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For more than 50 years, nuclear methods have been applied to chemical analysis at the National Institute of Standards and Technology. Radiochemical, instrumental, and prompt-gamma activation analysis are used, as well as neutron depth profiling and other techniques. The history of this group in methods development and the certification of Standard Reference Materials, among other applications, is reviewed.

Prompt gamma neutron activation analysis has become an important part of the analytical toolkit, practiced at several research reactors worldwide. An extensive review of the physics, engineering, and applications of the technique was published in 2004: the present work gives an overview and survey of the literature in the succeeding dozen years.

The recent expansion of the National Institute of Standards and Technology (NIST) Center for Neutron Research facility has offered a rare opportunity to perform an accurate measurement of the cold neutron spectrum at the exit of a newly-installed neutron guide. Using a combination of a neutron time-of-flight measurement, a gold foil activation measurement, and Monte Carlo simulation of the neutron guide transmission, we obtain the most reliable experimental characterization of the Advanced Liquid Hydrogen Cold Neutron Source brightness to date. Time-of-flight measurements were performed at three distinct fuel burnup intervals, including one immediately following reactor startup. Prior to the latter measurement, the hydrogen was maintained in a liquefied state for an extended period in an attempt to observe an initial radiation-induced increase of the ortho (o)-hydrogen fraction. Since para (p)-hydrogen has a small scattering cross-section for neutron energies below 15 meV (neutron wavelengths greater than about 2.3 A), changes in the o- p hydrogen ratio and in the void distribution in the boiling hydrogen influence the spectral distribution. The nature of such changes is simulated with a continuous-energy, Monte Carlo radiation-transport code using 20 K o and p hydrogen scattering kernels and an estimated hydrogen density distribution derived from an analysis of localized heat loads. A comparison of the transport calculations with the mean brightness function resulting from the three measurements suggests an overall o- p ratio of about 17.5(±1) % o- 82.5% p for neutron energies

A permanent, full-time instrument for prompt-gamma activation analysis is nearing completion as part of the Cold Neutron Research Facility (CNRF). The design of the analytical system has been optimized for high gamma detection efficiency and low background, particularly for hydrogen. Because of the purity of the neutron beam, shielding requirements are modest and the scatter-capture background is low. As a result of a compact sample-detector geometry, the sensitivity (counting rate per gram of analyte) is a factor of four better than the existing Maryland-NIST thermal-neutron instrument at this reactor. Hydrogen backgrounds of a few micrograms have already been achieved, which promises to be of value in numerous applications where quantitative nondestructive analysis of small quantities of hydrogen in materials is necessary.

A new instrument for cold neutron prompt gamma-ray activation analysis is being designed as part of the recent expansion of the cold neutron guide hall at the NIST Center for Neutron Research. This instrument has a 10-fold increase in neutron flux and lower gamma-ray and neutron background compared to the PGAA instrument it will replace at NG7. Monte Carlo based simulation sofware and experimental setups are used in the design phase to mitigate background while preserving high neutron fluence. The new instrument will also provide more space for samples and for experimental setup compared to the old facility.

It has been difficult to characterize the thermal to epithermal neutron flux ratio (f) and the measure of the nonideal epithermal neutron flux distribution (α) for the RT-2 pneumatic rabbit facility at the NIST National Bureau of Standards Reactor (NBSR). In a previous paper, only cadmium-covered irradiations yielded physically reasonable parameters. New measurements were performed using chromium, manganese, cobalt, zinc, zirconium, molybdenum, antimony, gadolinium, lutetium, and gold. The neutron temperature (T n ) in RT-2 measured using bare lutetium and gold foils gave unphysical values. The bare foil methods for measuring f and α gave inconsistent results. The underlying reasons are demonstrated via MCNP simulation results for cumulative reaction rates of selected isotopes. To determine expected intervals for f, α and T, parametric methods were explored. Measured reaction rate probability per target atom (R p ) values for the listed elements were fitted to a modified Westcott curve using an iterative least-squares method to verify consistency of measurements and nuclear data. An advanced parametric approach using a detailed MCNP model of the NBSR was used to calculate neutron flux characterization parameters.

In an attempt to improve the accuracy of neutron activation analysis, gamma-ray spectrometry and least-squares methods developed for other nuclides have been applied to redetermine the decay constants of 90mY and 97Ru. Several irradiated samples of each pure element were counted continually through several half-lives, acquiring up to 100 spectra with good statistics. Photopeaks from each nuclide were evaluated with a region of interest integration routine, and each data point corrected for rate-related losses before fitting to an exponential function by a nonlinear least-squares procedure. The half-lives found are 3.204 ± 0.008 h for 90mY and 2.836 ± 0.014 days for 97Ru, where the uncertainty is an estimate of the 95 % confidence level. Although (by Chi squared criteria) the fits to the decay curves were very good and the uncertainty of the resulting half-lives an order of magnitude smaller than the previously published uncertainty, care is necessary before assigning a best value with a totally defensible uncertainty to the overall data set.

An automated delayed-neutron activation analysis system has been installed at the NIST research reactor. This work involved characterization of the transfer time of the system, evaluation of blanks, and tests of the system’s analytical capabilities through quantitative analysis for uranium in several natural matrix standard reference materials (SRMs). The calibration curve was shown to be linear up to at least 20 μg of uranium, and the well-thermalized reactor irradiation position makes the system insensitive to thorium and oxygen. For SRMs 1646a Estuarine Sediment and 2710a Montana Soil the values determined for this work agree with the reference and certified values, respectively. The mass fraction of uranium in SRM 695 Multi-Nutrient Fertilizer is the first reported for this material. For this system and the irradiation, transfer, and counting times used, the limit of detection for natural uranium is 20 ng, which corresponds to approximately 200 pg of 235U.

For the ultimate sensitivity in trace radiochemical analysis, the radiation detector must have high efficiency and low background. A low-background gamma-ray spectrometer in regular use at NIST for over twenty years is being supplemented by a new system, improved in several ways. The new detector is much larger, a shield of iron reduces cosmic neutron background compared with lead, large plastic scintillators reduce the muon continuum background, and a digital data acquisition system gives new opportunities for optimization.

Nearly fifty years ago, two landmark papers appeared that should have cured the problem of ambiguous uncertainty statements in published data. Eisenhart’s paper in Science called for statistically meaningful numbers, and Currie’s Analytical Chemistry paper revealed the wide range in common definitions of detection limit. Confusion and worse can result when uncertainties are misinterpreted or ignored. The recent stories of cold fusion, variable radioactive decay, and piezonuclear reactions provide cautionary examples in which prior probability has been neglected. We show examples from our laboratory and others to illustrate the fact that uncertainty depends on both statistical and scientific judgment.

A nondestructive analytical method based on autoradiography and gamma spectrometry was developed to perform activity distribution analysis for particulate samples. This was applied to aerosols collected in Fukushima Japan, 40 km north of the Daiichi nuclear power plant for a 6 week period beginning shortly after the March 2011 tsunami. For an activity distribution of 990 “hot particles” from a small filter area, the hottest particle was nearly one Bq 137+134Cs but most of the activity in the filter was produced by particles having

A series of three hydrogen in titanium alloy Standard Reference Materials (SRMs 2452, 2453, and 2454) was prepared with hydrogen mass fractions bracketing the hydrogen specification limit of 125 mg/kg. Commercial titanium alloy Ti6Al4V (6 pct aluminum and 4 pct vanadium) was heated under vacuum in a furnace to remove native hydrogen, then it was doped with a measured quantity of hydrogen. Prompt gamma-ray activation analysis was used to determine hydrogen in the degassed material and finished SRMs. A combination of preparation data and PGAA measurement was used to certify the hydrogen mass fraction of each. The certified hydrogen mass fractions are 62.5 mg/kg ± 1.6 mg/kg for SRM 2452, 114 mg/kg ± 5 mg/kg for SRM 2453, and 211 mg/kg ± 4 mg/kg for SRM 2454.

Standard Reference Material (SRM) 1849 Infant/Adult Nutritional Formula has been issued by the National Institute of Standards and Technology (NIST) as a replacement for SRM 1846 Infant Formula, issued in 1996. Extraction characteristics of SRM 1846 have changed over time, as have NIST's analytical capabilities. While certified mass fraction values were provided for five constituents in SRM 1846 (four vitamins plus iodine), certified mass fraction values for 43 constituents are provided in SRM 1849 (fatty acids, elements, and vitamins) and reference mass fraction values are provided for an additional 43 constituents including amino acids and nucleotides, making it the most extensively characterized food-matrix SRM available from NIST.

Analytical chemists are scientific scavengers, using any available physical phenomenon to determine the composition of materials. Accuracy, unlike mere reproducibility, depends on understanding the measurement process, most usefully by stressing it until it bends. The use of neutron capture gamma rays for analysis involves some issues not encountered in conventional neutron activation analysis which, when understood, extend the utility and reinforce the value of nuclear methods of elemental analysis. These methods are being increasingly recognized as tools for SI-traceable metrology.

A new instrument for cold neutron prompt gamma-ray activation analysis (CNPGAA) is being designed and constructed at the NIST Center for Neutron Research (NCNR). The new instrument is expected to have lower gamma-ray and neutron background and better detection limits for most elements than the current cold neutron PGAA instrument. Other advantages over the current facility will include the ability to analyze larger samples and greater overall measurement capability due to the addition of scanning stages, cryostats, and sample changers.

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.

The basic assumptions of activation analysis are that the induced radioactivity is proportional to the amount of analyte, and that the quantity of radioactivity can be related simply to the number of counts observed. Quantitative measurement of activity (and of its uncertainty) is not always simple, especially when accuracy better than a few percent is sought. Recent work with 77Ge and 76As has demonstrated that the accuracy of half-lives in the literature is sometimes insufficient. Despite these and other problems, quantitative understanding and documentation of uncertainties can be accomplished, providing demonstrable quality assurance and supporting claims of traceability to the Systeme International.

An international round-robin study was undertaken under the auspices of ISO TC201/SC6 to determine the best analytical conditions and the level of interlaboratory agreement for the determination of the implantation dose of arsenic in silicon by secondary ion mass spectrometry (SIMS). Fifteen SIMS laboratories, as well as two laboratories that performed low energy electron-induced X-ray emission spectrometry (LEXES) and one that made measurements by instrumental neutron activation analysis (INAA) were asked to determine the implanted arsenic doses in three unknown samples using as a comparator NIST Standard Reference Material® 2134. The use of a common reference material by all laboratories resulted in better interlaboratory agreement than was seen in a previous round-robin that lacked a common comparator. The relative standard deviation among laboratories was less than 4% for the medium-dose sample, but several percent larger for the low- and high-dose samples. The high-dose sample showed a significant difference between point-by-point and average matrix normalization because the matrix signal decreased in the vicinity of the implant peak, as observed in a previous study. The dose from point-by-point normalization was in close agreement with that determined by INAA. No clear difference in measurement repeatability was seen when comparing Si2− and Si3− as matrix references with AsSi−.

Two prompt gamma-ray activation analysis (PGAA) facilities at the NIST Center for Neutron Research have been used routinely to perform elemental analyses of a variety of materials. Results from these analyses are usually expressed as mass fraction values with expanded uncertainties. The expanded uncertainty consists of the combined uncertainty multiplied by the appropriate coverage factor (k) required to achieve a 95% confidence interval. The combined uncertainty includes the uncertainties associated with preparation, irradiation, and γ-ray spectrometry of samples and standards, and corrections for γ-rays from the background or blanks where necessary. To determine the combined uncertainty, each component of uncertainty associated with each variable and constant in the basic measurement equation is evaluated. In this paper we present the PGAA measurement equation, a description of the potential sources of uncertainty for each component of the equation, and three examples of uncertainty evaluation. The examples are for determination of H in standard reference material (SRM) 2454, hydrogen in titanium alloy using the cold neutron PGAA facility, Cd in SRM 2702 Inorganics in Marine Sediment using the original thermal neutron PGAA facility, and N in SRM 3244 Ephedra-Containing Protein Powder using the recently designed thermal neutron PGAA facility.

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.

As a contribution toward improving the accuracy of neutron activation analysis, the half-life of 111mPd was measured by gamma-ray spectrometry. The uncertainty of this parameter is greater than desired for accurate work, largely because 111mPd represents a small part of the total activity of palladium exposed to neutrons. In this work, several irradiated samples of pure palladium were counted continually with high-resolution Ge gamma detectors through about ten half-lives. The 172 keV photopeak was integrated with a region-of-interest procedure, and each datum corrected for rate-related losses before fitting to an exponential function by a nonlinear least-squares procedure. The half-life found is 5.580 ± 0.032 h, where the uncertainty is an estimate of the 95 % confidence level, a substantial improvement over published values.

A new thermal neutron prompt γ-ray activation analysis (PGAA) instrument was designed and built to replace the original PGAA system at the NIST Center for Neutron Research. By placing a sapphire filter in the neutron beam shutter assembly, the fast neutron fluence rate was reduced by a factor of 5 and low-energy (50–200 keV) γ-ray intensities were reduced by factors of 5–10. The thermal neutron fluence rate was reduced by only a factor of 1.13. A new external beam tube, sample chamber, beam stop, and support structure were built and a new detection system installed. The new beam tube is made of two cylindrical aluminum sections lined with a lithiated polymer. Both sections are kept under vacuum to reduce the number of neutrons scattered by air into the beam tube walls. The sample chamber is also fabricated from aluminum and lined with lithiated polymer, and may be evacuated to minimize the number of neutrons scattered and absorbed by air. The beam tube and sample chamber assembly is suspended from the aluminum support structure. The detection system consists of a 40% efficient (relative) germanium detector (resolution 2.0 at 1332.5 keV) and a bismuth germanate Compton suppressor. The detection system is shielded by lead, surrounded by borated and lithiated polyethylene, and placed on a table attached to the support structure. The new, more compact beam stop is welded to the support structure. Capture γ-ray photopeaks from H, B, C, N, Na, Al, Fe, Ge, I and Pb in the background spectrum were either of lower intensity or eliminated with the new PGAA instrument. The more efficient detection system, positioned closer to the sample, yielded element sensitivity increases of 5–50%. Limits of detection have been greatly reduced compared with those of the original instrument due to reduced Compton and scattered γ-ray backgrounds (especially in the low-energy region), increased sensitivities, and reduction of background γ-ray photopeak intensities.

This study was undertaken to compare endogenous lithium concentrations in human blood and its components from normal donors versus bipolar patients. The patients were not on lithium therapy at the time that the blood samples were donated and had not received any lithium therapy for at least 2 yr. Blood components were separated by centrifugation. The analytical method for lithium as developed in this laboratory consists of thermal-neutron activation of freeze-dried samples. 3H is produced via the reaction 6Li + n = 3H + 4He, and high-sensitivity rare gas mass spectrometry is used to measure 3He formed from beta-decay of 3H. Boron measurements are made concurrently using 4He from the reaction 10B + n = 4He + 7Li. Seven normal donors and seven patients with a diagnosis of bipolar disorder participated in this study. Measurements of lithium and boron were made in whole blood, plasma, and red cells. Red cell-plasma ratios R(Li) and R(B) were calculated after corrections were made for trapped plasma in the red cells. The results show that bipolar patients may have higher concentrations of lithium in blood, plasma, and red cells (p = 0.08, 0.02, and 0.02, respectively) and may have higher R(Li) values than normal donors (p = 0.01). No evidence was found for bipolar-normal differences in these four parameters for boron. Although our sample size is admittedly very small, the results clearly show that the endogenous red cell ratio R(Li) and plasma or red cell lithium concentrations may become useful diagnostic indicators for bipolar illness if the analytical methods are further developed.

We report further measurements of lithium and boron bound to human plasma proteins using the techniques of gel chromatography, thermal-neutron activation, and high-sensitivity helium isotope mass spectrometry. The plasma sample was donated by a bipolar patient who had never been on lithium therapy. The plasma lithium-binding pattern for the bipolar patient is distinctly different from that previously observed in this laboratory for plasma donated by a normal individual. In the bipolar case, virtually all of the lithium is bound to low-molecular-weight proteins (approx 1000 amu), whereas in the normal case, most of the lithium eluted from the gel column was bound to five high-molecular-weight proteins (approx 50,000 amu to approx 1,000,000 amu). The gel elution profiles for boron were roughly similar for the normal and bipolar cases. The lithium results are in agreement with our previous speculation that lithium-binding plasma proteins are missing or exist in very low concentrations in some individuals suffering from affective disorders.

Prompt-gamma activation analysis (PGAA) differs from conventional neutron activation analysis in the set of elements measured, the irradiation conditions, and the nature of the gamma-ray spectra. Each of these affects the conduct of the measurements and interpretation of the data. In its recent development, the k0 standardization framework provides a solution to many of the problems of this analytical method, and may provide a bridge to greater certainty of analysis.

137Cesium and other contaminants have leaked from single-shell storage tanks (SSTs) into coarse-textured, relatively unweathered unconsolidated sediments. Contaminated sediments were retrieved from beneath a leaky SST to investigate the distribution of adsorbed 137Cs+ across different sediment size fractions. All fractions contained mica (biotite, muscovite, vermiculatized biotite), quartz, and plagioclase along with smectite and kaolinite in the clay-size fraction. A phosphor-plate autoradiograph method was used to identify particular sediment particles responsible for retaining 137Cs+. The Cs-bearing particles were found to be individual mica flakes or agglomerated smectite, mica, quartz, and plagioclase. Of these, only the micaceous component was capable of sorbing Cs+ strongly. Sorbed 137Cs+ could not be significantly removed from sediments by leaching with dithionite citrate buffer or KOH, but a fraction of the sorbed 137Cs+ (5-22%) was desorbable with solutions containing an excess of Rb+. The small amount of 137Cs+ that might be mobilized by migrating fluids in the future would likely sorb to nearby micaceous clasts in downgradient sediments.

We have been exploring ways to evaluate the activity of radioactive particles that have been detected by phosphor plate digital autoradiography based on photostimulated luminescence (PSL). A PSL system with 25 μm pixel digitization has been applied to particle analysis problems, both qualitatively and quantitatively. Two data evaluation methods are currently employed: (1) bulk area signal measurement, and (2) discrete event counting which may include spectral evaluation. The first method is conventional, whereas the second method requires high spatial resolution and is presented here for the first time. The counting methods can discriminate between alpha and background counts. The unshielded background signal accumulation rate was determined by the bulk area method. Using the spectral method of evaluation for α-particle events, the mean signal intensity per recorded α-particle was measured, and the detective quantum efficiency (DQE) was found to be nominally 100%. We present a comparison to gamma-spectrometry for sub-Bq 137Cs activities, and demonstrate an application for the qualitative assay of International Atomic Energy Agency swipe samples collected from uranium enrichment facilities.

Prompt gamma-ray activation analysis (PGAA) is an important nuclear analytical technique that complements conventional neutron activation analysis (NAA). When a target is placed in a beam of neutrons, gamma-rays emitted upon neutron capture are measured by a shielded germanium detector, yielding quantitative elemental analysis. The radiation is penetrating and the analysis both nondestructive and independent of the chemical form of the element(s) being measured. The technique is most useful for measurement of light elements (H, B, C, N, Si, P, S, Cl) which can not be easily measured by other methods. Best sensitivity is achieved with neutron beams from research reactors. Although sample preparation is minimal, care must be taken to select proper standards and blanks, and numerous corrections must sometimes be applied to the data from the complex spectra. PGAA has proven useful for multielement analysis of a wide variety of different materials spanning a broad range of scientific disciplines. Of particular importance has been the measurement of hydrogen in materials.

Standard reference material (SRM) 2134 Arsenic Implant in Silicon was produced at the National Institute of Standards and Technology (NIST) as a calibrant for secondary ion mass spectrometry. Instrumental neutron activation analysis was used as a primary method for certification of the arsenic implanted dose. A complete evaluation of all sources of uncertainty yielded an expanded relative uncertainty for the mean value of this SRM to be 0.38% at approximately the 95% level of confidence. No evidence indicating significant heterogeneity among samples was observed.

A simple and accurate method is presented to evaluate the burnup effects involved in the neutron activation of 197Au prior to any neutron flux characterisation, based on the spectrometry of the 198Au and 199Au decay gammas. The obtained burnup factor can be used as input for reactor neutron field characterisation techniques using 197Au(n,γ)198Au as a monitor. This way an iterative procedure is avoided.

Recent advances in instrumentation provide the capability to measure size, count rate, type of radiation, and the chemical composition of radioactive particles. We present a demonstration of these capabilities, using a laser-scanned phosphor imaging system and a charge injection device system for digital autoradiography, light and electron microscopy, energy dispersive X-ray spectrometry, and conventional radionuclide spectrometry. Response characteristics of the phosphor system that support these efforts are presented.

Applying thek 0 standardization method to prompt-gamma activation analysis (PGAA) offers similar benefits as in instrumental neutron activation analysis. It has been demonstrated that under constant flux conditionsk 0-factors obtained by normalizing to a titanium comparator, measured separately, yield consistent analytical sensitivity ratios. The ratio method has been generalized by using stoichiometric compounds for the determination ofk 0-factors. Since chlorine forms compounds with essentially everyelement and it also serves as a detector efficiency standard,k 0 values have been determined relative to chlorine as an internal standard for several analytically important elements in two reactor facilities: the thermal guided beam at the BRR in Budapest and the cold-neutron beams at the NBSR at NIST.

In the past decade, the combination of readily accessible, reliable data in electronic form with well-tested spreadsheet programs has changed the approach to experiment planning and computation of results. This has led to a flowering of software applications based on spreadsheets, mostly written by scientists, not by professional programmers trained in numerical methods. Formal quality systems increasingly call for verified computational methods and reference data as part of the analytical process, a demand that is difficult to meet with most spreadsheets. Examples are given of utilities used in our laboratory, with suggestions for verification and quality maintenance.

Commercially available pulse generators for use in γ-ray spectroscopy to correct for dead-time and pile-up losses share the problem that the fall-time of the output pulses does not match the fall-time of the detector pulse. Upon pulse shaping in the main amplifier the pulser's signals result in a considerable undershoot of the amplifier's output signal, which cannot be restored by theP/Z network. As a result, peaks in the γ-ray spectrum are broadened. Moreover, amplitude stability of the generators is often poorer than the overall gain stability of the spectrometer. To overcome these problems a special pulse generator has been developed at the Interfaculty Reactor Institute, which simulates Ge-detector signals. It generates pulses with a constant frequency of 25 Hz using a crystal oscillator controlled mercury relay. The stability of the generator's amplitude and frequency is extremely high and the peak-shapes in the γ-ray spectrum are not distorted.

The cold neutron capture prompt γ-ray activation analysis (CNPGAA) spectrometer located in the Cold Neutron Research Facility (CNRF) at NIST has proven useful for the analysis of hydrogen and other elements in a wide variety of materials. Modifications of the instrument and the CNRF have resulted in improved measurement capabilities for PGAA. The addition of an atmosphere-controlled sample chamber and Compton suppression have reduced γ-ray background and increased signal-to-noise ratio. More recent revisions are expected to yield still further improvement in analytical capabilities. Replacement of the D2O ice cold source with a liquid H2 moderator is expected to yield a 5–10 fold increase in neutron capture rate, and improved neutron and γ-ray shielding will result in further reduction of the background. Other modifications to the instrument allow easier sample mounting and more precise positioning of samples in the neutron beam. Significant improvements in detection limits and analytical accuracy are expected.

Apparatus is being developed for short irradiation and rapid counting at the NIST Reactor, optimized for accurate neutron activation analysis via activation products ranging in half-life from about 500 ms to 500 s. This facility is designed to irradiate a sample either in a well-thermalized neutron flux at 3·1013 n·cm−2·s−1, or in a higher flux with a larger fast and epithermal component. The design transfer time for a 1-ml rabbit is 500 ms, measured to 10 ms precision. Timing information for both irradiation and counting will be transferred automatically to the activation analysis workstation computer. The γ-ray spectrometer system is selected and tuned for accurate measurement at high and varying counting rates, using loss-free counting (LFC) technology. A detailed calibration and characterization of this system has been performed. Accurate measurement requires that attention be paid to the systematic and random errors to which LFC is subject, but this requirement is minor compared to the advantages of undistorted spectral shape, the ability to solve the decay equations exactly, and the wider useful range of counting rates in the spectrometer system.

A neutron lens has been constructed to focus cold neutrons from the exit of a58Ni neutron guide, which delivers a beam to the Prompt-Gamma Activation Analysis (PGAA) station at the NIST Cold Neutron Research Facility. The lens compresses a neutron beam of cross section 50 mm× 45 mm onto a focal spot of diameter 0.53 mm (fwhm) wich an average gain of 80 in neutron current density. PGAA measurements have been performed to demonstrate the enhanced sensitivity and detection limits for various elements and the spatial resolution in one transverse dimension. For the two test particles (a gadolinium glass bead and cadmium metal of sizes less than 0.5 mm), the gain in the γ-count rate with the lens is a factor of 60, and the detection limit is improved by a factor of 20. The system can be used for two-dimensional mapping of samples on a sub-millimeter scale to complement other analytical techniques such as neutron depth profiling (NDP).

Radiochemical neutron activation analysis has proven to be a powerful tool for measuring trace mercury in a variety of materials. In a modification of an established NIST method, selenium interfering with the 203Hg indicator is removed by precipitating mercury as periodate, and the chemical yield is measured gravimetrically. The current method is better suited to multiple samples, less subject to explosion during the combustion step, provides a measurement of the yield for each sample, and involves less radiation exposure to personnel. The procedure has been applied to the certification of mercury in SRMs 1575a Pine Needles, 1632c Bituminous Coal, and 2702 Marine Sediment.

Methods developed to redetermine the 76As half-life were applied to four additional radionuclides. Several gamma-spectrometers were used to follow the decay of pure sources during 4-14 half-lives, comparing with a pulser stable to better than 2 . 10-8 per day. Complementary measurements (also for 76As) employed a pressurized ion chamber. Several least-squares methods were used to derive the best value of each decay constant. We find the half-lives to be 14.959±0.009 hours for 24Na, 12.339±0.011 hours for 42K, and 2.6924±0.0011 days for 198Au, where the uncertainties are the combined standard uncertainty u.

Cold neutron prompt gamma-ray activation analysis (CNPGAA) has proven useful for the analysis of hydrogen in titanium alloys. The analysis is nondestructive, measures the entire sample, and the results are independent of the chemical form of hydrogen present. We have used the technique to measure H mass fractions as low as 50 mg/kg in titanium-alloy jet-engine compressor blades and to measure hydrogen in standards for neutron tomography.

At the National Institute of Standards and Technology, there are two techniques for chemical analysis that use neutron beams from the reactor for target irradiation: neutron depth profiling (NDP) and prompt γ-ray activation analysis (PGAA). There are two facilities for each technique, one equipped with a thermal neutron beam and the other, with a cold neutron beam. In addition, focused beams of cold neutrons will be used to measure the two-dimensional element distributions by PGAA and three-dimensional distributions by NDP. This paper includes a brief description of the facilities, the measurement capabilities of each, some recent applications of NDP and PGAA, and neutron focusing as applied to these techniques.

Determination of53Mn in meteorites by neutron activation analysis requires a thermal neutron flux high enough to ensure adequate production of54Mn from53Mn with a sufficiently low fast neutron component to minimize its production through fast neutron reactions. Thermal and fast neutron fluxes were mapped as a function of sample position within the NIST research reactor in order to determine the optimum position for irradiation of53Mn.

A focusing neutron lens using glass polycapillary fibers has been introduced successfully into a prompt gamma activation analysis (PGAA) instrument placed at the exit of a cold neutron guide. The neutron current density gain of the lens is 80, averaged over the focused beam size of 0.53 mm diameter. PGAA measurements have been made on submillimeter particles of gadolinium and cadmium. The results indicate that elemental sensitivities of measurements are increased by ∼ 60, and that particles of sizes smaller than 0.5 mm can be discerned using the focusing lens. The measured gain in prompt gamma signals for these particles is less than anticipated, probably due to alignment difficulties. Gamma ray background associated with the lens is discussed and improvements are suggested.

In the course of making high-accuracy measurements of arsenic, we found that the most recently published and compiled half-life of 76As did not agree with our data as well as the earlier accepted value. To redetermine this parameter, 76As sources were measured on four Ge gamma detector systems, and an exponential function was fitted to the decay data by two different nonlinear least-squares methods. We obtained T1/2 = 1.09379 days with a standard uncertainty of 0.00045 days. This result is 1.5% higher than the most recent value, but is in agreement with the older, less precise, consensus value.

Two computer programs in use for over a decade in the Nuclear Methods Group at NIST illustrate the utility of standard software: programs widely available and widely used, in which (ideally) welltested public algorithms produce results that are well understood, and thereby capable of comparison, within the community of users.Sum interactively computes the position, net area, and uncertainty of the area of spectral peaks, and can give better results than automatic peak search programs when peaks are very small, very large, or unusually shaped.Mean combines unequal measurements of a single quantity, tests for consistency, and obtains the weighted mean and six measures of its uncertainty.