects and cost taxpayers billions. To help fight this situation, gamma spectroscopists expend a significant amount of energy generating and maintaining their identification and interference libraries. However, there has been an increased dependence by laboratories relying on the instrument manufacturers to generate robust “turn-key” systems that quantify gamma-emitting radionuclides with minimum setup and maintenance. In this paper, a possible solution of possible “turn-key” identification and interference library will be given. 419 ESTIMATION OF EXPANDED UNCERTAINTIES FOR IODINE MEASUREMENT IN BIOLOGICAL REFERENCE MATERIALS BY EPITHERMAL INAA AND ANTICOINCIDENCE GAMMA-RAY SPECTROMETRY. R. Acharya and A. Chatt*, SLOWPOKE-2 Facility, Trace Analysis Research Centre, Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3, CANADA The determination of low levels of iodine in biological materials is generally difficult by INAA and sometimes even by EINAA using cadmium filters due to high dead times. Additionally, the background in the region of the 443-keV photopeak of 128I is often dominated by Compton background from the γ-rays of 24 Na, 56Mn, 38Cl, 42K, 28Al and 82Br. Epithermal instrumental neutron activation analysis methods in conjunction with anticoincidence gamma-ray spectrometry (EINAA-AC) have been developed in this work for the determination of ppb levels of iodine in selected biological reference materials (RMs) and standard reference materials (SRMs) issued by NIST. These methods reduce the background which in turn help improve the detection limits for iodine. They appear to be superior to preconcentration as well as radiochemical NAA methods under the experimental conditions used if the iodine levels are about 40 ppb or higher. We have developed both conventional and pseudo-cyclic EINAA-AC methods using Cd+B filters in a neutron flux of 1x1011 cm-2 s-1 at the Dalhousie University SLOWPOKE-2 reactor facility. We have obtained an iodine content of 92.3±7.6 µg.kg-1 with a detection limit of 40 µg.kg-1 for NIST SRM 1575 (Pine Needles); to our knowledge this value has been obtained for the first time by a non-destructive NAA method. Our value for the iodine content of NIST SRMs 8418 (Wheat Gluten) is 64±6 µg.kg-1 compared to the certified value of 60±13 µg.kg-1. The expanded uncertainties at 95% confidence level following the ISO guidelines have been evaluated in detail and will be presented.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 420 CHARACTERIZATION OF ORGANOHALOGEN SPECIES IN COD FISH USING A MULTITECHNIQUE APPROACH. C.S. Bottaro, J.W. Kiceniuk and A. Chatt*, SLOWPOKE-2 Facility, Trace Analysis Research Centre, Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3, CANADA Many of the organohalogens are persistent organic pollutants (POPs) and are of much interest because of their known and potential toxic effects on living organisms. Numerous chlorinated compounds have been released directly into the environment as pesticides (e.g. DDT, Toxaphenes) or as byproducts of industrial activities (e.g. chlorophenols). One of the problems associated with the determination of total extractable organohalogens (EOX) is that a large amount of the extracted material cannot be accounted for by summing the quantities of known compounds. For example, between 74% and 99% of extractable organochlorines (EOCl) in several species of Canadian fish cannot be accounted for by techniques such as gas chromatography/mass spectrometry (GC/MS) which are currently employed widely for the quantification of total EOCl. It is for this reason, techniques such as neutron activation analysis (NAA) must be employed to measure the total amount of the halogens present. Little information is available for the majority of the EOCl. We have concentrated our efforts in developing a multi-technique approach for the separation, detection, identification, and measurement of EOCl species in cod ovaries. We have developed liquid-liquid extraction methods for the separation of organochlorines from the ovaries and esterification to preconcentrate certain species of interest. We have used neutron activation analysis (NAA) for the quantitation of Cl in EOCl, mass spectrometry (MS) for the qualitative detection of Cl as well as for identification of individual compounds, and nuclear magnetic resonance (NMR) spectrometry for the additional characterization of EOCl compounds. Details of the methods and results will be presented. 421 AN APPLICATION OF NUCLEAR TECHNIQUES TO ASSESS PRODUCING OIL AND GAS WELLS AT RISK OF NORM CONTAMINATION AND FURTHER OUR UNDERSTANDING OF THE CAUSES OF NORM ENRICHMENT. M.J.M. Duke. SLOWPOKE Nuclear Reactor Facility, University of Alberta, Edmonton, Alberta, CANADA. Increased quantities of NORM are often encountered by the oil and gas industry. The high solubility of radium, radon and lead in brines provides an effective means to transport NORM from within the Earth’s crust to the surface in formation waters. Changes in physio-chemical conditions at, or near surface, and/or the mixing of waters of different chemistries, can cause precipitation of radionuclides and an increase in their concentration in scales and sludges. Build-up of NORM has important economic, environmental and safetyrelated implications. Models, or criteria, with which to identify producing wells at greatest risk of NORM contamination would be beneficial because 226Ra-contaminated materials released to the environment will remain an extremely long-term issue in regards to potential human exposure unless remedial action is taken. Within Canada the issue of NORM has become more significant in recent years with the lowering of the release limits for diffuse NORM from 10 Bq/g to 0.3 Bq/g for many members of the U- and Th-decay series. This study reports on a pilot project to develop and test a fairly rapid means to identify those producing wells at risk of NORM contamination based on the measurement of 222Rn in co-produced natural gas and 226Ra in brines. Chemical and radiometric analyses of the brines (via ENAA, ICP, and high resolution gamma-ray spectrometry) also provide insight into the transport and enrichment of NORM. . 422 DETERMINATION OF TOTAL TIN AND ORGANOTIN COMPOUNDS IN SEX GONADS OF SHELLFISH BY NEUTRON ACTIVATION ANALYSIS. M. Fukushima1,*, Y. Nakano2, K. Isaac-Olive3, and A. Chatt3. 1Department of Science and Engineering, Ishinomaki Senshu University, Ishinomaki, Miyagi 986-8580, JAPAN. 2Kyoto University Research Reactor Institute, Kumatori, Sennan-gun, Osaka 590-0494, JAPAN. 3SLOWPOKE-2 Facility, Trace Analysis Research Centre, Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3, CANADA. Tributyltin and triphenyltin compounds have been widely used in paints applied to fisheries vessels and equipment, for example in ship bottoms and firm nets. These are highly toxic tin compounds and can cause

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI serious problems to marine organisms, especially shellfish. The transfer of these compounds to human beings through food chain is a potential threat to their health. Since sex gonads of organisms contain high amounts of lipids, it is quite possible that the organotin compounds may be accumulated there. We have analyzed sex gonads of shellfish and some other fish species. Male and female sex gonads of Giant Scallop, sea-urchine, and cods from Japan were collected and freeze dried. They were irradiated for 10 min at the SLOWPOKE-2 Reactor in Dalhousie University (Canada) or at the Kyoto University Research Reactor (Japan). The samples were allowed to decay for 1min and counted for 10 min. The 332.1 keV gamma-ray 125m Sn (t1/2 = 9.52 min) was used to assay the tin content of the samples. The samples containing high levels of total tin were treated with an acetone-hexane mixture to extract organotin compounds. The extracts were filtered, concentrated by freeze drying, and irradiated in the same way to analyze for tin. Very high levels of total tin, for example 440±37 µg.g-1 and 154±1 µg.g-1, were found in the male sex gonads of two Giant Scallops. Details of the methods and results will be presented. 423 RADIOANALYTICAL METHODS AS TOOLS IN METALLOPROTEIN RESEARCH. D. Behne. D. Alber, A. Kyriakopoulos, Hahn-Meitner-Institut Berlin, Department "Molecular Trace Element Research, in the Life Sciences", Glienicker Str. 100, D-14109 Berlin, GERMANY The biological functions of many proteins depend on a metal or metalloid which is needed either as part of the active center of an enzyme or as a structural component. However, relatively few members of these “metalloproteins” have so far been detected. In most cases the presence of metals or metalloids in a protein cannot be recognized from its genetic code. The identification of novel metalloproteins and the elucidation of their characteristics and functions are therefore of great interest in many fields of the life sciences, especially with regard to their diagnostic and therapeutic use in molecular medicine. For these studies procedures have been developed in which radioanalytical procedures such as neutron activation analysis and radiotracer techniques are combined with biochemical and molecular biological methods. Information on the distribution of the metals and metalloids in the organism and on their possible sites of action is obtained by separation of tissues, cells and subcellular compartments and neutron activation analysis of the elements in the isolated fractions. For the detection of novel metalloproteins laboratory animals and cell cultures are labeled with radiotracers of the elements in question. After separation of the proteins by gel electrophoretic or chromatographic methods, the metal- and metalloid-containing proteins are determined via their tracer activity. The identification of a novel metalloprotein is then achieved by purification of the labeled protein and analysis of its amino acid sequence using MALDI-MS of the peptide fragments, mRNA determination and cDNA synthesis. In this survey the application of radioanalytical methods in metalloprotein research will be presented and discussed. 424 SELENIUM IN LEAVES OF NATIVE TREES OF THE ATLANTIC FOREST. E. J. França, E. A. De Nadai Fernandes, M. A. Bacchi and J. R. Ferreira. Centro de Energia Nuclear na Agricultura, Universidade de São Paulo, Piracicaba, CP 96 13400-970, BRAZIL. Selenium is remarkably concerning as an environmental contaminant. It is considered the most toxic essential trace element and is commonly found in plants. Although the essentiality of selenium for plant growth has not been conclusively established, its uptake is due to chemical similarity to sulphur. Aiming at the investigation of natural background contents in forestry plants, selenium was evaluated in the leaves of eight tree species growing in the “Parque Estadual Carlos Botelho”. This site is a representative natural reserve of the Atlantic Forest with high priority in terms of biodiversity conservation. The k0-method NAA (neutron activation analysis) and AFS (atomic fluorescence spectrometry) were used for the determination of selenium in the leaves. The understory species Euterpe edulis, Gomidesia flagellaris, Gomidesia spectabilis and Sloanea monosperma showed concentrations of selenium in the range of 0.2-0.7 mg kg-1. High contents of selenium in plants in relation to soil may suggest its accumulation in the understory trees.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 425 BIOPROSPECTION IN THE SÃO PAULO STATE FORESTS ENVISAGING REFERENCE MATERIALS OF TROPICAL TREES. E. J. França*1, E. A. De Nadai Fernandes1, M. A. Bacchi1 and P. Bode2. 1Centro de Energia Nuclear na Agricultura, Universidade de São Paulo, Piracicaba, CP 96 13400-970, BRAZIL. 2 Interfaculty Reactor Institute, Delft University of Technology, Mekelweg 15, 2629 JB Delft, THE NETHERLANDS. Bioprospection encompasses search, investigation and exploitation of the biodiversity for commercially valuable genetic information and chemical compounds obtention. Due to the different kinds of forest in the São Paulo state, Brazil, there is huge plant diversity available for bioprospection purposes. The major part of these forests is restricted to the conservation units, which includes the Atlantic Forest, one of the hottest hotspots of the global biodiversity. For the analytical quality control of samples from such complex environment, similar matrix certified reference materials are needed. Nevertheless, reference materials of tropical plants are still scarce. Multielementar determinations using instrumental neutron activation analysis (INAA) performed in leaves of plants growing in the tropical forests indicated a chemical diversity related to the number of elements and the magnitude of concentrations. Tree leaves of the Semideciduous Forest showed high concentration values of lanthanides and bromine. The Atlantic Forest trees present appreciable concentrations of selenium in their leaves. Therefore the selection of plant species to produce reference materials can be realized complementarily to other characteristics like the chemical compounds for medical purposes, the ecological relevance of the specie for the biodiversity conservation, and the extinction risk. These facts have stimulated the preparation of reference materials of native tree leaves envisaging the biodiversity conservation of the São Paulo state together with the improvement of the analytical quality of the environmental studies in progress. 426 ANALYSIS OF RADIATION DETECTION SYSTEMS FOR DETECTING THE ILLICIT TRAFFICKING OF NUCLEAR MATERIALS. M. Gregson*1 And W.S. Charlton1, 1Nuclear Engineering Teaching Laboratory, University Of Texas At Austin, Austin, Tx 78758, USA One of the key systems used to detect and deter the smuggling of special nuclear material (SNM) are portal monitors. These monitors are passive radiation detection systems designed to detect neutron and/or gammaray emissions from weapons material (specifically plutonium and high-enriched uranium). There are several types of portal monitors including pedestrian, vehicle, and rail systems. The detection of smuggled SNM on railroad cars is of paramount importance to apprehend potential smugglers. A study was performed to analyze various rail portal monitors to determine the optimal configuration of monitors to provide the largest possible detection signature. MCNP-4C was used to simulate the transportation of SNM placed on a railroad car. A portal monitor consisting of a plastic scintillator and six 3He tubes was used to detect the emitted radiations. A moving railroad car passing a stationary detector was modeled. The counts in the detector were calculated as a function of detector position, material position on the car, and car speed. From this data, the maximum speed that a railcar may travel and still detect small amounts of SNM can be computed. This data will provide a means for optimizing monitors and rail site protocols for detection of illicit nuclear smuggling events. 427 INCREASING MARKET FOR THE BRAZILIAN ORGANIC ORANGE JUICE. E. A. De Nadai Fernandes1, C. Turra1, M. A. Bacchi1, F. S. Tagliaferro1, P. Bode2, 1 Centro de Energia Nuclear na Agricultura, Universidade de São Paulo (CENA/USP), P.O. Box 96, 13400-970, Piracicaba, SP, BRAZIL, 2Interfaculty Reactor Institute, Delft University of Technology (IRI/TUDelft), 2629JB, Delft, THE NETHERLANDS Brazil is both the world largest producer of citrus and exporter of citrus juices. The citriculture plays a relevant role in the national agriculture, being responsible for 9.3% of GNP and for a significant workforce. The country has also the potential to be the world largest producer of organic orange juice. Organic

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI agriculture is just a one-hand trend growing worldwide and has been practiced in more than 120 countries. Brazil has the fifth largest area of organics, of which 1994 hectares are occupied with certified organic citrus. At present, there are main four industries in the country producing organic orange juice for internal and external consumption. Attempts have been done to establish an elemental pattern for citrus in order to verify the authenticity of juices, the origin of citrus and the variety used in the production of orange juice. A comprehensive sampling of organic and conventional orange juices, including the frozen concentrated orange juice (FCOJ), has been performed in the local market. The chemical characterization of the juices was done by normal and large-scale instrumental neutron activation analysis (INAA). Data statistical treatment with multivariate analysis has explored the similarities among the samples providing discrimination between conventional and organic juices. 428 CAFÉS DO BRASIL: COFFEES OF GOOD QUALITY. E. A. De Nadai Fernandes1, C. F. 1 Moreira , F. S. Tagliaferro1, P. Bode2, 1Centro de Energia Nuclear na Agricultura, Universidade de São Paulo (CENA/USP), P.O. Box 96, 13400-970, Piracicaba, SP, BRAZIL, 2 Interfaculty Reactor Institute, Delft University of Technology (IRI/TUDelft), 2629JB, Delft, THE NETHERLANDS Time has come to learn the taste of a good cup of coffee like it is being done for decades with a good glass of wine. A change in attitude for appreciation of the quality of coffee is needed. There are many similarities between coffee and wine, both existing from ordinary to excellent quality. In the case of wine, however, there is a specific marketing to help consumers in identifying the products. A similar strategy is being implemented in Brazil for coffees, especially those with controlled origin and certification, proposing an aggressive international dissemination of the culture and the pleasure of drinking coffee. Brazil is responsible for one third of the coffee in the world, produced in various states in the country under different climatic conditions. Therefore, a great selection of coffee varieties namely Acaiá, Bourbon, Caimor, Catuaí, Catucaí, Iapar, Icatú, Mundo Novo, Obatã and Tupi can be found in the market. Brazil is changing from conventional to organic system to meet the international demand for this special coffee. In an attempt to chemically characterize the Brazilian coffees, about 100 samples were analysed by INAA. A databank was set and robust statistics used to discriminate the different types of coffee. 429

PLUTONIUM, AMERICIUM, PROTACTINIUM, URANIUM AND THORIUM ISOTOPES DETERMINATION IN ENVIRONMENTAL SAMPLES BY SF ICP-MS. M. Agarande, A. M. Neiva-Marques, P. Bouisset, Institut de Radioprotection et Sûreté Nucléaire, Environmental Radioactivity Measurement Laboratory, Bois des Rames F-91400 Orsay (FRANCE) Alpha spectrometry is the most commonly used analytical tool for the determination of Pu, Am, Pa, U and Th long live radionuclides. Thermal ionisation mass spectrometry (TIMS) and acceleration mass spectrometry (AMS) are also still considered as primary methods for the determination of their isotope ratios. Spectrometers with plasma ion sources now offer another efficient alternative method with the development of sector field inductively coupled plasma mass spectrometry (SF ICP-MS). This paper summarizes the development work performed and results obtained using this technique for the analysis of such radionuclides. Isotopic ratios and ultra trace levels of man made radionuclides like 239, 240, 241 plutonium, and 241 americium but also naturally occurring species like 231 protactinium, 234, 235, 238 uranium and 230, 232 thorium were determined in different field samples and reference materials using a micro concentric nebulizer as an introduction system for the mass spectrometer. Prior to the mass spectrometric measurements these elements were isolated from major elements by different selective precipitations. In further steps, they were purified by anion exchange. Results obtained for samples isotope ratios, included plutonium isotope ratios, are also discussed. 430 DETECTION OF WOOD DISCOLORATION IN A CANKER FUNGUS- INOCULATED JAPANESE CEDAR BY NEUTRON RADIOGRAPHY. T. Yamada1, Y. Aoki2, M. Yamato2, M. Komatsu2,

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI D. Kusumoto2, K. Suzuki2, and T. M. Nakanishi2. 1Experimental Station at Tanashi, University Forests, The University of Tokyo, Nishitokyo, Tokyo 188-0002, Japan. 2Graduate School of Agricultural and Life Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657, JAPAN Since neutron radiography (NRG) is a promising method to know the water distribution within a living woody plant, this method was applied to trace the development of discolored tissue in the wood of Japanese cedar (Cryptomeria japonica) after the canker fungus infection. Japanese cedar seedlings were wound inoculated with a virulent or avirulent isolate of a canker fungus, Guignardia cryptomeriae. Three, 7, 13 and 22 days after the inoculation, the seedlings were irradiated with thermal neutron beam at a research reactor, JRR-3M, installed at Japan Atomic Energy Research Institute. The image on the X-ray film was obtained by a gadrinium converter. The whiteness in the image corresponds to water content in the sample. Discolored tissue and surrounding dry zone induced by the fungal inoculation was detected as dark area, indicating water deficient part, with high resolution. Through image analysis, dry zone was detected as early as 3 days after inoculation, whereas no obvious change in wood color was observed until later stage. Neutron images also showed the difference in the size of water deficient part due to the tissue damage caused by the treatment. Expansion rate of damaged tissue was most rapid in the seedlings inoculated with a virulent isolate. Neutron beam used in this experiment had no effect on the growth rate of the fungus on a medium, showing that NRG is an effective method for pathological research of trees. 431 GAMMA ACTIVITY MEASUREMENTS IN AEROSOL SAMPLES COLLECTED IN FRANCE SINCE 1970. E. Barker, P. Bouisset, X. Cagnat, O. Masson, Institut de Radioprotection et de Sûreté Nucléaire, Environmental Radioactivity Measurement Laboratory. Bât. 501,Bois des Rames F-91400 Orsay (FRANCE) Spatial and temporal evolution study of atmospheric radioactivity in aerosols as well as dry and wet deposition, gives information about radionuclides origin, concentration variations and impact of accidents such as Chernobyl (1986 Ukraine) or Algeciras (1998 Spain). In the frame of IRSN’s french observatory, aerosol samples are collected since 1970 from stations located in France (6 stations in the northern hemisphere and 2 stations located in the southern hemisphere at Papeete and at Saint-Denis de la Réunion). Long chronological successions of natural radionuclides (7Be, 210Pb and 40K) and of artificial radionuclides (137Cs) are presented. Evolution of the natural 7Be concentration shows two cycles, one of 1 year and the other of 11 years. Cesium 137 coming from atmospheric nuclear tests and the accident of Chernobyl, gradually diminishes since 1986 and presents a one year cycle. A change of phase of 6 months is observed in the 137Cs results since the beginning to the end of the 80’s. This shows a changing in the 137Cs storage, first atmospheric compartment followed by soil compartment. In France (northern hemisphere), in 2002, 137Cs, 7 Be, 40K, 210Pb levels are respectively around 0.5 µBq.m-3, 3300 µBq.m-3, 10 µBq.m-3 and 600 µBq.m-3. In the southern hemisphere’s locations, 7Be and 40K levels are in the same order as northern hemisphere ones. For 137Cs and 210Pb, levels are respectively 10 and 6 times lower than northern hemisphere levels. 432 BETA SPECTROMETRY PERFORMANCES FOR DIRECT MEASUREMENT OF ENVIRONMENTAL SAMPLES USING PIPS DETECTOR. P. Bouisset, A. Courti, R. Gurriaran, Institut de Radioprotection et de Sûreté Nucléaire, Environmental Radioactivity Measurement Laboratory. bâtiment 501,Bois des Rames F-91400 Orsay (FRANCE) Rapid identification and quantification of beta-gamma emitters are of interest for many applications: postaccidental situation, expertise application or in situ studies. The actual gross-beta measurement can not separate the major radioactive components. A direct measurement method of these radionuclides has been developped, based of the PIPS (Passivated Implanted Planar Silicon) detectors in a coincidence configuration. Pure elements (such as 36Cl, 90Sr, 137Cs, 134Cs, 60Co..) have been tested in point source measurement configuration. Monte-Carlo simulation (Geant code) has been used to generate reference spectra for large geometry configurations.. These reference spectra represent the data base used for the

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI complex deconvolution of spectra acquired for a real sample. We present the capability of this new approach in the case of small contaminated soil samples. 433 TRACE LEVEL ELEMENTAL AND ISOTOPIC ANALYSES IN NUCLEAR AND ENVIRONMENTAL SCIENCES. Gregory C. Eiden, Orville T. Farmer III, Charles J. Barinaga, Scott A. Lehn, John F. Wacker, Steven L. Petersen, Tapas C. Maiti, James M. Kelley, Khris B. Olsen, and Harry S. Miley, National Security Division, Pacific Northwest National Laboratory*, Richland, Washington, USA The sensitivity of inductively coupled plasma mass spectrometry (ICP-MS) has improved in recent years to the point that this method is now competitive with traditional radiochemical and mass spectrometry methods for the determination of environmental levels of many radionuclides. Mass spectrometry is of obvious interest when either long-lived or stable fission products are to be determined. The sensitivity of thermal ionization mass spectrometry (TIMS) and ICP-MS is such that radiometric counting is more sensitive only for short-lived species. ICP-MS and radiometric counting have comparable sensitivity for species with halflives in the range of 1-10 years, i.e., radiometric counting is more sensitive for species that are shorter-lived than this. We have found that in the most favorable cases, ICP-MS is as sensitive as radiometric counting for species with half-lives as short as 1 month. Which technique is more sensitive depends on such factors as the mode of decay, decay branching ratios, and background radiation for radiometric counting. For mass spectrometry, critical factors include ionization efficiency, instrument transmission efficiency, and isobaric interferences. The greatest gains in ICP-MS performance have been made by addressing efficiency, background, and interferences. For any of these methods, the sample size and chemical yield of the sample preparation chemistry must also be considered. At PNNL, we have long-standing programs which rely on radiometric counting and atom counting. ICP-MS is a recent addition to this mix of techniques. We will present recent results concerning the limits of isotope ratio measurement precision that can be achieved with quadrupole-based ICP-MS, primarily focused on actinide measurements. We will discuss the strengths and limitations of each of the above instrumental approaches to addressing low-level measurements of interest in nuclear forensics, environmental monitoring, and other applications. *PNNL is operated by Battelle for the U.S. Department of Energy under contract DE-AC06-76RLO 1830. 434 MEASUREMENT OF CHLORINE-36 IN NUCLEAR WASTES AND EFFLUENTS. VALIDATION OF A RADIOCHEMICAL PROTOCOL WITH AN IN-HOUSE REFERENCE SAMPLE. C. Fréchou* and J-P Degros. Commissariat à l'Energie Atomique, Solid and Liquid Wastes Characterization Laboratory, CE – Saclay Bât 459, F-91191 Gif sur Yvette Cedex – FRANCE Cl-36 is a beta emitter with a very low specific activity. It is produced during the irradiation of nuclear fuel, in the reactor core of power plants, from neutron capture by stable 35Cl that may be present at trace level in any part of the irradiated material. Due to its long half life (T=3.01.105a), Cl-36 may be significant in impact assessment studies of disposal sites of nuclear wastes. Considering these different elements, the National Radioactive Waste Management Agency (Andra-France) request information on the Cl-36 contents of the wastes packages destined to be stored at Andra sites. As for other halogens, the measurement of Cl-36 is a difficult analytical task in view of its potential losses during the different chemical steps and also because of the lack of international certified reference sample needed to validate the chemical and measurement procedures. This paper will describe the methodology used to constitute a solid reference sample with a known content of stable and radioactive chlorine. The radiochemistry used to extract and purify Cl-36 before measuring it by liquid scintillation will be described. Data on the accuracy, repeatability and uncertainty of this protocol will be presented following the results of the measurement replications on the constituted "inhouse" reference material.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 435 TRACE ELEMENTS IN NAIL POLISH AS A SOURCE OF CONTAMINATION OF NAIL CLIPPINGS, USED IN EPIDEMIOLOGICAL RESEARCH. P.C.Favaro1,2, P. Bode2, E. A. De Nadai Fernandes1,. 1CENA, University of São Paulo, Piracicaba, BRAZIL, 2Interfaculty Reactor Institute, Delft University of Technology, THE NETHERLANDS. Nail clippings are one of the bio-indicators for the trace element status of humans, and intensively used in epidemiological studies. Because of the many studies dealing with the role of Selenium in relation to cancer, a vast amount of information is available on e.g. the relation between Se and intake and on sources of contamination. Since epidemiologists are considering the use of nail clippings to study other trace elements as well, additional studies are needed to assess related sources of contamination. Remainder of nail polish is a trivial one, especially since there is no consensus if it is safe to clean nail clippings prior to analysis. Cosmetics may contain very high levels of inorganic components, resulting in element concentrations up to thousands of ppm's. As a start, we determined the trace element levels in several brands of nail polish to estimate the possible degree of contamination. 436 DAMN LIES AND POISSON STATISTICS:AN EXPERIMENTAL VERIFICATION OF THE LIMITS OF POISSON STATISTICS IN NUCLEAR COUNTING. D.R. Lane-Smith, Durridge Company, Inc., Bedford, MA 01730, USA. Several years of data are analyzed to show the deviation from the expected scatter of readings, due to multiple decays of atoms in the counting cycle. The RAD7 Electronic Radon Detector works by counting the individual decays of various polonium isotopes inside the measurement chamber. It performs a highresolution real-time spectral analysis of the alpha energies to identify the isotope involved in each count. Four such instruments are used as standards in the DURRIDGE calibration system, monitoring a constant radon concentration of close to 35 pCi/L. The last four years of data from these instruments provides a wealth of material from which to determine the actual statistical distribution of a) 218-Po counts, b) 214-Po counts, c) the sum of the two, 218-Po plus 214-Po counts (that is used to calculate the radon concentraion in 'Normal' mode), and 210-Po counts. Nearly half the 214-Po counts in each 6-hour cycle arise from later decays of 218-Po atoms already counted. The resulting normal-mode deviation from Poisson statistics for long cycle times is demonstrated. 437 THE MULTI-ELEMENT GAMMA ASSAY (MEGA) SYSTEM: A LARGE ULTRA-LOWBACKGROUND COUNTER FOR ENVIRONMENTAL SAMPLES. C. E. Aalseth1, H. S. Miley1, 1Pacific Northwest National Laboratory, Richland, WA 99352, USA The exploitation of multiple-gamma coincidence signatures has long been recognized as a powerful tool for discriminating against source-associated backgrounds. However, typical coincidence-counting systems usually sacrifice either energy resolution, using large NaI detectors, or efficiency, using HPGe detectors. Additionally, for the lowest-level measurement scenarios, cosmic-ray backgrounds and the imperfect radiopurity of commercial cryostat materials limit sensitivity. The Multiple-Element Gamma Assay (MEGA) System is being built to address these realities and produce an advanced laboratory capability for assay of environmental samples. The system uses an array of 18 HPGe detectors (each of 70% relative efficiency) installed in high-purity electroformed copper cryostats and instrumented with detector electronics allowing pulse-shape discrimination of the detector signals. Operation of the MEGA system will achieve dramatic increases in sensitivity by simultaneously providing: • exotic multi-coincidence detection and HPGe energy resolution for reducing sample-associated backgrounds • high absolute detection efficiency via an array of HPGe crystals • underground siting for mitigation of cosmic-ray backgrounds • unique PNNL ultra-low-background detector technology

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI • unique PNNL pulse-shape discrimination methods for background rejection Multidimensional analysis tools are under development and will be applied to data from the MEGA instrument. Pacific Northwest National Laboratory is operated by Battelle Memorial Institute for the US Department of Energy under Contract DE-AC06-76RLO 1830. 438 A PORTABLE NaI(Tl) BASED MULTI-COINCIDENCE RADIONUCLIDE ANALYSIS SYSTEM WITH GERMANIUM-LIKE SENSITIVITY AND SELECTIVITY. Craig E. Aalseth, Harry S. Miley, Todd W. Hossbach, and L. Eric Smith,, National Security Division, Pacific Northwest National Laboratory*, Richland, WA, USA In the wake of the events of September 11, 2001, the need has greatly increased for a rapidly-deployable, high-selectivity radionuclide analysis system for the first responder. A typical crisis-response scenario is for samples to be taken blindly or with minimal in-field screening with low-selectivity (i.e. singles NaI(Tl) spectroscopy) measurements. These samples would then be sent to a radiochemistry laboratory for a detailed and time-consuming analysis. A less-traveled path is to operate a high-resolution germanium detector in the field for higher-quality screening and more immediate results. While no field technique is more sound than a complete radiochemical laboratory analysis, this general approach does not answer the need to measure short-lived isotopes or to select only the most valuable samples to expedite to a laboratory. Efforts are underway at Pacific Northwest National Laboratory (PNNL) to develop a man-portable, briefcase-sized radionuclide detection system to perform detailed analysis of below-background samples at or near the point of collection. Using a pair of NaI(Tl) detectors and applying multidimensional background estimation, interference-removal techniques, and a multi-coincidence data library derived from the ENSDF, it is possible to perform multidimensional spectral analysis resulting in germanium-like selectivity and sensitivity. Automated sample analysis is accomplished with an intelligent software solution coupled to the PNNL multicoincidence data library. As a result, the system will be ideally suited for rapid field deployment and requires minimal technical expertise to operate. *PNNL is operated by Battelle for the U.S. Department of Energy under contract DE-AC06-76RLO 1830. 440 THE NUCLEAR EDUCATION AND STAFFING CHALLENGE: REBUILDING CRITICAL SKILLS IN NUCLEAR SCIENCE AND TECHNOLOGY. N.A. Wogman,1* L.J. Bond,1 and R.E. Leber.2 1 National Security Directorate, Pacific Northwest National Laboratory, P.O. Box 999, Richland WA 99352 USA. 2Science Program Chairman, Division of Arts and Sciences, Heritage College, 3240 Fort Road, Toppenish WA 98948 USA The Nation, Department of Energy (DOE) and its National Laboratories, including the Pacific Northwest National Laboratory (PNNL), are facing a serious attrition of nuclear capabilities through the effects of aging staff. It is expected that there will be a significant loss of senior nuclear science and technology staff at PNNL within five years. To counter this impact, an Integrated Nuclear Strategy and a laboratory-level Advanced Nuclear Science and Technology Initiative (ANSTI) are being developed to provide a roadmap that diagnoses the key issues and proposes a path forward. PNNL’s nuclear legacy is firmly rooted in the DOE Hanford site, the World War II Manhattan Project, and subsequent programs. Historically, PNNL was a laboratory where 70% of its activities were nuclear, and now 40% of its current business science and technology are nuclear- oriented. Programs in the areas of Nuclear Legacies, Global Security, Homeland Security and National Defense, Radiobiology and Nuclear Energy involve more than 900 of the 3,500 current laboratory staff, and these include more than 420 certified nuclear/radiological workers. This paper will present the current challenges faced by PNNL and an emerging three-fold strategy that has been proposed to solve the nuclear staffing issues. They are RECRUIT, RETRAIN and RETAIN. The strategy seeks to maintain and replenish the human nuclear capital needed to support core DOE missions.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 441 GRADUATE STUDIES IN RADIOCHEMISTRY AT COLORADO STATE UNIVERSITY. S.A. Ibrahim. Department of Environmental and Radiological Health Sciences, Colorado State University, Fort Collins, CO, 80523, USA The Department of Environmental and Radiological Health Sciences (ERHS) at Colorado State University (CSU) has recently established a specific area of specialization in radiochemistry within its existing graduate program. The program main objective is to increase the pool of appropriately educated and trained radiochemists in the USA. This undertaking is supported in part, through the sponsorship of the U.S. Department of Energy (DOE), Office of Nuclear Energy, Science and Technology, Radiochemistry Education Award Program, administered by South Carolina University Research and Education Foundation. The programs core curriculum is designed to provide in-depth integrated coverage of radiochemistry and related areas, linked with a summer internship at selected DOE-supported laboratories. The internship component is intended to provide students with hands-on experience with various laboratory activities and interaction with radiochemistry personnel. Laboratory facilities participating in the internship program include: the Carlsbad Environmental Monitoring & Research Center, The Savannah River Ecology Laboratory, Los Alamos National Laboratory and Argonne National Laboratory. Three (3) highly qualified students were recruited and admitted into the program with full financial support (stipends and tuition) for the current academic year 2002-03, and all are making good progress toward their M.S. degree. Program details are featured at the following web site: http://www.cvmbs.colostate.edu/erhs/academic_programs/graduate/radiochem/erhs_radiochem.htm . The ERHS department and CSU are committed to the success and long-term viability of this program and is providing all instructional facilities and equipment needed. 442 THE LIVING TEXTBOOK OF NUCLEAR CHEMISTRY. W. Loveland*, A. Gallant, and C. Joiner, Dept. of Chemistry, Oregon State University, Corvallis, OR 97331, USA. The Living Textbook of Nuclear Chemistry (http://livingtextbook.orst.edu) is a website, which is a collection of supplemental materials for the teaching of nuclear and radiochemistry. It contains audio-video presentations of the history of nuclear chemistry, tutorial lectures by recognized experts on advanced topics in nuclear and radiochemistry, links to data compilations, articles, and monographs, an audio course on radiochemistry, on-line editions of textbooks, training videos, etc. All content has been refereed. 443 AN ATTEMPT TO IDENTIFY SOURCE OF RAW MATERIALS OF ARCHAEOLOGICAL CERAMICS FROM THE CENTRAL AMAZON. C.S. Munita*1, E.G. Neves2, E. Soares3, J.B. Petersen4, R.P. Paiva1, C. Zoppe1, S. Schreiber1, P.M.S. Oliveira5 . 1Instituto de Pesquisas Energéticas e Nucleares – IPEN-CNEN/SP, C.P. 11049, 05422-970, São Paulo, SP, Brazil. 2Museu de Arqueologia e Etnologia – USP, Av. Prof. Almeida Prado, 1466, 05508-900, São Paulo, SP, Brazil. 3Departamento de Geociências, Universidade Federal do Amazonas, Campus Universitário, 69077-000, Manaus, AM, Brasil. 4Department of Anthropology, University of Vermont, Burlington VT, USA. 5Instituto de Matemática e Estatística – USP, C.P. 66281, 05315-970, São Paulo, SP, BRAZIL Studies on the provenance of archaeological artifacts and the sources of raw materials provide insight into the interpretation of archaeological data. It is assumed that the chemical composition of the fired ceramic is indicative of chemical composition of the principal material - clay. Such studies can lead to the formulation of appropriate criteria by which to classify ceramic artifacts within a specific regional perspective, but also can provide hard evidence for material and cultural exchange among different farther-flung populations in the past. Paste analyses provide important information about the organization of ceramic production and distribution, revealing the emergence and demise of source communities and the movement of their ceramic products. In this work 37 ceramic and clay samples from two archaeological sites, were analyzed. Arsenic, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, U, Yb and Zn by INAA, were determined. The geographical provenience of the clay samples was confined to a relatively small region, for

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI those samples were collected near the sites. Consequently the clays in the different sampling loci may not differ greatly in their composition and the method of analysis must be sensitive enough to cope with this problem. Values derived from concentrations data first were converted to base 10 log values and submitted to three multivariate statistical methods: cluster analysis, principal components analysis and canonical discriminant analysis including the calculation of Mahalanobis distance. Bivariate plots were employed to display the structure groups in a reduced dimensional space. . 444 THE IMPACT OF MEASUREMENT UNCERTAINTY ON THE PHYSICAL MEANING OF EPITHERMAL NEUTRON FLUX CHARACTERIZATION BY BARE MULTI-MONITOR METHOD. P. Bode*1, M. A. Bacchi2 ,E. A. De Nadai Fernandes2, M. J. J. Koster-Ammerlaan1. 1Interfaculty Reactor Institute, Delft University of Technology, THE NETHERLANDS. 2CENA, University of São Paulo, Piracicaba, BRAZIL. The ratio of the thermal and epithermal neutron flux, f, and the epithermal flux parameter, α, vary with space (i.e. position inside the irradiation container) and with time, elapsed after start-up of the reactor operation. Routine application of the bare multi-monitor method has given evidence that uncertainties in the physical parameters, in the monitor composition and in the measurement process itself can have a dramatic effect on f and α thus determined. Results have been observed which are highly questionable as a physical reflection of the actual shape of the neutron spectrum in the irradiation position. As such, this seems to violate the hitherto usurped statement that the physical process in activation analysis is fully understood, a cornerstone of having INAA accepted as method with high metrological value. This work demonstrates the impact of measurement uncertainty on the determination of the neutron flux parameters and its consequences to the selection of monitor elements. Results obtained for different sets of elements, irradiated at two light water research reactors, are presented and evaluated according to the uncertainty budget established for each measurement condition. 445 RADIOTRACER STUDY OF EUROPIUM INTERACTION WITH HUMIC ACID USING ELECTROPHORESIS, ULTRAFILTRATION, AND DIALYSIS. J. Mizera*1,2, G. Masnerová2, and P. Beneš2. 1 Nuclear Physics Institute, Academy of Sciences of the Czech Republic, CZ-250 68 Řež near Prague, Czech Republic2. Department of Nuclear Chemistry, Czech Technical University, Břehová 7, CZ115 19 Prague 1, CZECH REPUBLIC . Three independent speciation techniques – the free liquid / moving boundary electrophoresis, ultrafiltration, and equilibrium dialysis - combined with the radiotracer method (using 152Eu) have been compared at the study of Eu interaction with humic acid (HA). The degree of complexation of Eu in 10 mg/L Aldrich HA solutions was determined within a broad range of metal loading (Eu total concentration 10-8 – 10-4 mol L-1), at pH 4 and 6, ionic strength 0.01 and 0.1 (NaClO4). Uncertainty of the determination given by sorption losses of Eu on the walls and membranes of the experimental devices, and the effect of kinetic lability of the Eu-HA complexes are discussed. From the anodic electrophoretic mobilities determined, additional information on the charge of the Eu-HA complexes was obtained. The dependencies of the degree of complexation and the Eu-HA charge on Eu loading, pH and ionic strength have been interpreted with a simple model of HA as a mixture of two types of binding sites: less acidic - strongly binding - slowly dissociating, and more acidic - weakly binding - rapidly dissociating. 446 ACTINIDE/RADIOCHEMISTRY EDUCATION AT CLEMSON UNIVERSITY R.A. Fjeld, J. D. Navratil, and T.A. DeVol, Department of Environmental Engineering and Science, Clemson University, Clemson, SC 29634, USA

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI A graduate level program in actinide/radiochemistry was initiated in the Fall of 2000 at Clemson University with support from the Westinghouse Savannah River Company and the Department of Energy. The goals of the program are to prepare students for careers in actinide and radiochemistry and to conduct applied actinide and radiochemistry research with an emphasis on environmental and waste management related problems at Department of Energy facilities. During the past three years the basic infrastructure was developed. Specific accomplishments include the hiring of a new faculty member, the development an actinide chemistry course, the expansion of the environmental radiation laboratory, the establishment of an environmental radiochemistry focus area, the recruitment of graduate students, the initiation of a summer program for recruiting undergraduates into the field, the addition of new laboratory space, and the acquisition of equipment to support both the instructional and research programs. With the infrastructure now in place, the focus has turned to ensuring the long-term viability of the program by expanding the student base, especially at the PhD level, by continuing the very successful undergraduate student recruiting program, and by adding post-doctorates who can assist the faculty in expanding the research base. 447 MEASUREMENT OF RADIONUCLIDES USING ION CHROMATOGRAPHY AND ON-LINE RADIATION DETECTION. R. A. Fjeld1, T. A. DeVol1, and F. D. Leyba2. 1Department of Environmental Engineering and Science, Clemson University, Clemson, SC 29643 USA. 2Department of Chemistry, Newman University, Wichita, KS 67213, USA. A system has been developed for the measurement of transuranic and beta emitting radionuclides in waste streams and environmental samples. It uses ion chromatography for elemental selectivity and flow-through scintillation counting with dual parameter pulse height and pulse shape analysis for alpha/beta detection and discrimination. Relatively rapid analyses (less than four hours) of multiple alpha- and beta-emitting radionuclides are possible when the ion chromatograph is coupled to the on-line, flow-through detector. In this on-line mode, minimum detectable concentrations are on the order of 100 kBq/m3 (4000 pCi/L) for aqueous samples. If counting is done off-line, analysis times are longer (1 – 4 days), and minimum detectable concentrations decrease to typical environmental limits – on the order of 100 Bq/m3 (4 pCi/L) for aqueous samples and 100 Bq/kg (4 pCi/g) for solid samples. The system was successfully tested for surrogates (spiked groundwater from the southeastern U.S. and spiked basalt from the northwestern U.S.) and actual samples (supernatant from a high activity drain tank and sludge from a high level waste tank, both from the U. S. Department of Energy’s Savannah River Site). Based on these tests, it is concluded that the system is capable of analyzing alpha and beta emitters in samples that are representative of those encountered at contaminated former weapons sites. 448 NUCLEAR CHEMISTRY AND RADIOCHEMISTRY INSTRUCTION AT THE SAN JOSÉ STATE UNIVERSITY SUMMER SCHOOL. W. Frank Kinard, Department of Chemistry and Biochemistry, College of Charleston, Charleston, SC 29424-0001 and Herbert B. Silber, Department of Chemistry and Nuclear Science Facility, San José State University, San José, CA 95192-0101, USA The Summer School in Nuclear Chemistry and Radiochemistry has been operating continuously at San José State University since 1984. A history of the U.S. Department of Energy/American Chemical Society sponsored Nuclear Summer Schools from 1984 to 1996 has been published in the Journal of Radioanalytical and Nuclear Chemistry, 1997, 219, 231-236. This presentation will update the changes that have been made in the SJSU program since that time and outline some of the recent approaches to lecture and laboratory instruction. Particular emphasis will be given to the laboratory portion of the course where students receive instruction in the handling of radioactive materials, the use of a neutron source, separations chemistry, and various counting techniques. Additional information on the impact of the program will be presented through follow-up information on some of the graduates of the SJSU program. The Nuclear Summer School is supported by a grant from the Department of Energy via the American Chemical Society.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI 449 THE ACS/DOE SPONSORED NUCLEAR AND RADIOCHEMISTRY SUMMER SCHOOL AT BROOKHAVEN NATIONAL LABORATORY. K.L. Kolsky. Medical Department, Brookhaven National Laboratory, Upton, NY 11973, USA. The American Chemical Society/DOE Office of Science sponsors two Summer Schools in Nuclear and Radiochemistry, one at Brookhaven National Laboratory (http://www.bnl.gov/ncss), and one at San Jose University. As part of their fellowship awards, students at BNL receive 6 college credits, three each for a lecture course and a laboratory course, through the State University of New York at Stony Brook (SUNYSB). The lecture course is intended to be a survey course with major focus on nuclear mass and stability, nuclear structure and reactions and nuclear medicine applications. Visiting lecturers have come from various institutions in the US: universities (ex. MSU, Clark, SUNYSB, MIT) companies (AMETEK), and national laboratories (LANL). In 2002, students also traveled to the Environmental Measurements Laboratory in Manhattan for additional lectures. For FY 2003, a visit to the Millstone Reactor is planned. While at BNL, students tour various facilities/programs such as RHIC, PET facilities, and the NSLS. The laboratory program gives students hands on experience with  , and spectroscopy, neutron activation analysis, radiopharmaceutical chemistry, x-ray fluorescence studies, and radiochemistry. As part of the school, two all day symposiums are held, one focusing on Nuclear Medicine, and one focusing on Graduate Studies and Employment Opportunities. The success of this school regarding future employment of graduates in Nuclear Science will be discussed. 450 POSSIBILITIES OF THE SHORT-TERM THERMAL AND EPITHERMAL NEUTRON ACTIVATION FOR ANALYSIS OF MACROMYCETES (MUSHROOMS). Z. Řanda, L.Soukal, and J. Mizera*. Nuclear Physics Institute, Academy of Sciences of the Czech Republic, CZ-250 68 Řež near Prague, CZECH REPUBLIC. Fruit-bodies of wild-growing macromycetes (mushrooms) of various genera and species collected in localities with different geochemical features and man-made burden in the Czech Republic were analyzed using the short-term instrumental neutron activation, with both thermal and epithermal neutrons. Analytical possibilities of these methods were compared. Na, Mg, Al, Cl, K, Ca, V, Mn, Cu, and Br were determined regularly, whereas S, Ti, Ba, and Dy were determined occasionally with thermal neutron activation at irradiation-decay-counting times mode 1-10-10 min. Because of high content of K and P in the macromycete dry matter (2-7 % and 1-1.5 %, respectively) and also high Cl content in some genera (up to 2.5%), all “1/v” absorbers, epithermal neutron activation in Cd-box (1 mm thick wall) substantially suppresses their macroactivities and enhances sensitivity in determination of elements with significant resonance integrals. Cu, Se, Rb, Ag, Hf, and sometimes Ba are determinable in the mode 60-30-60 s, while K, Cu, As, Br, Rb, In, I, U (in some species also Co, Zn, Cs, Ba,and Hg) in the mode 1-13-13 min. However, Na, Mg, Al and Cl determination is not possible this way, as the (n,p) and (n,α) interfering reactions with fast neutrons and high K and P content make great interference contributions. Information about content of the essential and toxic elements in mushrooms is important in nutritional studies, because mushrooms form non-negligible part of diet in many countries. 451 SIMULTANEOUS DETERMINATION OF TRACE URANIUM AND VANADIUM IN BIOLOGICAL SAMPLES BY RADIOCHEMICAL NEUTRON ACTIVATION ANALYSIS, U.Repinc*, L.Benedik. Department of Environmental Sciences, Jožef Stefan Institute, Ljubljana-1000, SLOVENIA Accurate and reliable data on microgram and nanogram quantities of some essential and toxic elements in many environmental samples are still scarce. Radiochemical neutron activation analysis is an excellent method for determining uranium and vanadium; it offers unique possibilities for their trace analysis using selective radiochemical separation. Radiochemical neutron activation analysis for simultaneous determination of uranium and vanadium at trace levels in a single sample is described. This method is based on a short irradiation of up to 10 min.

METHODS AND APPLICATIONS OF RADIOANALYTICAL CHEMISTRY - MARC VI Immediately after irradiation the sample was rapidly wet ashed in a long-necked silica Kjeldahl flask over a gas flame by nitric and sulphuric acids and then with perchloric acid. According to the very short half-lives of the induced nuclides, it is necessary to complete the separation of vanadium (52V, t1/2 = 3.75 min) first and then uranium (239U, t1/2 = 23.5 min). The solution was transferred to a separatory funnel with 5 M nitric acid, and uranium extracted with TBP. Vanadium is not extracted by TBP and stays in the aqueous phase. The aqueous phase was run off into a second separatory funnel containing hydrochloric acid and potassium permanganate, and vanadium extracted into a toluene solution of BPHA reagent (N-benzoyl-N-phenyl hydroxylamine) which gives a violet chelate with vanadium(V) in strongly acidic medium. The chemical yield of the radiochemical procedure of each sample aliquot was determined with a re-irradiation procedure of the vanadium carrier. When the measurement of 52V is complete, the TBP phase containing the uranium fraction was cleaned up with 5 M nitric acid containing 0.2 % HF. The chemical yield was determined from gamma counting of the 185.7 keV peak of added 235U carrier. The method was tested by the analysis of reference materials and the results showed good agreement with the reference values. 452 A RADIOTRACER TECHNIQUE FOR THE MIGRATION OF INORGANIC CONTAMINANTS INTO DRY FOOD FROM PACKAGING MADE FROM RECYCLED PAPER AND BOARD. D J S Aston & S J Parry, Department of Environmental Science & Technology, Imperial College of Science, Technology & Medicine, London, UK Recycling of wastepaper is believed to increase the concentrations of metals in recycled paper. Therefore it is important to carry out research on whether migration occurs from this recycled paper product into foodstuffs that it is in contact with. It is necessary to ascertain whether migration occurs into all or only certain types of dry food, which elements migrate and to what extent. A study was carried out for the UK Food Standards Agency to investigate whether there is migration into these foodstuffs and at levels that could pose a risk to human health. A radiotracer method was developed to assess the measurement of inorganic contaminants migrating into real food. This radiotracer method has been applied to the study of 10 samples of recycled paper and board. The only elements detected in the migration study were Zn and Fe, at concentrations close to the detection limit. The values represented no hazard and were insignificant compared to the recommended daily allowance. Shaking the samples did not result in any significant migration. In just one case contamination from Zn was close to the detection limit and represented 0.1% migration (0.001 mg/dm2). When ‘Tenax’ was tested as a food simulant no Zn was detected (