Neutron activation analysis of concrete for cross-border nuclear security

The dissolution of the Soviet Union coupled with the growing sophistication of international terror organizations has brought about a desire to ensure that a sound infrastructure exists to interdict smuggled nuclear material prior to leaving its country of origin. To combat the threat of nuclear trafficking, radiation portal monitors (RPMs) are deployed around the world to intercept illicit material while in transit by passively detecting gamma and neutron radiation. Portal monitors in some locations have reported abnormally high background counts. The higher background data has been attributed, in part, to the naturally occurring radioactive materials (NORM) in the concrete surrounding the portal monitors. Higher background increases the minimum detectable activity (MDA) and can ultimately lead to more material passing through the RPMs undetected. This work employed two different neutron activation analysis (NAA) methods for the purpose of developing a process to characterize the concrete surrounding the RPMs. Thermal neutron instrumental NAA (INAA) and fast NAA (FNAA) were conducted on six samples from three different composition concrete slabs. Comparator standards and quality control materials were used to help ensure that the methods were both precise and accurate. The combination of INAA and FNAA accounted for 84–100% of the total elemental composition of the samples. Knowing the composition of the concrete will allow RPM customers to choose suitable materials prior to installation, thereby increasing the ability of the monitors to detect radiological and nuclear materials.     

Time series evaluation of radiation portal monitor data for point source discrimination

Time series of data from radiation portal monitors are evaluated for radioactive sources by comparing background to vehicle spectra over time with a “spectral-distance” metric, isolating the contribution of anomalous radiation. This may diminish systematic fluctuations from vehicular background attenuation and allow time-shape filtering for discriminating compact sources. To examine this, a wavelet function similar in size to the expected source profile filters the spectral-distance output. Spectra from chosen isotopes are injected into data from a U.S. port of entry. The resulting data are analyzed with gross-counting, spectral-distance, and spatial algorithms. Combined spectral/spatial filtering is shown to enhance sensitivity and discrimination of compact versus distributed sources.     

Design,construction, and use of a shipping case for radioactive sources used in the calibration of portal monitors in the radiation portal monitoring project

The Pacific Northwest National Laboratory is working with US Customs and Border Protection to assist in the installation of radiation portal monitors. Our challenge was to provide radioactive sources—both gamma and neutron emitting, to a number of ports of entry where radiation portal monitors are being installed and calibrated. A portable shipping case has been designed such that it meets the DOT requirements for a “limited quantity” shipment. Over three hundred shipments, both domestic and international, were made in FY2008 using this type of shipping case.     

Empirical correction of crosstalk in a low-background germanium γ–γ analysis system

The Pacific Northwest National Laboratory (PNNL) is currently developing a custom software suite capable of automating many of the tasks required to accurately analyze coincident signals within gamma spectrometer arrays. During the course of this work, significant crosstalk was identified in the energy determination for spectra collected with a new low-background intrinsic germanium (HPGe) array at PNNL. The HPGe array is designed for high detection efficiency, ultra-low-background performance, and sensitive γ–γ coincidence detection. The first half of the array, a single cryostat containing seven HPGe crystals, was recently installed into a new shallow underground laboratory facility. This update will present a brief review of the germanium array, describe the observed crosstalk, and present a straight-forward empirical correction that significantly reduces the impact of this crosstalk on the spectroscopic performance of the system.     

Simultaneous separation of simulated radionuclides strontium and neodymium using in situ hydrotalcite synthesis

Aerosol collections were initiated at several locations by Pacific Northwest National Laboratory (PNNL) shortly after the Great East Japan earthquake of May 2011. Aerosol samples were transferred to laboratory high-resolution gamma spectrometers for analysis. Similar to treaty monitoring stations operating across the Northern hemisphere, iodine and other isotopes which could be volatilized at high temperature were detected. Though these locations are not far apart, they have significant variations with respect to water, mountain-range placement, and local topography. Variation in computed source terms will be shown to bound the variability of this approach to source estimation.     

Voltammetric measurement of arsenic in natural waters

There are several U.S. EPA approved methodologies for the determination of arsenic in ground water. Such technologies are lab-based, time intensive and can lead to a large capital cost for multi-sample analysis. In light of the number of sites found to contain arsenic at levels higher than the maximum contaminant level (MCL), on-site screening and monitoring systems are an attractive alternative. This review article summarizes several examples in the recent literature to illustrate the breadth of work in voltammetric analysis of arsenic in environmental samples. Also, included are recent voltammetric results, obtained with a microfabricated gold array and a field portable potentiostat, at an arsenic contaminated site in southern New Jersey.     

Radiochemistry at the University of Missouri-Columbia: A joint venture with chemistry,nuclear engineering,molecular biology,biochemistry, and the Missouri University Research Reactor (MURR)

Summary The United States, the Department of Energy (DOE) and its National Laboratories, including the Pacific Northwest National Laboratory (PNNL), are facing a serious attrition of nuclear scientists and engineers and their capabilities through the effects of aging staff. Within the DOE laboratories, 75% of nuclear personnel will be eligible to retire by 2010. It is expected that there will be a significant loss of senior nuclear science and technology staff at PNNL within five years. 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/radiological, and now just under 50% of its current business science and technology are nuclear and radiologically oriented. Programs in the areas of nuclear legacies, global security, nonproliferation, homeland security and national defense, radiobiology and nuclear energy still involve more than 1,000 of the 3,800 current laboratory staff, and these include more than 420 staff who are certified as nuclear/radiological scientists and engineers. This paper presents the current challenges faced by PNNL that require an emerging strategy to solve the nuclear staffing issues through the maintenance and replenishment of the human nuclear capital needed to support PNNL nuclear science and technology programs.     

Source injection distribution functions for alarm algorithm testing

Developing and testing improved alarm algorithms is a priority of the Radiation Portal Monitor Project (RPMP) at PNNL. Improved algorithms may reduce the potential impediments that radiation screening presents to the flow of commerce, without affecting the detection sensitivity to sources of interest. However, assessing alarm-algorithm performance involves calculation of both detection probabilities and false alarm rates. For statistical confidence, this requires a large amount of data from drive-through (or “dynamic”) scenarios both with, and without, sources of interest, but this is usually not feasible. Instead, an “injection-study” procedure is used to approximate the profiles of drive-through commercial data with sources of interest present. This procedure adds net-counts from a pre-defined set of simulated sources to raw, gross-count drive-through data randomly selected from archived RPM data. The accuracy of the procedure — particularly the spatial distribution of the injected counts — has not been fully examined. This report describes the use of previously constructed and validated MCNP computer models for assessing the current injection-study procedure. In particular, this report focuses on the functions used to distribute the injected counts throughout the raw drive-through spatial profiles, and for suggesting a new class of injection spatial distributions that more closely resemble actual cargo scenarios.     

The use of energy information in plastic scintillator material

Plastic scintillator material is often used for gamma-ray detection in many applications due to its relatively good sensitivity and cost-effectiveness compared to other detection materials. However, due to the dominant Compton scattering interaction mechanism, full energy peaks are not observed in plastic scintillator spectra and isotopic identification is impossible. Typically plastic scintillator detectors are solely gross count detectors. In some safeguards and security applications, such as radiation portal monitors for vehicle screening, naturally-occurring radioactive material (NORM) often triggers radiation alarms and results in innocent or nuisance alarms. The limited energy information from plastic scintillator material can be used to discriminate the NORM from targeted materials and reduce the nuisance alarm rate. An overview of the utilization of the energy information from plastic scintillator material will be presented, with emphasis on the detection capabilities and potential limitations for safeguards and security applications.     

The use of a robust resistant regression method for personal monitor validation with decay of trapped materials during storage

The stability of trapped materials stored in thermally desorbable monitors is not essential. When monitors are stored in defined conditions and the decay is well characterized, a decay curve and a corresponding correction curve with 95% confidence envelopes can be established. Even if “wild” or outlier data are present, the robust and resistant regression methods described and illustrated enable reasonable curves and confidence envelopes to be obtained. The methods are applied to validation of the Simtec Adsorbs Type CM ethylene oxide monitor stored at 4°C after diffusive sampling of 2 ppm (3.6 mg m^?3) ethylene oxide for 4 h. The monitors are shown to comply with the U.S. OSHA requirements for up to eleven days of storage.     

Screening people for illicit substances: a survey of current portal technology

The need to implement more effective, cost efficient, non-intrusive ways of screening people for concealed drugs, explosives and weapons is a major security initiative for the U.S. and elsewhere. A new generation of portals suitable for security checkpoints is under development. These will be able to find contraband with high probabilities of detection, and low false-alarm rates. Some portals image the body using either low dose X-rays or millimeter wave interrogation, and analyze the radiation back-scattered from the body, providing images of concealed objects. Other portals operate essentially as anomaly detectors, finding objects on the human body. A series of portals is also under development that can harvest and analyze vapors or particles of the contraband substances. Some of the issues surrounding portal development include perceived safety issues, privacy issues, and operational issues such as ease of operation, non-invasiveness, and ease of interpretation. It is believed that portal technology will mature, and the cost of portals will fall sufficiently to make widespread deployment of portals at security checkpoints a reality within the next decade.     

Effectiveness of oak leaves as bioindicators of environmental pollution

The purpose of this study was to use instrumental neutron activation analysis (INAA) to investigate the effectiveness of oak tree leaves as indicators of atmospheric pollution. Leaves were sampled from several different cities in southwestern Ontario, Canada and tested for 16 different trace elements (U, Dy, Ba, Ti, Sr, I, Br, Mg, Cu, Na, V, K, Al, Mn, Cl and Ca). The results show promise for the use of oak leaves as multielemental environmental monitors due to their apparent ability to reflect the overall pollution levels of the vicinity in which they grow. Oak leaves were found to be superior to both birch and maple leaves for monitoring most of the elements studied.     

Utilization of a mixed-bed column for the removal of iodine from radioactive process waste solutions

A boron carbide capsule was previously designed and tested by Pacific Northwest National Laboratory (PNNL) and Washington State University (WSU) for spectral-tailoring in mixed spectrum reactors. The presented work used this B₄C capsule to create a fission product sample from the irradiation of highly enriched uranium (HEU) with a fast fission neutron spectrum. An HEU foil was irradiated inside of the capsule in WSU’s 1 MW TRIGA reactor at full power for 200 min to produce 5.8 × 10¹³ fissions. After 3 days of cooling, the sample was shipped to PNNL for radiochemical separations and analysis by gamma and beta spectroscopy. Fission yields for products were calculated from the radiometric measurements and compared to measurements from thermal neutron induced fission (analyzed in parallel with the non-thermal sample at PNNL) and published evaluated fast-pooled and thermal nuclear data. Reactor dosimetry measurements were also completed to fully characterize the neutron spectrum and total fluence of the irradiation.     

Highly Selective Removal of Perfluorinated Contaminants by Adsorption on All‐Silica Zeolite Beta

Perfluorinated alkylated substances (PFASs) are widely used in industrial and commercial applications, leading to a widespread occurrence of these persistent and harmful contaminants in our environment. Removal of these compounds from surface and waste waters is being mandated by European and U.S. governments. Currently, there are no treatment techniques available that lower the concentrations of these compounds for large water bodies in a cost‐ and energy‐efficient way. We hereby propose a hydrophobic, all‐silica zeolite Beta material that is a highly selective and high‐capacity adsorbent for PFASs, even in the presence of organic competitors. Advanced characterization data demonstrate that the adsorption process is driven by a very negative adsorption enthalpy and favorable steric factors.     

Highly Selective Removal of Perfluorinated Contaminants by Adsorption on All-Silica Zeolite Beta

Perfluorinated alkylated substances (PFASs) are widely used in industrial and commercial applications, leading to a widespread occurrence of these persistent and harmful contaminants in our environment. Removal of these compounds from surface and waste waters is being mandated by European and U.S. governments. Currently, there are no treatment techniques available that lower the concentrations of these compounds for large water bodies in a cost- and energy-efficient way. We hereby propose a hydrophobic, all-silica zeolite Beta material that is a highly selective and high-capacity adsorbent for PFASs, even in the presence of organic competitors. Advanced characterization data demonstrate that the adsorption process is driven by a very negative adsorption enthalpy and favorable steric factors.     

Quartz Crystal Microbalance with Dissipation Monitoring (EQCM-D) for in-situ studies of electrodes for supercapacitors and batteries: A mini-review

Herein the application of a recently introduced new method of tracking in-situ the intercalation-induced deformations of supercapacitor and Li-battery electrodes is reviewed. The method is based on the use of multi-harmonic electrochemical quartz microbalance with dissipation monitoring, EQCM-D (in-situ hydrodynamic spectroscopy) which enables a permanent control of the electrodes' state-of-health by probing their mechanical properties. The potential-dependent frequency and resonance width changes are fitted to a chosen hydrodynamic admittance model allowing thus quantification of the electrode deformations under different charging conditions. Intercalation of different alkaline metal cations into layered MXene electrode serves as a readily understandable working example of quantifying such electrodes deformations. Further method developments including in-situ viscoelastic characterization of composite porous electrodes are envisaged in the near future.     

Design and construction of an ultra-low-background 14-crystal germanium array for high efficiency and coincidence measurements

Physics experiments, environmental surveillance, and treaty verification techniques continue to require increased sensitivity for detecting and quantifying radionuclides of interest. This can be done by detecting a greater fraction of gamma emissions from a sample (higher detection efficiency) and reducing instrument backgrounds. A current effort for increased sensitivity in high resolution gamma spectroscopy will produce an intrinsic germanium (HPGe) array designed for high detection efficiency, ultra-low-background performance, and useful coincidence efficiencies. The system design is optimized to accommodate filter paper samples, e.g. samples collected by the Radionuclide Aerosol Sampler/Analyzer (RASA). The system will provide high sensitivity for weak collections on atmospheric filter samples, as well as offering the potential to gather additional information from more active filters using gamma cascade coincidence detection. The current effort is constructing an ultra-low-background HPGe crystal array consisting of two vacuum cryostats, each housing a hexagonal array of 7 crystals on the order of 70% relative efficiency per crystal. Traditional methods for constructing ultra-low-background detectors are used, including use of materials known to be low in radioactive contaminants, use of ultra pure reagents, clean room assembly, etc. The cryostat will be constructed mainly from copper electroformed into near-final geometry at PNNL. Details of the detector design, simulation of efficiency and coincidence performance, HPGe crystal testing, and progress on cryostat construction are presented.     

H2S Removal from Groundwater by Chemical Free Advanced Oxidation Process Using UV-C/VUV Radiation

Sulfide species may be present in groundwater due to natural processes or due to anthropogenic activity. H₂S contamination poses odor nuisance and may also lead to adverse health effects. Advanced oxidation processes (AOPs) are considered promising treatments for hydrogen-sulfide removal from water, but conventional AOPs usually require continuous chemical dosing, as well as post-treatment, when solid catalysts are applied. Vacuum-UV (VUV) radiation can generate ·OH in situ via water photolysis, initiating chemical-free AOP. The present study investigated the applicability of VUV-based AOP for removal of H₂S both in synthetic solutions and in real groundwater, comparing combined UV-C/VUV and UV-C only radiation in a continuous-flow reactor. In deionized water, H₂S degradation was much faster under the combined radiation, dominated by indirect photolysis, and indicated the formation of sulfite intermediates that convert to sulfate at high radiation doses. Sulfide was efficiently removed from natural groundwater by the two examined lamps, with no clear preference between them. However, in anoxic conditions, common in sulfide-containing groundwater, a small advantage for the combined lamp was observed. These results demonstrate the potential of utilizing VUV-based AOP for treating H₂S contamination in groundwater as a chemical-free treatment, which can be especially attractive to remote small treatment facilities.     

Monitoring of environmental contaminants: 10 years of application of k0-I INAA

Examples of the application of k ₀ standardized instrumental neutron activation analysis (k ₀ -INAA) to aerosols and biological monitors in the last 10 years at Instituto Tecnológico e Nuclear (ITN) are given. As an analytical technique, INAA, in association with the k ₀ method was applied to these materials in four different projects, aiming at monitoring concentrations of heavy metals and others elements in the atmosphere in the Portuguese territory. In these studies we analysed the lichen Parmelia sulcata Taylor and olive tree bark as monitors as well as aerosol samples. For each project some representative results are presented, followed by a discussion of the application of this technique to environmental studies.