Search

The near real-time detection of airborne particles-of-interest is needed for avoiding current/future threats. The incorporation of imprinted particles into a micelle-based electrochemical cell produced a signal when brought into contact with particle analytes (such as SARS-COV-2), previously imprinted onto the structure. Nanoamp scales of signals were generated from what may've been individual virus-micelle interactions. The system showed selectivity when tested against similar size and morphology particles. The technology was compatible with airborne aerosol sampling techniques. Overall, the application of imprinted micelle technology could provide near real-time detection methods to a host of possible analytes of interest in the field.The online version contains supplementary material available at 10.1557/s43579-022-00242-0.

The long-lived positron emitter

Cyclotron-produced astatine-211 (211At) shows tremendous promise in targeted alpha therapy (TAT) applications due to its attractive half-life and its 100% α-emission from nearly simultaneous branched alpha decay. Astatine-211 is produced by alpha beam bombardment of naturally monoisotopic bismuth metal (209Bi) via the (α, 2n) reaction. In order to isolate the small mass of 211At (specific activity = 76 GBq·µg−1) from several grams of acid-dissolved Bi metal, a manual milliliter-scale solvent extraction process using diisopropyl ether (DIPE) is routinely performed at the University of Washington. As this process is complex and time consuming, we have developed a fluidic workstation that can perform the method autonomously. The workstation employs two pumps to concurrently deliver the aqueous and organic phases to a mixing tee and in-line phase mixer. The mixed phases are routed to a phase settling reservoir, where they gravity settle. Finally, each respective phase is withdrawn into its respective pump. However, development of a phase boundary sensor, placed in tandem with the phase settling reservoir, was necessary to communicate to the system when withdrawal of the denser aqueous phase was complete (i.e., the intersection of the two phases was located). The development and optimization of the autonomous solvent extraction system is described, and the 211At yields from several ~1.1 GBq-level 211At processing runs are reported.

Zirconium-89 (89Zr), produced by the (p, n) reaction from naturally monoisotopic yttrium (natY), is a promising positron emitting isotope for immunoPET imaging. Its long half-life of 78.4 h is sufficient for evaluating slow physiological processes. A prototype automated fluidic system, coupled to on-line and in-line detectors, has been constructed to facilitate development of new 89Zr purification methodologies. The highly reproducible reagent delivery platform and near-real time monitoring of column effluents allows for efficient method optimization. The separation of Zr from dissolved Y metal targets was evaluated using several anion exchange resins. Each resin was evaluated against its ability to quantitatively capture Zr from a load solution high in dissolved Y. The most appropriate anion exchange resin for this application was identified, and the separation method was optimized. The method is capable of a high Y decontamination factor (>105) and has been shown to remove Fe, an abundant contaminant in Y foils, from the 89Zr elution fraction. Finally, the method was evaluated using cyclotron bombarded Y foil targets; the method was shown to achieve >95% recovery of the 89Zr present in the foils. The anion exchange column method described here is intended to be the first 89Zr isolation stage in a dual-column purification process.

Zirconium-89 (89Zr) is a long-lived (t1/2 = 78.4h) positron-emitting isotope that is useful for positron emission tomography (PET) based diagnostic imaging using radiolabeled antibodies. Hydroxamate resin columns are predominantly used for the purification of 89Zr from cyclotron bombarded natY targets dissolved in strong HCl. 89Zr is conventionally eluted from the resin in 1M oxalic acid (H2C2O4), a complexant that is conducive to follow-on binding of 89Zr through a transchelation process to the deferoxamine siderophore. In the present study, we determined that a lower concentration of H2C2O4 eluent (0.8M) is adequate to efficiently remove 89Zr from a column containing 100mg hydroxamate resin. As a result, less buffering agents are needed to be added to the 89Zr product fraction prior to labeling. A simple automated fluidic system prototype has been developed to perform the steps required for 89Zr purification using a hydroxamate resin column (column conditioning in HCl, Y target dissolution, dissolved target solution load onto column, column washes using HCl and water, and 89Zr elution). The system performance was evaluated using several cyclotron bombarded Y targets; 89Zr product fractions demonstrated excellent chemical recoveries from these targets, with 1.0mL product volumes yielding 89±2% of the column elution peak activity and 84±2% of 89Zr recovered from the target (at EOB). These results compare favorably with previously published 89Zr product volumes and yields, despite the lower concentration of H2C2O4 eluent employed. Transchelation of resulting 89Zr product fractions was performed to assess product quality. The effective specific activity (ESA) ranged between 44(7) and 109(22) TBq·mmole-1, while the bindable metals concentration, a metric introduced for assessing and comparing product purity, ranged between 43(7) and 115(27) nmole·g-1.

Ammonium bifluoride (ABF, NH 4 F·HF) is a well-known reagent for converting metal oxides to fluorides and for its applications in breaking down minerals and ores in order to extract useful components. It has been more recently applied to the decomposition of inorganic matrices prior to elemental analysis. Herein, a sample decomposition method that employs molten ABF sample treatment in the initial step is systematically evaluated across a range of inorganic sample types: glass, quartz, zircon, soil, and pitchblende ore. Method performance is evaluated across two variables: duration of molten ABF treatment and ABF reagent mass to sample mass ratio. The degree of solubilization of these sample classes are compared to the fluoride stoichiometry that is theoretically necessary to enact complete fluorination of the sample types. Finally, the sample decomposition method is performed on several soil and pitchblende ore standard reference materials, after which elemental constituent analysis is performed by ICP-OES and ICP-MS. Elemental recoveries are compared to the certified values; results indicate generally good to excellent recoveries across a range of alkaline earth, rare earth, transition metal, and actinide elements.

The growing interest but limited availability of 89Zr for PET led us to test targets for the 89Y(p,n) reaction. The goal was an easily constructed target for an 11MeV Siemens cyclotron. Yttrium foils were tested at different thicknesses, angles and currents. A 90° foil tolerated 41µA without damage and produced ~800 MBq/h, >20mCi, an amount adequate for radiochemistry research and human doses in a widely available accelerator. This method should translate to higher energy cyclotrons.

Astatine-211 (211At) is a promising cyclotron-produced radionuclide being investigated for use in targeted alpha therapy. The wet chemical isolation of trace quantities of 211At, produced within several grams of Bi metal deposited onto an aluminum cyclotron target assembly, involves a multi-step procedure. Because the 211At isolation method is labor-intensive and complex, automation of the method is being developed to facilitate routine processing at the University of Washington and to make it easier to transfer the process to other institutions. As part of that automation effort, a module useful in the initial step of the isolation procedure, dissolution of the Bi target, was designed and tested. The computer-controlled module performs in-line dissolution of Bi metal from the target assembly using an enclosed target dissolution block, routing the resulting solubilized 211At/Bi mixture to the subsequent process step. The primary parameters involved in Bi metal solubilization (influent HNO3 concentration and flow rate) were optimized prior to evaluation of the system using replicate 211At-bearing cyclotron irradiated targets. The results indicate that the system performs in a predictable and reproducible manner, with cumulative Bi and 211At recoveries following a sigmoidal function.

Destructive analysis, complete with radiochemical separation of the radionuclide(s) of interest from the sample matrix and potential interferences, is a fundamental and often critical component of radioanalytical measurements. Faster automated methods for radiochemical separation and analysis are needed to support radioanalytical laboratories. In addition, automation is required to move destructive analysis methods from the laboratory to on-line monitoring applications at nuclear facilities, and to sense radionuclides in the environment, at-site or in situ . Automation offers many significant advantages, including more consistent analytical protocols, increased reliability, improved safety, and reduced worker exposure to radioactivity, as well as shorter analysis times, higher throughput, and lower costs. In addition, automation can enable measurements that are not currently considered feasible, because they are too costly and time consuming for manual laboratory analysis, or too difficult to deploy on-line or at-site. Currently, radiochemical automation is either practiced or under development in the following areas: analysis of spent fuel to support nuclear safeguards, analysis of environmental samples related to management of nuclear sites, bioassay samples, automated monitoring for industrial-scale nuclear processes, sensing systems for radionuclides in environmental water samples, heavy element research, and medical isotope generation. This chapter presents principles and selected applications of automation in radiochemical separations, analysis, monitoring, and sensing, with comprehensive citations to the literature.

Production of the important 99mTc medical isotope parent, molybdenum-99 (99Mo), via the fissioning of high- and low-enriched uranium (HEU/LEU) targets followed by target dissolution in acid and solution-phase purification of 99Mo is time-consuming, generates quantities of corrosive radioactive waste, and can result in the release of an array of radionuclides to the atmosphere. An alternative 99Mo purification method has been devised that has the potential to alleviate many of these issues. Herein, we demonstrate the feasibility of a rapid Mo/Tc gas-phase separation from UO2. The results indicate that volatile [99Mo]Mo can be captured downstream of the reacted solid mixture on a column bed (trap) of alumina; the majority of the captured [99Mo]Mo can be subsequently eluted from the alumina trap with a few milliliters of water. >1.0 × 105 single pass decontamination of U and the collected [99Mo]Mo product is demonstrated. This simple thermo-fluorination technique has the potential to provide a rapid methodology for routine 99Mo production.

In ultralow Pu analyses, the gold standard is thermal ionization mass spectrometry (TIMS), which requires pure sources to achieve its performance. This purity is achieved through step-wise purifications. In this work single, anion-exchange beads were trapped in the tubing to allow for dynamic solution cycling over the surface of the beads to improve the rates of metal complex uptake. Rates of Pu sorption on single ∼900 μm SIR-1200 and ∼620 μm Reillex-HPQ beads were determined for single beads trapped in a tube with syringe pump driven dynamic solution cycling over the bead, improving sorption and desorption rates. A static control was used as a comparison. Using 238Pu to enable facile activity-based measurements, rates were determined by measuring the residual Pu after contact with beads using liquid scintillation analysis (LSA) for fixed periods of time. Syringe pump driven dynamic solution cycling results in ∼5 and ∼15-fold improvements in the sorption rates for SIR-1200 and Reillex-HPQ. Impacts on desorption were also examined.

The development of a tandem column purification method for the preparation of high-purity 89Zr(IV) oxalate is presented. The primary column was a macroporous strongly basic anion exchange resin on styrene divinylbenzene co-polymer. The secondary column, with an internal volume of 33 μL, was packed with hydroxamate resin. A condition of inverted selectivity was developed, whereby the 89Zr eluent solution for the primary column is equivalent to the 89Zr load solution for the secondary column. The ability to transfer 89Zr from one column to the next allows two sequential column clean-up methods to be performed prior to the final elution of the 89Zr(IV) oxalate. This approach assures delivery of high purity 89Zr product and assures a 89Zr product that is eluted in a substantially smaller volume than is possible when using the traditionally-employed single hydroxamate resin column method. The tandem column purification process has been implemented into a prototype automated fluidic system. The system is configured with on-line gamma detection so column effluents can be monitored in near-real time. The automated method was tested using seven cyclotron bombarded Y foil targets. It was found that 95.1 ± 1.3% of the 89Zr present in the foils was recovered in the secondary column elution fraction. Furthermore, elution peak analysis of several 89Zr elution profile radiochromatograms made possible the determination of 89Zr recovery as a function of volume; a 89Zr product volume that contains 90% of the mean secondary column elution peak can be obtained in 0.29 ± 0.06 mL (representing 86 ± 5% of the 89Zr activity in the target). This product volume represents a significant improvement in radionuclide product concentration over the predominant method used in the field. In addition to the reduced 89Zr product elution volume, titrations of the 89Zr product with deferoxamine mesylate salt across two preparatory methods resulted in mean effective specific activity (ESA) values of 279 and 340 T Bq·mmole−1 and mean bindable metals concentrations ([MB]) of 13.5 and 16.7 nmole·g−1. These ESA and [MB] values infer that the 89Zr(IV) oxalate product resulting from this tandem column isolation method has the highest purity reported to date.

Magnetic nanoparticles are well known to possess chemically active surfaces and large surface areas that can be employed to extract a range of ions from aqueous solutions. Additionally, their superparamagnetic properties provide a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. Herein, two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes, were evaluated for their ability to collect trace levels of a chemically diverse range of alpha emitting radioactive isotopes (polonium (Po), radium (Ra), uranium (U), and americium (Am)) from a wide range of aqueous solutions. The nanomaterials include commercially available magnetite (Fe(3)O(4)) and magnetite modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1. Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the alpha-emitting radionuclide spikes from ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. We show that the uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified ground water was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. Overall, the results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions.

Zirconium-89 (

© 2017 The Royal Society of Chemistry. Solid sampling and analysis methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), are challenged by matrix effects and calibration difficulties. Matrix-matched standards for external calibration are seldom available and it is difficult to distribute spikes evenly into a solid matrix as internal standards. While isotopic ratios of the same element can be measured to high precision, matrix-dependent effects in the sampling and analysis process frustrate accurate quantification and elemental ratio determinations. Here we introduce a potentially general solid matrix transformation approach entailing chemical reactions in molten ammonium bifluoride (ABF) salt that enables the introduction of spikes as tracers or internal standards. Proof of principle experiments show that the decomposition of uranium ore in sealed PFA fluoropolymer vials at 230 °C yields, after cooling, new solids suitable for direct solid sampling by LA. When spikes are included in the molten salt reaction, subsequent LA-ICP-MS sampling at several spots indicate that the spikes are evenly distributed, and that U-235 tracer dramatically improves reproducibility in U-238 analysis. Precisions improved from 17% relative standard deviation for U-238 signals to 0.1% for the ratio of sample U-238 to spiked U-235, a factor of over two orders of magnitude. These results introduce the concept of solid matrix transformation (SMT) using ABF, and provide proof of principle for a new method of incorporating internal standards into a solid for LA-ICP-MS. This new approach, SMT-LA-ICP-MS, provides opportunities to improve calibration and quantification in solids based analysis. Looking forward, tracer addition to transformed solids opens up LA-based methods to analytical methodologies such as standard addition, isotope dilution, preparation of matrix-matched solid standards, external calibration, and monitoring instrument drift against external calibration standards.

Zirconium-89 (

Radioactive contamination, be it from accidental or intentional release, can create an urgent need to assess water and food supplies and the environment, and monitor human health. In the event of such an emergency, rapid and efficient methods may be needed to assess contamination levels in scores of samples within a short time frame. Internalized exposure to radionuclides that decay by alpha (α) emission can be especially hazardous, given the strongly ionizing nature of the α particle. Unfortunately, the determination of α-emitting radionuclides using traditional radioanalytical methods is typically labor and resource intensive and time consuming. In an effort to devise methods that are fast, require little labor and laboratory expendables, and minimize the use of toxic or corrosive reagents, researchers at PNNL have evaluated superparamagnetic nanoparticles as extracting agents for α-emitting radionuclides from chemically unmodified and acidified (pH 2) aqueous systems. It is demonstrated that bare magnetite nanoparticles exhibit strong affinity for two representative α-emitting radionuclides ((241)Am and (210)Po) from two representative aqueous matrices (river and ground water). Furthermore, use of the superparamagnetic properties of these nanomaterials to concentrate the analyte-bearing solids from the bulk aqueous solution has been demonstrated. The nanoparticle concentrate can be either directly dispensed into a scintillation cocktail, or first dissolved and then added to a scintillation cocktail as a solution for an α-emission assay by liquid scintillation analysis. Despite the severe quenching caused by the metal oxide suspensions in the cocktail, the authors have demonstrated that modern liquid scintillation analyzers can report accurate α activity count rates; the upper limits of nanoparticle suspension concentrations in a cocktail are reported for cases wherein normal instrument count mode and a quench correction protocol are used. Discussions are provided on the presented sample processing and analysis method, the improvement (lowering) of minimum detectable activity concentrations using the nanoparticle-based assay method, and the quenching effects of nanoparticle suspensions in a scintillation cocktail.

The growing interest but limited availability of 89Zr for PET led us to test targets for the 89Y(p,n) reaction. The goal was an easily constructed target for an 11 MeV Siemens cyclotron. Yttrium foils were tested at different thicknesses, angles and currents. A 90° foil tolerated 41 μA without damage and produced ~800 MBq/h, > 20 mCi, an amount adequate for radiochemistry research and human doses in a widely available accelerator. This method should translate to higher energy cyclotrons.

A sample preparation sequence for actinide isotopic analysis by thermal ionization mass spectrometry (TIMS) is described that includes column-based extraction chromatography as the first separation step, followed by anion-exchange column separations. The sequence is designed to include a wet ashing step after the extraction chromatography to prevent any leached extractant or oxalic acid eluent reagents from interfering with subsequent separations, source preparation, or TIMS ionization. TEVA resin and DGA resin materials, containing extractants that consist only of C, N, O, and H atoms, were investigated for isolation of plutonium. Radiotracer level studies confirmed expected high yields from column-based separation procedures. Femtogram-level studies were carried out with TIMS detection, using multiple monoisotopic spikes applied sequentially throughout the separation sequence. Pu recoveries were 87% and 86% for TEVA and DGA resin separations, respectively. The Pu recoveries from 400 μL anion-exchange column separation sequences were 89% and 93% for trial sequences incorporating TEVA and DGA resin. Thus, a prior extraction chromatography step in the sequence did not interfere with the subsequent anion-exchange separation when a simple wet ash step was carried out in between these column separations. The average measurement efficiency for Pu, encompassing the chemical separation recoveries and the TIMS ionization efficiency, was 2.73% ± 0.77% (2σ) for the DGA resin trials and 2.67% ± 0.54% for the TEVA resin trials, compared to 3.41% and 2.37% (average 2.89%) for two control trials. These compare with an average measurement efficiency of 2.78% ± 1.70%, n = 33 from process benchmark analyses using Pu spikes processed through a sequence of oxalate precipitation, wet ash, iron hydroxide precipitation, and anion-exchange column separations. We conclude that extraction chromatography can be a viable separation procedure as part of a multistep sequence for TIMS sample preparation.

Two automated systems have been developed to perform column-based radiochemical separation procedures. These new systems are compared with past fluidic column separation architectures, with emphasis on using disposable components so that no sample contacts any surface that any other sample has contacted, and setting up samples and columns in parallel for subsequent automated processing. In the first new approach, a general purpose liquid handling robot has been modified and programmed to perform anion exchange separations using 2 mL bed columns in 6 mL plastic disposable column bodies. In the second new approach, a fluidic system has been developed to deliver clean reagents through disposable manual valves to six disposable columns, with a mechanized fraction collector that positions one of four rows of six vials below the columns. The samples are delivered to each column via a manual 3-port disposable valve from disposable syringes. This second approach, a hybrid of fluidic and mechanized components, is a simpler more efficient approach for performing anion exchange procedures for the recovery and purification of plutonium from samples. The automation architectures described can also be adapted to column-based extraction chromatography separations.

In the event of an accidental or intentional release of radionuclides into a populated area, three things must occur in a timely manner: food and drinking water supplies must be determined to be safe to eat / drink, civilians and/or military personnel must be surveyed to ensure that they do not have external contamination, and they must be screened to ensure that significant ingestion or inhalation of radionuclides has not occurred (this paper is concerned with the latter). In the event of such a disaster, the volume of radiobioassays to be performed would be tremendous. If the event released significant levels of β- or α-emitting radionuclides, in vivo assays would be ineffective. Therefore, highly efficient and rapid analytical methods for radionuclide detection from submitted spot urine samples (≤ 50 mL) would be required. At present, the quantitative determination of α-emitting radionuclides from urine samples is highly labor intensive, and requires significant sample preparation and analysis time. Sorbent materials that provide effective collection and enable rapid assay could significantly streamline the radioanalytical process. We have demonstrated the use of paramagnetic nanoparticles as a novel class of extracting media for four α-emitting radionuclides of concern (Po, Ra, Am, and U) from chemicallymore » unmodified and pH 2 human urine. Herein the initial experimental sorption results are presented along with a novel method that utilizes paramagnetic nanoparticles for the extraction of radionuclides from unmodified human urine followed by the magnetic field-induced collection of the particles for subsequent α-counting-source preparation. Additionally, we construct a versatile human dose model that determines the detector count times required to estimate internal human dose at specific protective action thresholds. The model provides a means to assess a method’s detection capabilities and use fundamental health physics parameters and actual experimental data as core variables. The modeling shows that with effective sorbent materials, rapid screening for internalized α-emitters is possible from a 50 mL spot urine sample volume collected within one week of exposure/intake.« less

Colipila, a new member of the Helotiales, is erected for two previously undescribed lignicolous species resembling Dasyscyphella and Lachnum by macroscopy. Species of Colipila are characterized by their long, entirely smooth, hyaline, thin-walled, multiseptate, subulate to basally fusoid hairs that tend to be curved on the stipe and lower flanks, and dimorphic, partly strongly protruding paraphyses which closely resemble the hairs. The type species, C. masduguana, is recorded repeatedly in southern France on rotten decorticated branches and trunks of Castanea sativa on the moist forest floor in sub-Mediterranean regions with siliceous soils, but also once on Quercus robur in a temperate forest with calcareous soil. The second species, C. pilatensis, was found on wood of an unidentified member of Rosaceae in a calcareous region of the Northern Alps and is known only from the holotype. The phylogenetic position of C. masduguana within the Helotiales was not resolved based on the analysis of nuclear LSU ribosomal DNA sequences. A key to the species of Colipila is provided.

Characterization of SuperLig® 620 solid phase extraction resin was performed in order to develop an automated on-line process monitor for 90Sr. The main focus was on strontium separation from barium, with the goal of developing an automated separation process for 90Sr in high-level wastes. High-level waste contains significant 137Cs activity, of which 137mBa is of great concern as an interference to the quantification of strontium. In addition barium, yttrium and plutonium were studied as potential interferences to strontium uptake and detection. A number of complexants were studied in a series of batch Kd experiments, as SuperLig® 620 was not previously known to elute strontium in typical mineral acids. The optimal separation was found using a 2 M nitric acid load solution with a strontium elution step of ~0.49 M ammonium citrate and a barium elution step of ~1.8 M ammonium citrate. 90Sr quantification of Hanford high-level tank waste was performed on a sequential injection analysis microfluidics system coupled to a flow-cell detector. The results of the on-line procedure are compared to standard radiochemical techniques in this paper.

We have developed automated sensor and monitoring devices for trace radionuclides in water, using preconcentrating columns and radiometric detection. The preconcentrating minicolumn sensor concept combines selective capture and detection in a single functional unit. We have demonstrated quantification of radionuclides such as technetium-99 to levels below drinking water standards in an equilibration-based process that produces steady state signals, signal proportional to concentration, and easy re-equilibration to new concentration levels. Alternatively, monitors can be developed with separate separation and detection units that are fluidically linked. We have demonstrated detection of strontium-90 to levels below drinking water standards by this approach. We are developing autonomous systems for at-site monitoring on the Hanford Site in Washington State.

We report a convenient method for the generation of volatile uranium hexafluoride (UF6) from solid uranium oxides and other U compounds, followed by uniform deposition of low levels of UF6 onto sampling coupons. Under laminar flow conditions, UF6 is shown to interact with surfaces within a fixed reactor geometry to a highly predictable degree. We demonstrate the preparation of U deposits that range between approximately 0.01 and 500ngcm(-2). The data suggest the method can be extended to creating depositions at the sub-picogramcm(-2) level. The isotopic composition of the deposits can be customized by selection of the U source materials and we demonstrate a layering technique whereby two U solids, each with a different isotopic composition, are employed to form successive layers of UF6 on a surface. The result is an ultra-thin deposit that bears an isotopic signature that is a composite of the two U sources. The reported deposition method has direct application to the development of unique analytical standards for nuclear safeguards and forensics. Further, the method allows access to very low atomic or molecular coverages of surfaces.

Direct determination of 99Tc in groundwater using a sensor device represents a substantial challenge due to the short range of beta-particles, the presence of radiological interferences, and low-level detection requirements. This paper describes a radiochemical sensing method for selective detection of 99Tc(VII) in water. The sensing approach uses a dual-function composite sensor microcolumn that incorporates both selective sorption and scintillating properties. Analyte detection is carried out in a reagentless equilibration sensing regime using chemically unmodified groundwater. The sensor method was implemented in a prototypical probe device that integrates the sensor element, scintillation detection, data acquisition, and instrument control components in a single functional instrument compatible with a 3.5" well casing geometry. The feasibility of rapid 99Tc analysis in Hanford groundwater (Hanford Site, USA) below regulatory drinking water level of 33 Bq/l was demonstrated.

The present study evaluated the feasibility of direct measurement of alpha emitting radionuclides in liquids using passivated ion implanted planar silicon (PIPS) diode detectors. The performance characteristics and durability of PIPS diode detectors enabled direct detection of alpha particles from liquid samples by placing the diode detector in close proximity to the liquid sample. Factors affecting the sensitivity and accuracy of direct detection of alpha-emitters in solution and interferences of beta/gamma emitters have been examined. Direct assay of liquid samples using PIPS diode detectors can enable rapid and straightforward detection methodologies suitable for process control applications.

A fully automated analysis procedure and instrument for the measurement of total 99Tc in aged nuclear waste has been developed. The overall analysis approach is based on a fully automated wet radiochemical analysis method. Microwave-assisted sample oxidation is used prior to a chemical separation step in order to oxidize all of the non-pertechnetate species to pertechnetate. Separation of the pertechnetate from interfering radioactive and stable matrix species is carried out using an anion-exchange column. The separated 99Tc is quantified using a flow-through solid cell scintillation detector. The instrument is capable of an analysis time of

The determination of transuranic (TRU) content in nuclear wastes, reactor materials, process solutions, and various other matrices is required in support of material assessment, environmental restoration, and waste processing activities. We have found that direct measurement of TRU is possible using surface passivated ion implanted planar silicon diode detectors. The performance and durability of modern silicon diodes enables direct detection of alpha-particles, with retention of some spectral information, through small air gaps or under direct contact with liquid or solid samples. We will present results on the performance of silicon diode detectors for the determination of TRU in liquids.

Direct alpha-energy spectroscopy in liquids is possible by placing a chemically selective polymer thin film upon the surface of passivated silicon diodes. By utilizing polymer thin films with high affinity for actinides, we have been able to selectively concentrate actinides of interest upon the diode surface, resulting in a substantial increase in sensitivity relative to a direct measurement. With this film coated diodes, we were able to obtain in-situ alpha spectra with energy resolution comparable to that of conventional alpha-spectroscopy. The response of the thin film coated diode was found to be linear over 104. The sensitivity and reversibility is a function of the membrane complexation chemistry.

A sequential injection (SI) separation system has been developed for separation and analysis of Am, Pu, and Np isotopes using on-line inductively coupled plasma mass spectrometry (ICP MS) detection. On-line actinide separations were carried out using an actinide-specific extraction chromatographic material (TRU-resin, Eichrom Industries, Inc. USA). Separations are demonstrated and characterized that are compatible with on-line ICP MS detection and address isobaric (241Am/241Pu, 244Pu/244Cm, 238U/238Pu), molecular (238UH/239Pu), and spectral (238U/237Np) interferences encountered in the analysis of Am, Pu and Np isotopic composition using ICP MS. The effects of reductive sample treatment on the extent of U matrix removal were investigated. Uranium separation factors were limited by the formation of U(IV) species, which exhibited separation behaviors similar to that of Pu(IV) and Np(IV). Nevertheless, separation factors as high as 3.0 × 105 can be achieved at the 0.1 mg ml−1 U concentration levels using Fe(II) sulfamate as a reductant. The sequential injection (SI) ICP MS technique has been applied towards analysis of Am, Pu, and Np isotopes in a dissolved vitrified nuclear waste sample. Results obtained using the automated separation technique with ICP MS detection were in satisfactory agreement with results obtained using standard analytical methodologies.

A method for chemically selective radiometric sensing of non-γ-emitting radionuclides in solution is described. Using scintillating microspheres with selective radionuclide uptake properties, radiochemical separation and radiometric detection steps are integrated within a sensor device. These microspheres are loaded into a renewable minicolumn that serves to capture, preconcentrate, and separate radionuclides. The preconcentrating minicolumn also localizes and retains radionuclides within a detector of well-defined geometry and emits a photometric signal. The sensor material in the column can either be regenerated with eluent chemistries or be renewed by fluidic replacement of the beads. The latter method allows the use of materials that bind analytes irreversibly or are unstable under regeneration conditions. Radionuclide-selective scintillating microspheres were prepared by coimmobilization of scintillating fluors and selective organic extractants within the pores of an inert polymeric support. Preparation and characterization of microspheres, and their use for selective quantitative sensing of (99)Tc(VII), is described in detail. A sensor-based procedure for (99)Tc(VII) analysis was developed and successfully applied toward the determination of (99)Tc(VII) in groundwater samples from the Hanford site, using standard addition techniques for quantification. Using a 50-mL sample volume and signal accumulation time of 30 min, the detection limit for (99)Tc(VII) was 0.37 dpm/mL (9.8 pg/mL).

A novel approach to the automation of sorbent extraction separations is described. An advanced sequential injection renewable separation column (SI-RSC) instrument was designed and optimized for automatically packing a separation column on-line, using it for a separation, and then disposing of the used separation material. Column packing/separation material disposal steps are accomplished fluidically using a frit restriction. Using a 250-μL renewable column, procedures were developed for the separation and analysis of 90Sr, 241 Am, and 99 Tc in aged nuclear waste samples employing Sr-resin, TRU-resin, and TEVA-resin sorbent extraction materials (Eichrom Industries). The separation performance of the RSC was identical to that of a freshly packed conventional column of similar size. With a renewable column, it is not necessary to elute all species from the column, carryover on the column from one separation to the next is eliminated, the same instrument can be used for multiple separations requiring different sorbent extraction media without physical changes to the instrument (sorbent extraction medium is selected in software), and the sorbent extraction material can be recovered for analysis of noneluted species.

An automated procedure for the determination of (99)Tc in aged nuclear waste has been developed. Using advanced sequential injection (SI) analysis instrumentation, (99)Tc(VII) is separated from radioactive and stable interferences using a TEVA resin column that selectively retains pertechnetate ion from dilute nitric acid solutions. The separated (99)Tc is eluted with 6 M nitric acid and quantified on-line with a flow-through liquid scintillation detector. A stopped-flow technique has been optimized that improves the analysis precision and detection limit compared to continuous-flow detection, reduces consumption of liquid scintillation cocktail, and increases sample throughput by separating the next sample while the present sample is being counted. The detection limit is 30 pCi, or 2 ng, of (99)Tc, using a 15-min stopped-flow period. The analysis time is 40 min for the first sample and is reduced to 20 min for each subsequent sample. Processed nuclear waste samples from the Hanford site were successfully analyzed by this new method.

Executive Summary A 99Tc Process Monitoring (Tc-Mon) System has been designed and built for deployment at the recently constructed 200 West Pump & Treat (200W PT therefore, once they have reached their maximum useful capacity, the columns must be disposed of as radioactive waste. The Tc-Mon system’s primary duty will be to periodically sample and analyze the effluents from each of the two primary extraction columns to determine 99Tc breakthrough. The Tc-Mon system willmore » enable the CH2M Hill Plateau Remediation Company (CHPRC) to measure primary extraction column breakthrough on demand. In this manner, CHPRC will be able to utilize each extraction column to its maximum capacity. This will significantly reduce column disposal and replacement costs over the life of the plant. The Tc-Mon system was constructed by Burge Environmental, Inc. and was delivered to PNNL in June 2013 for setup and initial hardware and software performance testing in the 325 Building. By early July, PNNL had initiated an in-laboratory performance characterization study on the system. The objective was to fully calibrate the system and then evaluate the quality of the analytical outputs 1) against a series of clean groundwater samples prepared as 99Tc standards, and 2) on actual 200W P&T Plant grab samples containing 99Tc (and other radioactive and non-radioactive contaminants) at levels reported by the Waste Sampling and Characterization Facility. These grab samples included pre-treated (Pre-Resin) and post-treated (Post-Resin) 200W P&T Plant waters for May through August 2013. This report contains the following information: • The genesis of the 99Tc sensor and the Tc-Mon analytical system. • A description of the Tc-Mon system’s major hardware and software components. • A description of the operational principles behind the 99Tc sensor. • Results from the calibration of three components within the Tc-Mon system. The three systems requiring calibration are: 1. Sampling Chamber 2. Conductivity Sensor 3. 99Tc Sensor • Presentation of analytical results obtained on the fully calibrated Tc-Mon system. This includes a determination of the precision and accuracy of each system defined above. • Estimation of the 99Tc sensor’s minimum detectable activity and limit of quantification. • A brief discussion of potential chemical and radiological influences on the 99Tc sensor based on known contaminants in 200W P&T Plant water. • Observations regarding 99Tc sensor longevity.« less

An automated fluidic instrument is described that rapidly determines the total (99)Tc content of aged nuclear waste samples, where the matrix is chemically and radiologically complex and the existing speciation of the (99)Tc is variable. The monitor links microwave-assisted sample preparation with an automated anion exchange column separation and detection using a flow-through solid scintillator detector. The sample preparation steps acidify the sample, decompose organics, and convert all Tc species to the pertechnetate anion. The column-based anion exchange procedure separates the pertechnetate from the complex sample matrix, so that radiometric detection can provide accurate measurement of (99)Tc. We developed a preprogrammed spike addition procedure to automatically determine matrix-matched calibration. The overall measurement efficiency that is determined simultaneously provides a self-diagnostic parameter for the radiochemical separation and overall instrument function. Continuous, automated operation was demonstrated over the course of 54 h, which resulted in the analysis of 215 samples plus 54 hly spike-addition samples, with consistent overall measurement efficiency for the operation of the monitor. A sample can be processed and measured automatically in just 12.5 min with a detection limit of 23.5 Bq/mL of (99)Tc in low activity waste (0.495 mL sample volume), with better than 10% RSD precision at concentrations above the quantification limit. This rapid automated analysis method was developed to support nuclear waste processing operations planned for the Hanford nuclear site.

Catenulifera , typified by C. rhodogena (= Scopulariopsis rhodogena ), was established to accommodate the anamorphs of Hyphodiscus (Ascomycota , Helotiales ) and to delimit these taxa from members of Phialophora section Catenulatae . Catenulifera rhodogena has been inferred as monophyletic, but its relationship to ascomycetes with poorly differentiated phialidic anamorphs remains enigmatic. To test the hypothesis that C. rhodogena is closely related to morphologically similar species of Phialophora and to further explore the systematics of Catenulifera , we analyzed nuclear rDNA and β-tubulin gene sequences of isolates identified as C. rhodogena , Hyphodiscus hymeniophilus , P. brachyconia , P. brevicollaris and P. hyalina . ITS–LSU and ITS–LSU-β-tubulin phylogenies positioned all isolates except P. hyalina in a single, well-supported clade that consisted of three subclades. Subclade 1 included fungicolous isolates of C. rhodogena and H. hymeniophilus that did not fluoresce when exposed to long-wave UV light. Subclade 2 contained fungicolous and lignicolous strains of C. rhodogena that produced fluorescent colonies and possessed a 366 bp indel in the LSU rRNA gene. Neither lineage encompassed the ex-type strains of Cistella rubescens (= H. hymeniophilus ) or S. rhodogena , but the former isolate was inferred as sister to Subclade 2. Subclade 3 included all isolates of P. brachyconia , a species recognized here as C. brachyconia comb. nov. A fourth isolate of P. brachyconia that was extralimital to Subclade 3 is described as C. luxurians sp. nov. The positions of C. brevicollaris comb. nov., a species based on P. brevicollaris , and C. luxurians were not resolved in the ITS–LSU phylogeny. P. hyalina is not closely related to Catenulifera .

A preconcentrating minicolumn sensor for technetium-99 detection in water consists of a packed bed containing a mixture of anion-exchange resin and scintillating plastic beads. The column materials are contained in a transparent plastic flow cell placed between two photomultiplier tubes for radiometric detection. Upon retention of pertechnetate anions, the radioactive decay of Tc-99 results in detectable scintillation pulses that are counted in coincidence. In equilibration-based sensing mode, the sample is pumped through the packed bed until complete chromatographic equilibrium is achieved between the activity concentration in the water sample and the concentration on the anion-exchange resin. The analytical signal is the observed steady-state count rate at equilibrium. The sensitivity is related to a measurement efficiency parameter that is the product of the retention volume and the absolute radiometric detection efficiency. This sensor can readily detect pertechnetate to levels 10 times below the drinking water standard of 0.033 Bq/mL. The potential for other anions in natural groundwater and contaminated groundwater plumes to interfere with pertechnetate detection and quantification has been examined in detail, with reference to the groundwater chemistry at the Hanford site in Washington state. Individual anions such as nitrate, carbonate, chloride, and iodide, at natural or elevated concentrations, do not interfere significantly with pertechnetate uptake on the anion-exchange resin. Elevated chromate or sulfate anion concentrations can interfere with pertechnetate uptake by the resin, but only at levels substantially higher than typical concentrations in groundwater or contamination plumes. Nevertheless, elevated anion concentrations may reduce pertechnetate uptake and sensitivity of the sensor when present in combination. Chromate is retained on the anion-exchange resin from water at parts-per-billion levels, leading to an orange stain that interferes with pertechnetate detection by the absorption of scintillation light pulses (color quench). Radioactivity from radioiodine, tritium, and uranium is not expected to create a significant positive bias in groundwater analyses. A method of automated fluidic standard addition is demonstrated that corrects for matrix interferences leading to accurate analyses over a wide range of groundwater compositions. This method is developed for automated groundwater monitoring applications.

Strontium-90 is an environmental contaminant at several U.S. Department of Energy sites, including the Hanford site, Washington. Due to its high biological toxicity and moderately long half-life of approximately 29 years, groundwater and surface water contamination plumes containing 90Sr must be closely monitored. The highly energetic beta radiation from the short-lived 90Y daughter of 90Sr generates Cherenkov photons in aqueous media that can be detected by photomultiplier tubes with good sensitivity, without the use of scintillation cocktails. A laboratory-based automated fluid handling system coupled to a Cherenkov radiation detector for measuring 90Sr via the high-energy beta decay of its daughter, 90Y, has been assembled and tested using standards prepared in Hanford groundwater. A SuperLig 620 column in the system enables preconcentration and separation of 90Sr from matrix and radiological interferences and, by removing the 90Y present in the sample, creates a pure 90Sr source from which subsequent 90Y ingrowth can be measured. This 90Y is fluidically transferred from the column to the Cherenkov detection flow cell for quantification and calculation of the original 90Sr concentration. Preconcentrating 0.35 L sample volumes by this approach, we have demonstrated a detection limit of 0.057 Bq/L using a 5 mL volume Cherenkov flow cell, which is below the drinking water limit of 0.30 Bq/L. This method does not require that the sample be at secular equilibrium prior to measurement. The system can also deliver water samples directly to the counting cell for analysis without preconcentration or separation, assuming that the sample is in secular equilibrium, with a detection limit of 7 Bq/L. The performance of the analysis method using a preconcentrating separation column is characterized in detail and compared with direct counting. This method is proposed as the basis for an automated fluidic monitor for 90Sr for unattended at-site operation.

This report was revised in September 2008 to remove acid-extractable sodium data from Table 4.17. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc., asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is the fourth in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from a slant borehole installed beneath tank SX-108 (or simply SX-108 slant borehole).

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.14, 4.16, 5.20, 5.22, 5.43, and 5.45. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc. asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is one in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from Resource Conservation and Recovery Act (RCRA) borehole bore samples and composite samples.

This report was revised in September 2008 to remove acid-extractable sodium data from Table 5.15. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc., asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is one in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from borehole 41-09-39 installed adjacent to tank SX-109.

The use of acoustic streaming as a noncontact mixing platform to accelerate mass-transport-limited diffusion processes in small-volume heterogeneous reactions has been investigated. Single-bead anion exchange of plutonium at nanomolar and subpicomolar concentrations in 20 microL liquid volumes was used to demonstrate the effect of acoustic mixing. Pu uptake rates on individual approximately 760 microm diameter AG 1 x 4 anion-exchange resin beads were determined using acoustic mixing and compared with Pu uptake rates achieved by static diffusion alone. An 82 MHz surface acoustic wave (SAW) device was placed in contact with the underside of a 384-well microplate containing flat-bottomed semiconical wells. Acoustic energy was coupled into the solution in the well, inducing acoustic streaming. Pu uptake rates were determined by the plutonium remaining in solution after specific elapsed time intervals using liquid scintillation counting (LSC) for nanomolar concentrations and thermal ionization mass spectrometry (TIMS) analysis for the subpicomolar concentration experiments. It was found that this small batch uptake reaction could be accelerated by a factor of about 5-fold or more, depending on the acoustic power applied.

The development of in situ sensors for ultratrace detection applications in process control and environmental monitoring remains a significant challenge. Such sensors must meet difficult detection limit requirements while selectively detecting the analyte of interest in complex or otherwise challenging sample matrixes. Nowhere are these requirements more daunting than in the field of radionuclide sensing. The detection limit requirements can be extremely low. Nevertheless, a promising approach to radionuclide sensing based on preconcentrating minicolumn sensors has been developed. In addition, a method of operating such sensors, which we call equilibration-based sensing, has been developed that provides substantial preconcentration and a signal that is proportional to analyte concentration, while eliminating the need for reagents to regenerate the sorbent medium following each measurement. While this equilibration-based sensing method was developed for radionuclide sensing, it can be applied to nonradioactive species as well, given a suitable on-column detection system. By replacing costly sampling and laboratory analysis procedures, in situ sensors could have a significant impact on monitoring and long term stewardship applications. The aim of this review is to cover radionuclide sensors that combine some form of selective sorption with a radiometric detection method, and­as a primary aim­to comprehensively review preconcentrating minicolumn sensorsmore » for radionuclide detection. As a secondary aim, we will cover radionuclide sensors that combine sorption and scintillation in formats other than minicolumn sensors. We are particularly concerned with the detection of alpha- and beta-emitting radionuclides, which present particular challenges for measurements in liquid media.« less

Hexavalent chromium Cr(VI) is a notorious ground water contaminant toxic to humans and animals. Assessment of an exposure risk for aquatic receptors necessitates frequent Cr(VI) concentration data from a range of surface and groundwater locations at Cr(VI) contamination sites. In this work, we demonstrate that enhanced ultraviolet–visible (UV-vis) spectroscopy using a liquid waveguide capillary cell (LWCC) offers an easy-to-use and economical methodology for the determination of chromate anion CrO42− in Hanford natural waters without chemical pretreatment and generation of hazardous waste. Direct determination of CrO42− in actual surface and ground water samples with the complexities of competing ions, dissolved organics, and other potential interfering agents was achieved by measuring the chromate optical absorbance at 372 nm. For a 100 cm path length LWCC, the detection limit for chromate was found to be as low as 0.073 ppb. A quantitative relationship between the intensity of the absorbance signal and water pH allowed for the straightforward calculation of total Cr(VI) content in natural water. The described method is applicable for in-field monitoring of Cr(VI) in environmental water samples at trace levels.