Henry B. Spitz

A brief introduction to analytical methods in nuclear forensics

Nuclear forensic (NF) techniques are critical in responding to both environmental releases of nuclear materials and illicit trafficking activities involving both nuclear and counterfeit materials. Despite rising need, however, significant barriers exist to the future success of such research. This subset of analytical chemistry contains unique concerns (e.g. chronometry and impurity signatures), a wide variety of preparatory/instrumental approaches, and is in need of innovative solutions to current problems both in and out of the lab. The present work introduces existing NF research, development challenges and notes potential areas for advancement by highlighting several key analytical approaches. Examples of concerns and techniques discussed in this review include: chronometry, reference materials, separations, counting spectrometry, mass spectrometry and more.

Effect of leachability on environmental risk assessment for naturally occurring radioactive materials in petroleum oil fields.

Elevated concentrations of naturally occurring radioactive material (NORM), including 238U, 232Th, and their progeny found in underground geologic deposits, are often encountered during crude oil recovery. Radium, the predominant radionuclide brought to the surface with the crude oil and produced water, co-precipitates with barium in the form of complex compounds of sulfates, carbonates, and silicates found in sludge and scale. These NORM deposits are highly stable and very insoluble under ambient conditions at the earths surface. However, the co-precipitated radium matrix is not thermodynamically stable at reducing conditions which may enable a fraction of the radium to eventually be released to the environment. Although the fate of radium in uranium mill tailings has been studied extensively, the leachability of radium from crude oil NORM deposits exposed to acid-rain and other aging processes is generally unknown. The leachability of radium from NORM contaminated soil collected at a contaminated oil field in eastern Kentucky was determined using extraction fluids having wide range of pH reflecting different extreme environmental conditions. The average 226Ra concentration in the samples of soil subjected to leachability testing was 32.56 Bq g(-1) +/- 0.34 Bq g(-1). The average leaching potential of 226Ra observed in these NORM contaminated soil samples was 1.3% +/- 0.46% and was independent of the extraction fluid. Risk assessment calculations using the family farm scenario show that the annual dose to a person living and working on this NORM contaminated soil is mainly due to external gamma exposure and radon inhalation. However, waterborne pathways make a non-negligible contribution to the dose for the actual resident families living on farmland with the type of residual NORM contamination due to crude oil recovery operations.

Significant systemic therapeutic effects of high-LET immunoradiation by 212Pb-trastuzumab against prostatic tumors of androgen-independent human prostate cancer in mice

The purpose of this study was to determine therapeutic effects and systemic toxicity of 212Pb-trastuzumab in an orthotopic model of human prostate cancer cells in nude mice. TCMC-Trastuzumab was radiolabeled with 212Pb. The 212Pb-trastuzumab generated from the procedure was intact and had high binding affinity with a dissociation constant (of 3.9±0.99 nM. PC-3MM2 cells, which expressed a lower level of HER2 both in culture and in tumors, were used in therapy studies. A single intravenous injection of 212Pb-trastuzumab reduced tumor growth by 60-80%, reduced aortic lymph node metastasis, and prolonged the survival of tumor-bearing mice. Treatment with 212Pb-trastuzumab did not cause significant changes in body weight, serum glutamic pyruvic transaminase (SGPT), blood urea nitrogen (BUN), hematological profiles, and histological morphology of several major organs of tumor-bearing mice. These findings suggest that a systemic delivery of 212Pb-trastuzumab could be an effective modality for management of advanced human prostate cancer.

A new anthropometric phantom for calibrating in vivo measurements of stable lead in the human leg using x-ray fluorescence.

A new anthropometric phantom has been developed for calibrating in vivo measurements of stable lead deposited in bone using x-ray fluorescence. The phantom reproduces the shape of the mid shaft of the adult human leg and is fabricated using polyurethanes and calcium carbonate to produce materials that exhibit the same density, energy transmission, and calcium content as cortical bone, bone marrow, and muscle. The phantom includes a removable tibia fabricated using simulants for cortical bone and bone marrow to which a precise amount of stable lead has been added to cortical bone. The formulations used in fabricating the new anthropometric phantom are much more uniform in density and composition than the conventional phantom made from Plexiglas cylinders filled with plaster-of-Paris. The energy spectrum from an x-ray fluorescence measurement of the phantom using a 109Cd source is indistinguishable from an in vivo x-ray fluorescence measurement of the human leg, demonstrating that the materials used in the phantom exhibit the same radiological properties as human tissue. Likewise, results from x-ray fluorescence measurements of the phantom exhibit the same positional dependency as the human leg and vary by approximately 36% when, for example, the phantom containing 54 ppm of stable lead in the tibia was rotated by only 15 degrees. The detection limit for a 30 min 109Cd K shell x-ray fluorescence in vivo measurement is approximately 20 ppm determined from a background measurement using the new phantom containing no added lead in the muscle, bone, or bone marrow. The new anthropometric phantom significantly improves in vivo x-ray fluorescence calibration measurements by (1) faithfully reproducing the anatomy of the human leg, (2) having components that exhibit radiological properties similar to that of human tissue, and (3) providing a realistic calibration standard that can be used for in vivo x-ray fluorescence intercomparison measurements.

Estimation of skeletal burden of "bone-seeking" radionuclides in man from in vivo scintillation measurements of the head.

A method for estimating the skeletal burden of various “bone-seeking” lowenergy photon-emitting radionuclides, e.g. ”‘Pb, 241Am, and 238,9Pu, has been developed utilizing the technique of in vivo scintillation measurement of photon activity from the skull bones. In this procedure, the head (skull), which represents a structure comprising more than 12% of the skeletal mass, is surrounded by three NaI(Tl)CsI(Tl) dual crystal scintillation detectors to maximize counting efficiency and minimize detection variablity. In addition to measuring the low-energy photons (<lo0 keV) of important radionuclides known to deposit in or on the surfaces of bone, these detectors are employed to simultaneously monitor the higher energy gamma-ray spectra of “natural” radioactivity such as 40K. From this information it has been possible to optimize the accuracy of background correction, thereby minimizing the detectable levels of a “bone-seeking’’ contaminant. In addition, considerations of accurate “phantom” head construction and the precision of head counting methodology have been investigated. Once the amount of activity deposited in the skull bones has been determined, it is possible to estimate the contribution from the nuclide in the thoracic skeleton to in vivo measurements of activity in the lungs

School bus pollution and changes in the air quality at schools: a case study

Millions of children attending US schools are exposed to traffic-related air pollutants, including health-relevant ultrafine aerosols generated from school buses powered with diesel fuel. This case study was established in a midwestern (USA) metropolitan area to determine the concentration and elemental composition of aerosol in the vicinity of a public school during morning hours when the bus traffic in and out of the adjacent depot was especially intense. Simultaneous measurements were performed at a control site. The ambient aerosol was first characterized in real time using a particle size selective aerosol spectrometer and then continuously monitored at each site with a real-time non-size-selective instrument that detected particles of 20 nm to >1 microm. In addition, air samples were collected with PM2.5 Harvard Impactors and analyzed for elemental composition using the X-ray fluorescence technique (for 38 elements) and thermal-optical transmittance (for carbon). The measurements were conducted during two seasons: in March at ambient temperature around 0 degrees C and in May when it ranged mostly between 10 and 20 degrees C. The particle number concentration at the test site exhibited high temporal variability while it was time independent at the control site. Overall, the aerosol particle count at the school was 4.7 +/- 1.0 times (March) and 2.2 +/- 0.4 times (May) greater than at the control site. On some days, a 15 min-averaged particle number concentration showed significant correlation with the number of school bus arrivals and departures during these time intervals. On other days, the correlation was less than statistically significant. The 3 h time-averaged particle concentrations determined in the test site on days when the school buses operated were found to be more than two-fold greater (on average) than those measured on bus-free days at the same location, and this difference was statistically significant. Overall, the data suggest a possible association between the number of detected aerosol particles and the school bus traffic intensity. Analysis of the filter samples collected at the school site between 6:00 and 9:00 AM revealed higher concentrations of elemental carbon as compared to the control site (2.8 +/- 0.9 times in March and 3.1 +/- 1.1 times in May). The data collected in this case study suggest that school buses significantly contribute to exposure of children to aerosol pollutants (including diesel exhaust particles) in the school vicinity.

Measurement of the attenuation coefficient for Livermore Thoracic Phantom lungs fabricated using contemporary materials.

The University of Cincinnati has reproduced the original formulation for the Livermore Thoracic Phantom lungs using contemporary materials and has adopted the linear attenuation coefficient as the primary quality assurance parameter for evaluating the performance capabilities of these new lung phantoms. The Livermore Thoracic Phantom was originally fabricated in 1978 to intercalibrate detector systems used to measure plutonium and other low-energy, photon emitting radionuclides deposited in the respiratory tract. The linear attenuation coefficient is a critical performance indicator for these phantom lungs since the presence of any material with a high effective atomic number (where Z > or = 20) will make a significant change in the photoelectric cross section, the predominant mode of interaction for plutonium x rays. A set of test lungs was fabricated with KCl to introduce a known quantity of 40K in the phantom and to determine, by measurement and calculations, what change would be made to the attenuation coefficient at photon energies below 100 keV as a result of the modified formulation. The KCl increased the linear attenuation coefficient below 60 keV by more than a factor of two, which would produce a substantial systematic error in any subsequent calibration measurements performed with these modified phantom lungs. These results support use of the attenuation coefficient as an important performance indicator for the Livermore Thoracic Phantom lungs and also suggest that KCl not be added to the lung tissue substitute formulation as a means to incorporate 40K in the phantom for low energy calibrations.

Statistical analysis of real-time, environmental radon monitoring results at the Fernald Environmental Management Project.

A comprehensive real-time, environmental radon monitoring program is being conducted at the Fernald Environmental Management Project, where a large quantity of radium-bearing residues have been stored in two covered earth-bermed silos. Statistical analyses of radon measurement results were conducted to determine what impact, if any, radon emitted by the radium bearing materials contained in the silos has on the ambient radon concentration at the Fernald Environmental Management Project site. The distribution that best describes the outdoor radon monitoring data was determined before statistical analyses were conducted. Random effects associated with the selection of radon monitoring locations were accommodated by using nested and nested factorial classification models. The Fernald Environmental Management Project site was divided into four general areas according to their characteristics and functions: 1) the silo area, where the radium-bearing waste is stored; 2) the production/administration area; 3) the perimeter area, or fence-line, of the Fernald Environmental Management Project site; and 4) a background area, located approximately 13 km from the Fernald Environmental Management Project site, representing the naturally-occurring radon concentration. A total of 15 continuous, hourly readout radon monitors were installed in these 4 areas to measure the outdoor radon concentration. Measurement results from each individual monitor were found to be log-normally distributed. A series of contrast tests, which take random effects into account, were performed to compare the radon concentration between different areas of the site. These comparisons demonstrate that the radon concentrations in the production/administration area and the perimeter area are statistically equal to the natural background, whereas the silo area is significantly higher than background. The study also showed that the radon concentration in the silo area was significantly reduced after a sealant barrier was applied to the contents of the silos.

The Importance of Acid Digestion of Urine Prior to Spontaneous Deposition of 210po

Historically, radiochemical analysis of 210Po in urine has used spontaneous deposition of the nuclide directly from raw urine onto a suitable metal disc. Consequently, the urinary excretion fraction for Po in some current metabolic and dosimetric models is based on studies which inherently assume that metabolized (i.e., filtered out of the blood by the kidneys) 210Po is plated with the same efficiency as tracer 210Po which has been added to urine samples. Urine samples collected after intravenous administration of 210Po citrate to two species of nonhuman primates were divided and simultaneously analyzed via two methods: the historical procedure of plating 210Po from raw urine for one sample and a method which includes the addition of 208Po tracer and sample digestion with concentrated HNO3 prior to 210Po deposition for the other sample. A more significant amount of 210Po was consistently recovered when the urine was wet ashed then when it was not wet ashed. A temporal relationship was found to describe the change in the ratio of the deposition recoveries for the two methods. Possible mechanisms for this phenomenon and its dosimetric implications are discussed.

Uranium isotopic signatures measured in samples of dirt collected at two former uranium facilities

Nuclear forensics is a multidisciplinary science that uses a variety of analytical methods and tools to explore the physical, chemical, and isotopic characteristics of nuclear and radiological materials. These characteristics, when evaluated alone or in combination, become signatures that may reveal how and when the material was fabricated. The signatures contained in samples of dirt collected at two different uranium metal processing facilities in the United States were evaluated to determine uranium isotopic composition and compare results with processes that were conducted at these sites. One site refined uranium and fabricated uranium metal ingots for fuel and targets and the other site rolled hot forged uranium and other metals into dimensional rods. Unique signatures were found that are consistent with the activities and processes conducted at each facility and establish confidence in using these characteristics to reveal the provenance of other materials that exhibit similar signatures.