Efficient Retention and Alpha Spectroscopy of Actinides from Aqueous Solutions Using a Combination of Water-Soluble Star-like Polymers and Ultrafiltration Membranes.

We explored two approaches to recover uranium and plutonium from aqueous solutions at pH 4 and pH 7 using water-soluble star-like polyacrylamide polymers with a dextran core. In the first approach, a solution comprising a neutral or ionomer polymer was mixed with a radionuclide solution to form polymer-metal complexes that were then retained by ultrafiltration (UF) membranes under applied pressure. The same polymers were first deposited on the membrane in the second approach using pressure-driven flow. The applied polymers had an overall diameter of gyration of 120 nm, which exceeded the nominal diameter of the UF membrane pores. The polymers showed a high affinity to uranyl but could also be used to extract Pu from neutral or near-neutral pH solutions. Direct-flow single-step filtration and alpha spectrometry demonstrated that the UF membranes containing star-like copolymers could recover 99% of U and up to 60% of Pu from deionized water after filtering 15 mL solutions containing 25 ppm and 33 ppb of the actinides, correspondingly. The sorption capacity of the polymers for uranium could be measured as 1mg U per mg of the polymer after six subsequent filtration steps. Alpha spectroscopy of the deposited actinides revealed peculiarities of the structural organization of polymers and their complexes with U or Pu, depending on the approach. Though both approaches were efficient, the second approach (deposition of the polymer on the membrane followed by filtration) has an additional advantage of protecting the membrane pores from capillary collapse by filling them with the polymer chains. Therefore, these polymer-modified membranes could be used either in continuous or multi-step filtration process with drying after each step without deterioration of their sorption characteristics.

Polyamidoxime-based membranes for the rapid screening of uranium isotopes in water.

Traditional radiochemistry approaches for the detection of trace-level alpha-emitting radioisotopes in water require lengthy offsite sample preparations and do not lend themselves to rapid quantification. Therefore, a novel platform is needed that combines onsite purification, concentration, and isotopic screening with a fieldable detection system. This contribution describes the synthesis and characterization of polyamidoxime membranes for isolation and concentration of uranium from aqueous matrices, including high-salinity seawater. The aim was to develop a field portable screening method for the rapid quantification of isotopic distribution by alpha spectroscopy. Membranes with varying degree of modification were prepared by chemical conversion of nitrile groups to amidoxime groups on the surface of polyacrylonitrile ultrafiltration (UFPAN) membranes. Attenuated total reflectance Fourier-transform infrared spectroscopy was used to analyze changes in surface chemistry. Flow through filtration experiments conducted using deionized (DI) water and simulated seawater solutions indicated that the modified membrane was effective in capturing more than 95% of the uranium in the solution prior to breakthrough even in the presence of salt ions. Batch uptake experiments were conducted and compared with the flow through experimental data to elucidate likely binding mechanisms. Alpha spectra of uranium loaded membranes were analyzed, and the effects of solution matrix and degree of modification on peak energy resolution were studied. Peak energy resolutions of 24 ± 2 keV and 32 ± 6 keV full width at half maximum (FWHM) were obtained by loading uranium from DI and seawater solutions onto modified membranes. Full width at 10% maximum of the same spectra were calculated to be 63 ± 9 keV and 160 ± 34 keV to quantify differences seen in peak tailing. Calculations performed based on the results show that it would take less than 3 h of analysis time to screen a sample provided enough volumes of solution are available. This work offers a facile method to prepare polyamidoxime-based membranes for uranium separation and concentration at circumneutral pH values, enabling the rapid, onsite screening of unknown samples.

Membranes for the Capture and Screening of Waterborne Plutonium Based on a Novel Pu-Extractive Copolymer Additive.

This contribution describes the fabrication of plutonium-adsorptive membranes by non-solvent induced phase separation. The dope solution comprised poly(vinylidene fluoride) (PVDF) and a Pu-extractive copolymer additive of PVDF-g-poly(ethylene glycol methacrylate phosphate) (EGMP) in dimethylformamide (DMF). The effects of casting conditions on membrane permeability were determined for PVDF membranes prepared with 10 wt% PVDF-g-EGMP. Direct-flow filtration and alpha spectrometry showed that membranes containing the graft copolymer could recover Pu up to 59.9 ± 3.0% from deionized water and 19.3 ± 3.5% from synthetic seawater after filtering 10 mL of 0.5 Bq/mL 238Pu. SEM-EDS analysis indicated that the graft copolymer was distributed evenly throughout the entire depth of the copolymer membranes, likely attributing to the tailing observed in the alpha spectra for 238Pu. Despite the reduction in resolution, the membranes exhibited high Pu uptake at the conditions tested, and new membrane designs that promote copolymer surface migration are expected to improve alpha spectrometry peak energy resolutions. Findings from this study also can be used to guide the development of extractive membranes for chromatographic separation of actinides from contaminated groundwater sources.

Integration of ecosystem science into radioecology: A consensus perspective.

In the Fall of 2016 a workshop was held which brought together over 50 scientists from the ecological and radiological fields to discuss feasibility and challenges of reintegrating ecosystem science into radioecology. There is a growing desire to incorporate attributes of ecosystem science into radiological risk assessment and radioecological research more generally, fueled by recent advances in quantification of emergent ecosystem attributes and the desire to accurately reflect impacts of radiological stressors upon ecosystem function. This paper is a synthesis of the discussions and consensus of the workshop participant's responses to three primary questions, which were: 1) How can ecosystem science support radiological risk assessment? 2) What ecosystem level endpoints potentially could be used for radiological risk assessment? and 3) What inference strategies and associated methods would be most appropriate to assess the effects of radionuclides on ecosystem structure and function? The consensus of the participants was that ecosystem science can and should support radiological risk assessment through the incorporation of quantitative metrics that reflect ecosystem functions which are sensitive to radiological contaminants. The participants also agreed that many such endpoints exit or are thought to exit and while many are used in ecological risk assessment currently, additional data need to be collected that link the causal mechanisms of radiological exposure to these endpoints. Finally, the participants agreed that radiological risk assessments must be designed and informed by rigorous statistical frameworks capable of revealing the causal inference tying radiological exposure to the endpoints selected for measurement.

Functionalized Polymer Thin Films for Plutonium Capture and Isotopic Screening from Aqueous Sources.

The rapid screening of plutonium from aqueous sources remains a critical challenge for nuclear nonproliferation efforts. The determination of trace-level Pu isotopes in water requires offsite sample preparation and analysis; therefore, new methods that combine plutonium purification, concentration, and isotopic screening in a fieldable detection system will provide an invaluable tool for nuclear safeguards. This contribution describes the development and characterization of thin polymer-ligand films for the isolation and concentration of waterborne Pu for direct spectroscopic analyses. Submicron thin films were prepared through spin coating onto Si wafers and consisted of combinations of polystyrene (PS) with dibenzoylmethane, thenoyltrifluoroacetone, and di(2-ethylhexyl)phosphoric acid (HDEHP). Pu uptake studies from solutions at pH from 2.3 to 6.3 indicated that only films containing HDEHP exhibited significant recovery of Pu. High alpha spectroscopy peak energy resolutions were achieved for PS-HDEHP films over a range of film thicknesses from 30 to 250 nm. A separate study was performed to evaluate uptake from a primarily Pu(V) solution where it was observed that doubling the HDEHP loading in the film increased uptake of Pu by an order of magnitude. X-ray photoelectron spectroscopy (XPS) analysis revealed that HDEHP was highly concentrated within the first few nanometers of the film at the higher loading. XPS analysis also revealed that, in the presence of water, HDEHP was stripped from the surface layer of the film at circumneutral pH. While significant losses of ligand were seen in all samples, higher loadings of HDEHP resulted in measurable amounts of ligand retained after a 12-h soak in water. Findings of this study are being used to guide the development of thin-film composite membrane-based detection methods for the rapid, fieldable analysis of Pu in water.

A Mixed-methods Approach for Improving Radiation Safety Culture in Open-source University Laboratories.

The radiation safety culture of those working in university open-source radioactive material laboratories was assessed by conducting both surveys and behavioral observations. Baseline results (n = 82, 89% response rate) of assessed safety culture categories indicated safety practices and safety compliance were the most in need of improvement. Specific training based on these results was provided to laboratory members at Princeton University, with creative signage and a safety newsletter posted in and around laboratories for reinforcement, in a targeted effort to improve the radiation safety culture. Signage posted utilized pop cultural memes and other engaging graphics designed to raise awareness of appropriate safety practices and the minimum laboratory attire expected while working in radioactive material laboratories. Postintervention results (n = 38, 43% response rate) indicated improvement in 4 out of the 10 safety culture indicators considered as well as fewer instances of improper safety practices. Collaborative techniques and increased communication between researchers and radiation safety staff appear to have initiated an improvement in the radiation safety culture in open-source radioactive material laboratories at Princeton University.

Thermal Neutron Characterization and Dose Modeling of a 239PuBe Alpha-Neutron Source.

Determination of neutron dose can be challenging and requires knowledge of neutron flux as a function of energy. The goal of this project was to characterize the thermal neutron flux of a 37 GBq PuBe alpha-neutron source and model the associated neutron dose using version MCNPX of the Monte-Carlo N-Particle transport codes. The PuBe source was placed in a neutron howitzer, and foil activation (dysprosium foils with and without cadmium covers) was used at various distances to determine thermal neutron flux, which was then used to verify the MCNPX model representing the system. The model was then adapted for dosimetric modeling to enable future neutron dose-response studies.

Application of new covalently-bound diglycolamide sorbent in sequential injection analysis flow system for sample pretreatment in ICP-MS determination of 239Pu at ppt level.

Diglycolamide ligands are widely applied in the analysis of radionuclides, especially lanthanides and actinides. They are used in liquid-liquid extraction procedures or in solid-phase extraction sorbents where they are adsorbed on the surface of hydrophobic polymers. The main objective of this study was to synthesize the N,N,N'N'-tetrahexyl diglycolamide with one vinyl terminating group (vTHDGA) for further covalent immobilization on the polystyrene-divinylbenzene polymeric support. The obtained complexing resin (THDGA) was employed for the mechanized sample pretreatment in the Sequential Injection Analysis - Lab-on-Valve (SIA-LOV) flow system for the determination of 239Pu using ICP-MS detection. The analytical procedure was optimized in terms of selectivity towards several other radionuclides and elements forming potentially isobaric interferences in mass spectrometry. For 100 mL volume of sample to be analyzed, the method detection limit (MDL) was 96 mBq L-1 (42 pg L-1). The developed method was employed for the determination of 239Pu in real samples of a nuclear reactor coolant and spent fuel pool water from a nuclear reactor.

High effectiveness of pure polydopamine in extraction of uranium and plutonium from groundwater and seawater.

Sorption properties of polydopamine (PDA) for uranium and plutonium from an aqueous environment are reported at three different pH values (2, 4 and 6.5-7). In addition to deionized (DI) water, artificial groundwater (GW) and seawater (SW) were used with U uptake close to 100% in each case. PDA polymer has been identified as a material with extremely high sorption capacity Q max ∼500 mg g-1 of the polymer at pH 6.5 and high selectivity for uranium. Similar high sorption properties are revealed for plutonium uptake. PDA-uranyl and PDA-plutonium interactions responsible for the observed adsorption processes have been addressed with a set of experimental techniques including FTIR spectroscopy, electron microscopy and cyclic voltammetry.

Evaluation of Shiryaev-Roberts procedure for on-line environmental radiation monitoring.

Water can become contaminated as a result of a leak from a nuclear facility, such as a waste facility, or from clandestine nuclear activity. Low-level on-line radiation monitoring is needed to detect these events in real time. A Bayesian control chart method, Shiryaev-Roberts (SR) procedure, was compared with classical methods, 3-σ and cumulative sum (CUSUM), for quantifying an accumulating signal from an extractive scintillating resin flow-cell detection system. Solutions containing 0.10-5.0 Bq/L of 99Tc, as T99cO4- were pumped through a flow cell packed with extractive scintillating resin used in conjunction with a Beta-RAM Model 5 HPLC detector. While T99cO4- accumulated on the resin, time series data were collected. Control chart methods were applied to the data using statistical algorithms developed in MATLAB. SR charts were constructed using Poisson (Poisson SR) and Gaussian (Gaussian SR) probability distributions of count data to estimate the likelihood ratio. Poisson and Gaussian SR charts required less volume of radioactive solution at a fixed concentration to exceed the control limit in most cases than 3-σ and CUSUM control charts, particularly solutions with lower activity. SR is thus the ideal control chart for low-level on-line radiation monitoring. Once the control limit was exceeded, activity concentrations were estimated from the SR control chart using the control chart slope on a semi-logarithmic plot. A linear regression fit was applied to averaged slope data for five activity concentration groupings for Poisson and Gaussian SR control charts. A correlation coefficient (R2) of 0.77 for Poisson SR and 0.90 for Gaussian SR suggest this method will adequately estimate activity concentration for an unknown solution.

One-dimensional Spatial Distributions of Gamma-ray Emitting Contaminants in Field Lysimeters Using a Collimated Gamma-ray Spectroscopy System.

One-dimensional scans of gamma-ray emitting contaminants were conducted on lysimeters from the RadFLEX facility at the Savannah River Nationals Laboratory (SRNL). The lysimeters each contained a contamination source that was buried in SRNL soil. A source consisted of Cs, Co, Ba, and Eu incorporated either into a solid waste form (Portland cement and reducing grout) or applied to a filter paper for direct soil exposure. The lysimeters were exposed to natural environmental conditions for 3 to 4 y. The initial contaminant activities range from 4.0 to 9.0 MBq for the solid wasteforms and 0.25 to 0.47 MBq for the soil-incorporated source. The measurements were performed using a collimated high-purity germanium gamma-ray spectrometer with a spatial resolution of 2.5 mm. These scans showed downward mobility of Co and Ba when the radionuclides were incorporated directly into the SRNL soil. When radionuclides were incorporated into the solid waste forms positioned in the SRNL soil, Cs exhibited both upward and downward dispersion while the other radionuclides showed no movement. This dispersion was more significant for the Portland cement than the reducing grout wasteform. Europium-152 was the only radionuclide of those studied that showed no movement within the spatial resolution of the scanner from the original placement within the lysimeter. Understanding radionuclide movement in the environment is important for developing strategies for waste management and disposal.

Rapid Sample Preparation for Alpha Spectroscopy with Ultrafiltration Membranes.

This contribution describes a rapid, fieldable alpha spectroscopy sample preparation technique that minimizes consumables and decreases the nuclear forensics timeline. Functional ultrafiltration membranes are presented that selectively concentrate uranium directly from pH 6 groundwater and serve as the alpha spectroscopy substrate. Membranes were prepared by ultraviolet grafting of uranium-selective polymer chains from the membrane surface. Membranes were characterized by Fourier-transform infrared spectroscopy before and after modification to support functionalization. Membrane performance was evaluated using uranium-233 or depleted uranium in both deionized and simulated groundwater at pH 6. Functionalized membranes achieved peak energy resolutions of 31 ± 2 keV and recoveries of 81 ± 4% when prepared directly from pH 6 simulated groundwater. For simulated groundwater spiked with depleted uranium, baseline energy resolution was achieved for both isotopes (uranium-238 and uranium-234). The porous, uranium-selective substrate designs can process liters per hour of uranium-contaminated groundwater using low-pressure (<150 kPa) filtration and a 45 mm diameter membrane filter, leading to a high-throughput, one-step concentration, purification, and sample mounting process.

High-Resolution 4D Preclinical Single-Photon Emission Computed Tomography/X-ray Computed Tomography Imaging of Technetium Transport within a Heterogeneous Porous Media.

A dynamic 99mTc tracer experiment was performed to investigate the capabilities of combined preclinical single photon emission computed tomography (SPECT) and X-ray computed tomography (CT) for investigating transport in a heterogeneous porous medium. The experiment was conducted by continuously injecting a 99mTc solution into a column packed with eight layers (i.e., soil, silica gel, and 0.2-4 mm glass beads). Within the imaging results it was possible to correlate observed features with objects as small as 2 mm for the SPECT and 0.2 mm for the CT. Time-lapse SPECT imaging results illustrated both local and global nonuniform transport phenomena and the high-resolution CT data were found to be useful for interpreting the cause of variations in the 99mTc concentration associated with structural features within the materials, such as macropores. The results of this study demonstrate SPECT/CT as a novel tool for 4D (i.e., transient three-dimensional) noninvasive imaging of fate and transport processes in porous media. Despite its small scale, an experiment with such high resolution data allows us to better understand the pore scale transport which can then be used to inform larger scale studies.

Extractive scintillating polymer sensors for trace-level detection of uranium in contaminated ground water.

This contribution describes the synthesis of robust extractive scintillating resin and its use in a flow-cell detector for the direct detection of uranium in environmental waters. The base poly[(4-methyl styrene)-co-(4-vinylbenzyl chloride)-co-(divinylbenzene)-co-(2-(1-napthyl)-4-vinyl-5-phenyloxazole)] resin contains covalently bound fluorophores. Uranium-binding functionality was added to the resin by an Arbuzov reaction followed by hydrolysis via strong acid or trimethylsilyl bromide (TMSBr)-mediated methanolysis. The resin was characterized by Fourier-transform infrared spectroscopy and spectrofluorometry. Fluorophore degradation was observed in the resin hydrolyzed by strong acid, while the resin hydrolyzed by TMSBr-mediated methanolysis maintained luminosity and showed hydrogen bonding-induced Stokes' shift of ∼100 nm. The flow cell detection efficiency for uranium of the TMSBr-mediated methanolysis resin was evaluated at pH 4, 5 and 6 in DI water containing 500 Bq L-1 uranium-233 and demonstrated flow cell detection efficiencies of 23%, 16% and 7%. Experiments with pH 4, synthetic groundwater with 50 Bq L-1 uranium-233 exhibited a flow cell detection efficiency of 17%. The groundwater measurements show that the resins can concentrate the uranyl cation from waters with high concentrations of competitor ions at near-neutral pH. Findings from this research will lay the groundwork for development of materials for real-time environmental sensing of alpha- and beta-emitting radionuclides.

New Efficient Organic Scintillators Derived from Pyrazoline.

We report on the synthesis, spectroscopic and scintillation properties of three new pyrazoline core based fluorophores. Fluorescence properties of the fluorophores have been studied both in a solution state and in a solid polyvinyltoluene (PVT) resin matrix of different porosity. The synthesized fluorophores were found to be promising candidates for application in plastic scintillators for detection of ionizing radiation (alpha, beta particles, γ rays and neutrons) and demonstrated superior efficiency in comparison to the existing commercially used fluorophores (2-(1-naphthyl)-5-phenyloxazole (αNPO), 9,10-diphenylanthracene, etc.). Moreover, the suggested synthetic route allows functionalization of the fluorophores with a vinyl group for further covalent bound to the PVT or other vinyl polymer matrices, which dramatically improves chemical stability of the system simultaneously improving the photoluminescence quantum yield. Possible mechanisms of the enhanced scintillation properties are discussed based on preliminary quantum mechanical calculations and spectroscopic characteristics of the fluorophores under study.

Development of a novel method for the determination of aqueous inorganic 129I speciation.

The objective of this research was to develop a method suitable for the determination of aqueous concentrations of radioactive iodine as I2, I(-), and IO3(-). As one of the primary risk-drivers and contaminants of concern at nuclear waste repositories, the accurate determination of (129)I in aqueous systems is of significant concern. The redox-active nature of iodine makes its mobility and fate in the environment difficult to predict, thus underscoring the importance of species-specific determination of iodine concentrations. The developed method couples solid phase extraction with liquid scintillation counting, and scintillating anion exchange with a flow-cell detection system for a sequential measurement of each iodine species. Solid phase extraction disks were impregnated with polyvinylpyrrolidone for the selective extraction and stabilization of I2 with subsequent analysis by liquid scintillation counting. Aqueous I(-) was concentrated and measured by a previously developed flow-cell system utilizing scintillating anion-exchange resin. A subsequent chemical reduction of IO3(-) to I(-) in the effluent was used to quantify IO3(-) by the same flow-cell system. Nearly quantitative results were found for standardized single-species samples of I2 (95%), I(-) (101%), and IO3(-) (91%), respectively, while consistent measurements were obtained for multispecies samples using the developed method and algorithm.

Bayesian analyses of time-interval data for environmental radiation monitoring.

Time-interval (time difference between two consecutive pulses) analysis based on the principles of Bayesian inference was investigated for online radiation monitoring. Using experimental and simulated data, Bayesian analysis of time-interval data [Bayesian (ti)] was compared with Bayesian and a conventional frequentist analysis of counts in a fixed count time [Bayesian (cnt) and single interval test (SIT), respectively]. The performances of the three methods were compared in terms of average run length (ARL) and detection probability for several simulated detection scenarios. Experimental data were acquired with a DGF-4C system in list mode. Simulated data were obtained using Monte Carlo techniques to obtain a random sampling of the Poisson distribution. All statistical algorithms were developed using the R Project for statistical computing. Bayesian analysis of time-interval information provided a similar detection probability as Bayesian analysis of count information, but the authors were able to make a decision with fewer pulses at relatively higher radiation levels. In addition, for the cases with very short presence of the source (< count time), time-interval information is more sensitive to detect a change than count information since the source data is averaged by the background data over the entire count time. The relationships of the source time, change points, and modifications to the Bayesian approach for increasing detection probability are presented.

CUSUM analyses of time-interval data for online radiation monitoring.

Three statistical control chart methods were investigated to determine the one with the highest detection probability and the best average run length (ARL). The three control charts include the Shewhart control chart of count data, cumulative sum (CUSUM) analysis of count data (Poisson CUSUM), and CUSUM analysis of time-interval (time difference between two consecutive radiation pulses) data (time-interval CUSUM). The time-interval CUSUM (CUSUMti) control chart was compared with the Poisson CUSUM (CUSUMcnt) and the Shewhart control charts with experimental and simulated data. The experimental data were acquired with a DGF-4C (XIA, Inc.) system in list mode. Simulated data were obtained by using Monte Carlo techniques to obtain a random sampling of a Poisson process. All statistical algorithms were developed using R (R Development Core Team). Detection probabilities and ARLs for the three methods were compared. The time-interval CUSUM control chart resulted in a similar detection probability as that of the Poisson CUSUM control chart but had the shortest ARL at relatively higher radiation levels; e.g., about 40% shorter than the Poisson CUSUM at 10.0 counts per second (cps) (five times above the background count rate). Both CUSUM control charts resulted in a higher detection probability than that of the Shewhart control chart; e.g., 100% greater than the Shewhart control method at 4.0 cps (two times above the background count rate). In addition, when time-interval information was used, the CUSUM control chart coupled with a modified runs rule (mrCUSUMti) showed the ability to further reduce the time needed to respond to changes in radiation levels and keep the false positive rate at a required level.

Preparation of polymer-coated, scintillating ion-exchange resins for monitoring of 99Tc in groundwater.

The present study was oriented to prepare new scintillating anion-exchange resins for measurement of (99)TcO(4)(-) in natural waters. The organic fluor 2-(1-naphthyl)-5-phenyloxazole was diffused into (chloromethyl)polystyrene resin. Thereafter, a thin layer of poly[[2-(methacryloyloxy)ethyl]trimethylammonium chloride] was grafted from the resin surface by surface-initiated atom transfer radical polymerization as an attempt to overcome potential problems related to the leaching of fluor molecules during usage. The residual chloromethyl groups of the polymer-coated resin were aminated by reaction with two different tertiary amines, triethylamine (TEA) and methyldioctylamine (MDOA). Off- and on-line quantification of (99)Tc was achieved with high detection efficiencies of 60.72 ± 1.93% and 72.83 ± 0.81% for resin with TEA and MDOA functional groups, respectively. The detection limit was determined to be less than the maximum contaminant level (33 Bq L(-1)) established under the Safe Drinking Water Act. The two functionalized resins were demonstrated to be selective for pertechnetate from synthetic groundwater containing up to 1000 ppm Cl(-), SO(4)(2-), and HCO(3)(-) and up to 1200 ppb Cr(2)O(7)(2-) in an acidic medium.