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Instrumental neutron activation analysis may need to correct for matrix interferences caused by fast neutron induced threshold reactions. The very low Al mass fraction in bovine liver Standard Reference Material (SRM) has eluded certification due to such complications. Cold neutron beam irradiation absent fast neutrons provides a possible alternative, which has been applied for the first time to determine Al in bovine liver SRM 1577c. The Al mass fraction was determined to be (0.80 ± 0.15) mg/kg using the traditional single peak-fitting method, and (0.78 ± 0.23) mg/kg using a new physics model-based spectral fitting method.

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

A comprehensive approach to the analysis of human livers has been developed in a pilot program for a National Environmental Specimen Bank (NESB). Since 1980, the pilot NESB program has examined the collection, processing, storage and analysis of human livers. Sampling protocols, handling procedures and analytical methods have been developed and implemented considering the requirements for valid analytical results. Sampling and handling included the use of clean room technology, specific clean implements and packing materials made from titanium and Teflon and flash-freezing and preservation at liquid nitrogen temperature. Neutron activation analysis played a major role in the implemented analytical scheme. The scheme combined up to four analytical techniques to determine the distribution of 29 trace elements in 66 human livers.

Analytical techniques in the sucroenergetic sector can now for the first time be supported by an innovative matrix-matching reference material produced from sugarcane leaves. This will further enhance the validity of the measurement results and contribute significantly to the quality assurance of plant nutrition analysis. The candidate reference material obtained had a low residual moisture and appropriate particle size. Neutron activation analysis was used to determine the mass fraction of Al, Br, Ca, Cl, Ce, Co, Cs, Cu, Fe, Hf, K, La, Mg, Mn, Mo, Na, P, Rb, Sb, Sc, Sm, Sr, Th, V and Zn, and the Kjeldahl method for N. Statistical techniques were applied to evaluate minimum sample mass and within-bottle homogeneity (ANOVA, Tukey test and PCA) and between-bottles homogeneity (ANOVA). It is demonstrated in this paper that the material is homogeneous using 50 mg mass sample for most chemical elements. However, sample masses of 200 mg or greater are required for Co, Na, Sb and V.

The National Institute of Standards and Technology is developing a kelp powder standard reference material (SRM) in support of dietary supplement measurements. Edible seaweeds such as kelp and laver consumed as diet or dietary supplement contain tens of mg/kg arsenic. The speciation information of arsenic in the seaweed should be provided because the total arsenic alone does not fully address the safety issue of the dietary supplement as the value assignment is originally intended. The inability to avail all arsenic species for value assignment measurements prevented the certification of arsenic species in the candidate SRM; however, approximately 70 % of total arsenic extracted with a 1:1 volume fraction of methanol:water mixture allowed arsenic speciation values to be assigned to a procedure-defined extract, which may be used for method validation in research to improve upon current extraction and measurement practices. Arsenic species in kelp and laver were identified using electrospray ionization ion trap time of flight mass spectrometry (ESI-IT-TOF). Arsenosugars As(328), As(482), and As(392) were found in the kelp candidate SRM while As(328) and As(482) were found in GBW 08521, a certified reference material (CRM) of laver produced by the National Institute of Metrology of China (NIM). A discovery that the digests of kelp and laver contained only dimethylarsinic acid led to the conclusion that the seaweeds did not contain detectible levels of arsenobetaine, arsenocholine or trimethylarsine oxide that could overlap with the peaks of arsenosugars in the separation. The mean ± s of (5.68 ± 0.28) mg/kg and (13.43 ± 0.31) mg/kg found for As(482) and As(392) in kelp, respectively, using instrumental neutron activation analysis (INAA) demonstrated that value assignment measurement of arsenosugars was possible without arsenosugar calibration standards.

A new γγ coincidence system has been set up at NIST. It is operated with a digital data finder supported by new software developed at NIST. The system is used to explore possible enhancements in instrumental neutron activation analysis (INAA) and study applicability to neutron capture prompt gamma activation analysis (PGAA). The performance of the system is tested with certified reference materials for efficiency calibration and quantitative performance. Comparisons of INAA results based on conventional gamma-ray spectrometry data with INAA results based on coincidence data obtained from the same samples show improvements in the counting uncertainties and demonstrates the quantitative accuracy of the new system.

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

A material containing single-wall carbon nanotubes (SWCNTs) with other carbon species, catalyst residues, and trace element contaminants has been prepared by the National Institute of Standards and Technology for characterization and distribution as Standard Reference Material SRM 2483 Carbon Nanotube Soot. Neutron activation analysis (NAA) and inductively coupled plasma mass spectrometry (ICP-MS) were selected to characterize the elemental composition. Catalyst residues at percentage mass fraction level were determined with independent NAA procedures and a number of trace elements, including selected rare earth elements, were determined with NAA and ICP-MS procedures. The results of the investigated materials agreed well among the NAA and ICP-MS procedures and good agreement of measured values with certified values was found in selected SRMs included in the analyses. Based on this work mass fraction values for catalyst and trace elements were assigned to the candidate SRM.

The method of gammagamma coincidence counting has been applied to the determination of Cu via the (64)Cu annihilation gamma rays. Preliminary experiments show that at least an order of magnitude reduction in (24)Na interference may be obtained by employing the 511-511 keV coincidence peak rather than the singles 511-keV peak. The effect of the sample matrix on the yield of (24)Na pair-production events was investigated by a combination of experimental measurements and Monte Carlo calculations.

A combination of instrumental neutron activation analysis (INAA) and prompt gamma-ray activation analysis (PGAA) was used to value assign 35 elements in SRM soil 2709a (San Joaquin Soil). INAA with counting of short-lived radioisotopes was used for determination of Al, Au, Ca, Dy, K, Mg, Mn, Na, Ti, and V. Elements determined by INAA with counting of intermediate and long-lived radioisotopes included As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hf, La, Lu, Nd, Rb, Sb, Sc, Sm, Sr, Ta, Tb, Yb, Zn, and Zr. Thermal neutron PGAA was used for the determination of H, B, Si, K, Ti, Mn, Fe, Cd and Gd. Expanded uncertainties were determined for all values reported.

Instrumental neutron activation analysis as carried out at the National Institute of Standards and Technology (NIST) is inadequate for determining Al, Ni, and V at the levels found in the newly prepared Standard Reference Material® (SRM) 1577c Bovine Liver. To overcome shortcomings in the value assignment, the authors initiated a cooperative approach using NAA with previously established chemical separation procedures and with significantly different neutron energy spectra to determine Al and V with pre-irradiation separation of the elements at NIST, and V and Ni with post-irradiation separation at the Nuclear Physics Institute Řež. The determinations were confirmed with the analyses of several SRMs. The work supported the certification of mass fraction values for V and Ni in SRM 1577c.

Cold neutron prompt gamma activation analysis (PGAA) was used to determine the mass of hydrogen in Mg hydride thin films with varying hydrogenation times. The results suggest that hydrogenation of the Mg thin films remains unsaturated even after 48 h of treatment, contrary to the indications of inferential hydrogen measurement methods. To demonstrate PGAA as an effective combinatorial methodology for hydride thin films, a continuously varying composition gradient of thin MgyTi(1−y) hydride film with y ranging from 0.65 to 0.94 was prepared and analyzed by both PGAA and instrumental neutron activation analysis (INAA). The variation in the molar ratio of Mg, Ti, and H was obtained for nine 5 mm wide segments of the film.

Analyses for value assignment in the renewal Standard Reference Materials® SRM 1598a Animal Serum and SRM 1577c Bovine Liver included extensive characterization by neutron activation analysis (NAA). Conventional instrumental NAA procedures were complemented by pre-irradiation chemical separations for the determination of Al, V, Mn, and Cu, radiochemical separations for the determination of Ag, As, Cd, Cr, Cu, Mo, Sb, and Se, and the use of (anti-) coincidence gamma-ray spectrometry systems for the instrumental determination of Ag, Cr, and Hg. The previous materials, SRMs 1598, 1577, and 1577b, were analyzed together with the new materials for quality control.

The National Institute of Standards and Technology (NIST) is preparing a freeze-dried powdered bovine liver tissue Standard Reference Material (SRM) to replace SRM 1577b Bovine Liver as the stock of this material was exhausted during 2006. Like the original SRM 1577 issued in 1972, this renewal focuses on the key elements for diagnostic, nutritional, and toxicological measurements that are important to medical, veterinary, and environmental sciences investigations. NIST’s approach for value assignment included extensive characterization by neutron activation analysis (NAA). Difficulties in the determination of some elements present at very low levels were overcome by use of radiochemical separations. Twentyone elements were characterized in SRM 1577c by NAA. The previous materials, SRM 1577 and 1577b, served as quality control.

For accurate activation analysis, it is necessary to understand the neutron and gamma-ray environment experienced by a sample during irradiation. A new irradiation position was recently installed in the RT2 thimble of the NIST reactor. Modeling by MCNP was used to select the radial location in the reflector thimble and the size of the D2O shielding tank. After installation, the new rabbit was characterized for thermal, epithermal, and fast fluence rates, spectral parameters f and α, temporal stability, axial and radial flux gradients, and temperature.

Neutron-activation analysis (NAA) is an important technique for the accurate and precise determination of trace and ultra-trace elemental compositions. The application of γ γ coincidence counting to NAA in order to enhance specificity was first explored over 40 years ago but has not evolved into a regularly used technique. A γ γ coincidence spectrometer has been constructed at the National Institute of Standards and Technology, using two HPGe γ -ray detectors and an all-digital data-acquisition system, for the purpose of exploring coincidence NAA and its value in characterizing reference materials. This paper describes the initial evaluation of the quantitative precision of coincidence counting versus singles spectrometry, based upon a sample of neutron-irradiated bovine liver material.

Zeolites have important industrial applications including use as catalysts, molecular sieves and ion exchange materials. In this study, three zeolite materials have been characterized by the National Institute of Standards and Technology (NIST) as reference materials (RMs): zeolite Y (RM 8850), zeolite A (RM 8851) and ZSM-5 zeolite (RM 8852). They have been characterized by a variety of chemical and physical measurement methods: X-ray fluorescence (XRF), gravimetry, instrumental neutron activation analysis (INAA), nuclear magnetic resonance (NMR), calorimetry, synchrotron X-ray diffraction, neutron diffraction, laser light extinction, laser light scattering, electric sensing zone, X-ray sedimentation, scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM) and optical microscopy. The chemical homogeneity of the materials has been characterized. Reference values are given for the major components (major elements, loss on ignition [LOI] and loss on fusion [LOF]), trace elements and Si/Al and Na/Al ratios. Information values are given for enthalpies of formation, unit cell parameters, particle size distributions, refractive indices and variation of mass with variation in relative humidity (RH). Comparisons are made to literature unit cell parameters. The RMs are expected to provide a basis for intercomparison studies of these zeolite materials.

The determination of arsenic at natural levels in biological materials remains difficult. Many analytical techniques cannot detect the low levels present in typical biological tissues and other techniques suffer from interferences. This paper reviews uses of neutron activation analysis (NAA) at NIST to determine nanogram amounts of arsenic in biological reference materials with radiochemical (RNAA) or instrumental (INAA) procedures. INAA is compromised by high activities from 24Na, 82Br, and 32P that may be formed during irradiation of biological tissues, and result in detection limits as high as 0.1 mg. Lower detection limits have been achieved using state-of-the-art gamma-ray spectrometry systems in INAA and a variety of procedures in RNAA. These techniques and procedures were applied recently at NIST to the determination of arsenic in urine, nutritional supplements, and total diet samples.

Multi-element simultaneous electrothermal atomic absorption spectrometry (ETAAS) methods were developed for determining 11 elements, in three analytical groups (group-1, predominately crustal elements, Al, Cu, Fe, Mn, and Cr; group-2, tracers of coal and oil combustion as well as other anthropogenic sources, Se, As, Pb, and Ni; and group-3, tracers of municipal incinerator aerosol–Zn and Cd), in aqueous slurry of ambient fine airborne particles, collected, at 30 min intervals with the University of Maryland–Semicontinuous Elements in Aerosol Sampler-II (SEAS-II). Combined effects of acid (0.2% v/v nitric acid) and ultrasonic treatment (15 min) improved metals recovery and slurry stability. Linear calibration ranges were improved by using a 50 mL min−1 carrier gas flow (mini-flow) during the atomization stage. However, analytical sensitivity for group-1 and 3 elements was compromised. Palladium (4 μg) and hydrogen (5% in Argon) were found to be effective modifiers for group-1 and 2 elements. A fast furnace temperature program was developed for group-3. Detection limits for the eleven marker elements by the SEAS-II-ETAA approach were compared with traditional filter X-ray fluorescence, laser ablation-ICPMS, and instrumental neutron activation analysis (INAA) techniques used in air quality studies. The efficacy of the analytical method was evaluated by analyzing interim urban PM2.5 reference material, collected in Baltimore, by the National Institute of Standards and Technology (NIST) Gaithersburg, MD. Results obtained by the ETAAS methods agreed well with the results obtained by NIST using INAA.

A new radiochemical neutron activation analysis (RNAA) method has been developed for low-level determination of Si in biological materials, which is based on the 30Si(n,γ)31Si nuclear reaction with thermal neutrons. The radiochemical separation consists of an alkaline-oxidative decomposition followed by distillation of SiF4. Nuclear interferences, namely that of the 31P(n,p)31Si with fast neutrons, have been examined and found negligible only when irradiation is carried out in an extremely well-thermalized neutron spectrum, such as available at the NIST reactor. The RNAA procedure yields excellent radiochemical purity of the separated fractions, which allows the measurement of the β--activity of the 31Si by liquid scintillation counting. Results for several reference materials, namely Bowen’s Kale, Bovine Liver (NIST SRM 1577b), Non-Fat Milk Powder (NIST SRM 1549) and several intercomparison samples, Pork Liver-1, Pork Liver-2 and Cellulose Avicel, are presented and compared with literature values.

This work provides a systematic experimental approach to the demonstration of viability of instrumental neutron activation analysis (INAA) in chemical metrology. The practical approach was derived from a complete survey of uncertainty components that affect the INAA measurement process. These uncertainty components were classified by their magnitude and origin and subsequently minimized by appropriate steps in the INAA process. The process was tested with the INAA determination of Cr in SRM 1152A stainless steel; the Cr value is certified at 17.76% with an estimated uncertainty of 0.04% (0.23% relative). The INAA results from this procedure are in agreement with these specifications. Similar procedures have been applied to INAA multi-element determinations in a high temperature alloy. Agreement with available consensus values was demonstrated in the alloy. The guidelines on the determination of uncertainty were fully met, providing through INAA a valuable independent non-destructive tool in chemical measurements of metrological value such as required in the CCQM key comparisons.

NIST maintains a portfolio of more than 1300 standard reference materials (SRM), more than a third of these relating to measurements in the biological and environmental fields. As part of the continuous renewal and replacement efforts, a set of new marine sediments has been recently developed covering organic and inorganic determinations. This paper describes the steps taken in sample preparation, homogeneity assay, and analytical characterization and certification with specific emphasis on SRM 2702 inorganics in marine sediment. Neutron activation analysis showed the SRM to be highly homogeneous, opening the possibility for use with solid sampling techniques. The certificate provides certified mass fraction values for 25 elements, reference values for eight elements, and information values for 11 elements, covering most of the priority pollutants with small uncertainties of only several percent relative. The values were obtained by combining results from different laboratories and techniques using a Bayesian statistical model. An intercomparison carried out in field laboratories with the material before certification illustrates a high commutability of this SRM.

The optimization of neutron activation analysis with regard to detection limit and uncertainty of measurement using physical and chemical means is reviewed. Using selected examples it is demonstrated that radiochemical separation is the most effective means of optimization, especially in neutron activation analysis, because it yields the lowest detection limits and uncertainties.

A fast (14-MeV) neutron activation analysis procedure was employed to directly measure mass fractions of oxygen in coal samples. The procedure demonstrated sufficient precision and accuracy to determine a relative change of about 5% or more, in the oxygen mass fraction of about 12%. The procedure was applied to test samples of the newly developed SRM 1632c Trace Elements in Coal (Bituminous). The samples had been stored at three conditions: in liquid nitrogen vapor and at room temperature in the original containers packaged under argon, and for accelerated aging at 50 °C open to air. Following six months storage increments, duplicate samples of each of twelve bottles of the SRM were measured for each storage condition. In addition each sample was processed through ten separate analytical runs yielding a total of some 720 measurements per storage duration. Oxygen was determined by comparison to a primary standard potassium dichromate and the accuracy of the method was assessed through the analysis of replicate samples of three reference materials that are certified for oxygen content. The initial 6-months test period indicated uptake of oxygen in the open-air storage.

Instrumental neutron activation analysis (INAA) procedures were optimized for the analysis of small (1 mg) solid samples. This process included sample handling as well as detailed evaluation of high rate counting techniques, also in conjunction with rapidly decaying sources, to establish the necessary analysis environment for the determination of large numbers of samples with high reproducibility. The investigated materials included biological materials such as peach leaves (SRM 1547), lichen, and bovine liver, as well as environmental materials such as urban particulate matter (SRM 1648), and deep ocean sediment. The analytical data obtained with the INAA procedures were used to determine homogeneity values.

A contemporary PM2.5 (particulate matter smaller than 2.5 microns aerodynamic diameter) aerosol material from an urban site has been collected for the production of a new standard reference material that will be made available for the development of new PM2.5 air quality standards. Air particulate matter corresponding to the PM2.5 fraction was collected at an established Environmental Protection Agency monitoring site in Baltimore, Maryland. The air-sampling system that has been constructed for this collection separates fine particles with a cyclone separator and deposits them onto an array of Teflon membrane filters. The fine air particulate material is removed by ultrasonication or by mechanical means and collected for further preparation of standards. The composition of the collected PM2.5 aerosol, as well as the composition of the deposited PM2.5 aerosol, are determined by instrumental nuclear activation analysis and other techniques.

Arsenic (As) is widely found in marine organisms, mainly as organic arsenical compounds. With the introduction of regulations for As species in foodstuffs and for environmental control, it has become more important to quantify the amount of arsenic species present. To address this concern new reference materials (RMs) for validation and quality assurance of As speciation measurements are being developed, including a tuna fish tissue and a robalo liver tissue. Instrumental neutron activation analysis (INAA) is used in this work as a proven analytical tool for As determinations and for validating the As mass fraction determined by liquid chromatography coupled to inductively coupled mass spectrometry (LC–ICP-MS) in extracts of the candidate RMs and other fish samples including certified RMs. Various methods for the extraction of water-soluble As species were evaluated. The best results were acquired after methanol/acetone/water extraction yielding in 93 % extractable As in the tuna RM. This procedure was used for the LC–ICP-MS studies. The results demonstrate that INAA can account for 100 % of the distribution of As species in analytical processes. It complements LC–ICP-MS for the validation of the characterization of As species in the development of RMs for such species. Excellent agreement of measured results in certified RMs with the reported values confirms the validity of the applied procedures.

The most important fraction of aerosols with respect to human health is the respirable fraction, which has particles less than 10 μm in equivalent aerodynamic diameter (EAD), the so called PM 10 fraction. The collection of these respirable particles and the determination of their trace element composition is the focus of an IAEA Co-ordinated Research Programme (CRP). The IAEA Laboratory participated in this Programme and established collection sites for the air particulate samples on the grounds of the Atominstitute of the Austrian Universities in Vienna and the IAEA Laboratories, Seibersdorf, representing an urban residential site and a rural site. The collected samples as well as samples of simulated air filters (used also for blind controls) and control materials were analyzed sequentially and/or in sections by X-ray fluorescence (XRF), proton induced X-ray emission (PIXE), instrumental neutron activation analysis (INAA), and atomic absorption spectrometry (AAS). Results demonstrate the applicability of the PM-10 sampling approach, provided PIXE and/or INAA are used in the determinations. Reliable results can be obtained that will lead in comparable air pollution data for many regions in the world through CRP.

Microbeam X-ray spectrometry, energy-dispersive X-ray fluorescence analysis, and neutron activation analysis were evaluated for the detection of selenium contained in the selenoprotein glutathione peroxidase. The glutathione peroxidase had been previously separated using polyacrylamide gel electrophoresis. The use of Bragg-reflected polarized X-ray beams was employed in the X-ray fluorescence measurements to minimize the problem of scatter owing to the gel matrix. Current detection limits of selenium in a gel matrix are 2.1 ng in the bench-top microbeam X-ray system and 30–60 ng using XRF with polarized beams. Neutron activation analysis was used for qualitycontrol measurements, with a detection limit here of

A source of error in the gamma-spectrometric registration of the analytical signal in neutron activation analysis is its dependency on the overall count rate. Losses in the accuracy of quantitation occur due to hardware and software. This paper presents examples for solutions to these problems and demonstrates that accurate NAA can be accomplished under high-rate counting conditions with commercially available technology.

A new mussel tissue Standard Reference Material (SRM) has been prepared and analyzed for trace organic and inorganic constituents. SRM 1974 (Organics in Mussel Tissue (Mytilus edulis)) is a frozen mussel tissue homogenate that has been certified for the concentrations of nine polycyclic aromatic hydrocarbons (PAHs) from results obtained from gas chromatography-mass spectrometry and reversed-phase liquid chromatography with fluorescence detection. Noncertified concentrations for 19 additional PAHs are also reported. Gas chromatography with electron capture detection and gas chromatography with mass spectrometric detection were used to provide noncertified concentrations for 13 polychlorinated biphenyl congeners and 9 chlorinated pesticides. In addition to the organic contaminants, noncertified concentrations for 36 trace elements were determined primarily by instrumental neutron activation analysis. SRM 1974 is the first frozen tissue SRM for environmental measurements of organic and inorganic constituents.

A preirradiation separation procedure has been developed to separate Al, Cu, Mn, and V from biological materials. Chelex-100 resin is used as the separation medium, and the resin is irradiated directly. Three NIST biological Standard Reference Materials and five samples of human blood serum, obtained under carefully controlled conditions, have been analyzed by NAA following this separation.

A new marine sediment Standard Reference Material (SRM) has been prepared and analyzed for the determination of trace organic constituents. SRM 1941, Organics in Marine Sediment, has been certified for concentrations of 11 PAHs using results obtained from gas chromatography (GC) with flame ionization detection, gas chromatography-mass spectrometry, and liquid chromatography with fluorescence detection. Non-certified values for 24 additional PAHs are also reported. GC with electron capture detection was used to provide non-certified concentrations for 15 PCB congeners and 7 chlorinated pesticides. In addition to the organic contaminants, concentrations of 32 major and trace elements were determined using neutron activation analysis, and the sulfur content was also determined using isotope dilution thermal ionization mass spectrometry.

Instrumental neutron activation analysis (INAA) has been employed in the investigation of mass balance for mercury species analysis in the analytical process. A new human hair reference material (IAEA-085) was analyzed for methylmercury using a solid/liquid extraction procedure, with samples of extracts, residues, and untreated samples being analyzed by INAA. The certified reference material NIES CRM No. 13, human hair, was analyzed in parallel. From the results obtained through the mass balance studies, it was found that the extraction procedure was quantitatively complete, and that there was no difference between the mass balance of Hg and the total Hg in the untreated materials.

Neutron activation analysis (NAA) is an appropriate tool for the determination of trace elements in biological systems. The virtually blank-free NAA procedures fittingly complement precautions employed in sampling and sample preparation of biological matrices. Results from instrumental NAA procedures used to establish baseline values and time trends for elements in human tissues demonstrate the advantages as well as the limits of these procedures for nanomole and, in a considerable number of instances, subnanomole elemental levels. In addition, subnanomole mass fractions have been determined with extremely low limits of detection by employing NAA with radiochemical separations isolating very low levels of radioactivity from the matrix background. The elements reviewed in this article include Cr, Se, Pt, and others that have been determined by NAA at subnanomole levels in human tissues and body fluids and in biological macromolecules.

A working analytical procedure for selenium determinations by INAA, using gamma spectrometry with a germanium well-type detector, is presented. The spectral line at 400.7 keV is employed, enhanced with the effect of energy summing in true coincidence of cascade photons. The main advantage of the method is high efficiency and reliable, interference-free results; potential drawbacks are increases in input count rate and pile-up losses, decrease in resolution, and sensitivity to errors in sample-to-detector geometry. The procedure is applied to certification analysis of reference materials, large-area biomonitoring by oak leave samples, and determination of separated proteins.

Nuclear analytical techniques have an important role in the IAEA in life sciences programs relating to human health. A major effort has recently been devoted to the determination of dietary intakes of trace elements, including studies in some countries affected by the Chernobyl accident. The same accident stimulated interest in using 129I (as determined by NAA and other techniques) to trace the distribution of fission products in the environment. Other research topics concern solid wastes, air pollution, exposure to mercury in selected human populations, and osteoporosis (including NAA studies of trace elements in human bone). Much of the IAEA's work is concerned with analytical quality control; new reference materials in preparation include lichen (for trace elements) and human hair (for total and methyl mercury).

Analyses of selected tissues from the Alaska Marine Mammal Tissue Archival Project (AMMTAP) have provided comprehensive information related to levels of 36 trace elements and methyl-mercury in marine mammal tissues. Liver, kidney and muscle tissues from two northern fur seals, four ringed seals and six belukha whales were analyzed. The bulk of the investigated tissues and additional tissues from a total of 65 marine mammals are banked in the AMMTAP. The results are compared to literature values for trace element concentrations in marine mammal tissues and their relevance to environmental studies is discussed.

The National Biomonitoring Specimen Bank at the National Institute of Standards and Technology applies a variety of techniques for extensive characterization of banked samples. To determine a large number of trace elements in small samples at low levels, instrumental neutron activation analysis has been combined with voltammetry. The two methods produce high quality data for thirty pollutant and biological trace elements. Results on archived specimens of human livers and intercomparisons of the two methods are reported.

Several nuclear analytical methods have been applied to determine elemental concentrations in samples from the National Biomonitoring Specimen Bank. Various combinations of neutron activation analysis (NAA), prompt gamma activation analysis (PGAA), and X-ray fluorescence (XRF) used to obtain information on the inorganic constituents in four types of samples, human livers, marine bivalves, fish livers, and sediments, are described. Concentrations of at least 20–30 elements from a small test portion (~ 1 g wet weight) can be obtained by combining these methods. The dynamic ranges, sensitivities and multielement capabilities of the described methods are shown to provide the high quality data needed in a banking program.

The National Institute of Standards and Technology has developed a new Standard Reference Material 1941, "Organics in Marine Sediment." In addition to the organic constituents, over 30 elements have been determined by instrumental neutron activation analysis and prompt-gamma activation analysis. The homogeneity of the material was investigated and relative standard deviations of single-element concentrations in 250-mg samples were found to be 1% or less with regard to major inorganic constituents and rare earth elements. A slightly higher relative SD was found for elements that may stem from biological or anthropogenic input. The element concentrations determined in this work are discussed in comparison to concentrations in other similar reference materials. Concentrations for 31 elements will be included for information on the certificate.

A combination of two methods, polyacrylamide gel electrophoresis (PAGE) and neutron activation analysis (NAA), has been applied to solutions containing phosphoproteins for the purpose of protein quantification. The proteins were separated by molecular weight using PAGE, and then the whole gel was activated by neutron bombardment. Densitometric measurements of the developed bands from 32P, taken from autoradiographs of the activated gels, resulted in quantification of the phosphorus, and then the related protein. This PAGE/NAA method was applied to several phosphoprotein- containing materials, including commercial milk products and reference materials, i.e., IAEA A-11, milk powder, and SRM 1845, Cholesterol in Egg Powder.

A project to establish an archive of Alaskan marine mammal tissues was conceived in 1987 to be a part of the National Biomonitoring Specimen Bank (NBSB). Protocols and field collection of marine mammals, long-term storage, and analysis are summarized in this paper. Instrumental neutron activation analysis has been used for an initial evaluation of trace element content in samples of northern fur seal (Callorhinus ursinus) from the Pribilof Islands. The findings agree with previously observed trace element levels in northern fur seals. The archived specimens can be used in future studies when comparison of past and present pollution levels are needed.

The National Institute of Standards and Technology has developed a new Standard Reference Material 1941, “Organics in Marine Sediment.” In addition to the organic constituents, over 30 elements have been determined by instrumental neutron activation analysis and prompt-gamma activation analysis. The homogeneity of the material was investigated and relative standard deviations of single- element concentrations in 250-mg samples were found to be 1% or less with regard to major inorganic constituents and rare earth elements. A slightly higher relative SD was found for elements that may stem from biological or anthropogenic input. The element concentrations determined in this work are discussed in comparison to concentrations in other similar reference materials. Concentrations for 31 elements will be included for information on the certificate.

A straightforward method for demonstrating the powerful background reduction of Compton suppression spectrometers for neutron activation purposes is presented. The shorter acquisition time needed in Anti-Compton mode (A/C on) for peaks of appropriate counting statistics, compared to normal gamma counting (A/C off), allows a much higher sample throughput, thus compensating for the higher cost of the instrument. Two examples of artificial mixtures of radio- nuclides demonstrate the drastic time saving for measurement of monoenergetic decaying isotopes. The comparison of results from three different instruments proves the general usefulness of Compton suppression spectrometers for Neutron Activation Analysis of biological samples.

A neutron activation analysis scheme based upon a radiochemical separation of the activation products has been developed. The method utilizes the inherent sensitivity of the activation reaction198Pt(n, γ)199Pt and counting of the daughter nuclide199Au. This nuclide is radiochemically separated from interfering activities by homogeneous precipitation as elemental gold. The remaining interference of the secondary reaction197Au(n,γ)198 Au(n,γ)199Au from gold in the samples is quantitatively assessed and corrected. During this process accurate gold concentrations in the samples are obtained at ultratrace levels. The analysis scheme is applied to gold and platinum determinations in biological Standard Reference Materials and human liver specimens. Gold and platinum are determined at concentrations of 5·10−11 g/g, and at higher levels.

The US National Institute of Standards and Technology is currently in the process of certifying a Bovine Serum Standard Reference Material. In addition to elements normally considered to be of clinical interest, a number of other elements, which are analytically more difficult to determine yet are of importance from either a nutritional or toxicological viewpoint, are being determined by a variety of analytical techniques. Neutron activation analysis in combination with appropriate pre- or post-irradiation chemical separations, has been used to determine many of these difficult elements.

A comprehensive approach to the analysis of human livers was developed in a pilot program for the National Environmental Specimen Bank that employed a combination of four analytical techniques. Refinements in this approach were needed for improvement in detection limits, more effective sample usage and to reduce the number of analytical steps that were involved. Since neutron activation analysis (NAA) had determined most of the elements, expansion of NAA was chosen to achieve these goals. Modifications in the instrumental NAA procedures, including the use of a Compton Suppressor System, gave increased sensitivity for some low level elements, such as arsenic and chromium. Radiochemical procedures that followed the instrumental counts increased the sensitivity for the elements chromium, selenium, arsenic, molybdenum, silver, antimony, and tin. Results are given for two radiochemical procedures that were applied following the modified procedure, either the use of an inorganic ion exchange column or a liquid/liquid extraction, and these are compared to instrumental results.

Using 201 foods from the United States Food and Drug Administration's Total Diet Study (FDA TDS), a mixed diet composite (USDIET-I) was prepared to represent the intake of 25-30-year-old males in the United States. Proximate analyses, phytate determination, and assays for nutrient elements and selected toxic elements, as well as organic nutrients were carried out on this composite. As part of a quality control exercise for a coordinated research program, atomic absorption spectrophotometry, inductively coupled atomic emission spectrometry, colorimetry and neutron activation analysis were used to determine up to 30 elements in this diet material. A comparison of the daily intakes of As, Ca, Cd, Cu, Fe, Hg, K, Mg, Mn, Na, P, Se and Zn from the composite USDIET-I shows excellent to good agreement with FDA TDS values calculated from results of single food analyses. These USDIET-I results demonstrate the feasibility of the mixed diet concept as a viable approach for a reliable assessment of daily intakes, especially for a number of elements such as Cd, Cr, Hg and Mo that occur at low concentrations in individual food products. Simultaneously, stability of some organic nutrients during storage was also investigated. Initial findings suggest that this program may also be useful in the development of reference materials for organic nutrients, for which there is a great need. These aspects are discussed.

Lyophilized and radiation sterilized biological certified reference materials (CRMs) are believed to be stable in their chemical composition. Generally, the certifying agencies consider the certificates of these biological CRMs valid for a 5-year shelf life, i.e., apart from measurable moisture content, the chemical composition should not change during that time. The long-term behavior of fresh frozen material is not known. In this study the elemental compositions of the Bovine Liver Standard Reference Material (SRM 1577) and human liver tissue samples are evaluated over a time period of more than 7 years. The concentrations of selected elements were determined by neutron activation analysis at various times. The initial evaluation of zinc, selenium and arsenic results gives no indication of changes during 7 years storage of fresh frozen tissues, however, a trend towards lower arsenic concentrations has been observed in SRM 1577 during a 10-year period.