AUTOMATED RADIOANALYTICAL CHEMISTRY: APPLICATIONS FOR THE LABORATORY AND INDUSTRIAL PROCESS MONITORING

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1 AUTOMATED RADIOANALYTICAL CHEMISTRY: APPLICATIONS FOR THE LABORATORY AND INDUSTRIAL PROCESS MONITORING ABSTRACT Matthew J. O Hara*, Anne F. Farawila, Jay W. Grate Pacific Northwest National Laboratory PO Box 999, Richland, WA 99352, USA * matthew.ohara@pnl.gov The identification and quantification of targeted α- and β-emitting radionuclides via destructive analysis in complex radioactive liquid matrices is highly challenging. Analyses are typically accomplished at on- or off-site laboratories through laborious sample preparation steps and extensive chemical separations followed by analysis using a variety of detection methodologies (e.g., liquid scintillation, alpha energy spectroscopy, mass spectrometry). Analytical results may take days or weeks to report. When an industrial-scale plant requires periodic or continuous monitoring of radionuclides as an indication of the composition of its feed stream, diversion of safeguarded nuclides, or of plant operational conditions (for example), radiochemical measurements should be rapid, but not at the expense of precision and accuracy. Scientists at Pacific Northwest National Laboratory have developed and characterized a host of automated radioanalytical systems designed to perform reproducible and rapid radioanalytical processes. Platforms have been assembled for 1) automation and acceleration of sample analysis in the laboratory and 2) automated monitors for monitoring industrial scale nuclear processes on-line with near-real time results. These methods have been applied to the analysis of environmental-level actinides and fission products to high-level nuclear process fluids. Systems have been designed to integrate a number of discrete sample handling steps, including sample pretreatment (e.g., digestion and valence state adjustment) and chemical separations. The systems have either utilized on-line analyte detection or have collected the purified analyte fractions for off-line measurement applications. One PNNL system of particular note is a fully automated prototype on-line radioanalytical system designed for the Waste Treatment Plant at Hanford, WA, USA. This system demonstrated nearly continuous destructive analysis of the soft β-emitting radionuclide 99 Tc in nuclear tank waste feed solutions. The system is compact, fully self-calibrating, and analytical results can be immediately transmitted to on- or off-site locations. This platform exemplifies how automation can be integrated into reprocessing facilities to support the needs of international nuclear safeguards and reprocessing plant operational monitoring. INTRODUCTION Some spent nuclear fuel reprocessing facilities across the globe have historically produced concentrated plutonium-bearing streams from dissolved irradiated uranium fuel. Additionally, most schemes for closing the nuclear fuel cycle involve aqueous processing schemes that could potentially be configured to separate Pu. These Pu streams have the potential for diversion and subsequent utilization in a nuclear explosive device. The International Atomic Energy Agency (IAEA) seeks to inhibit the use of nuclear materials for military purposes. It 1

2 strives to monitor such reprocessing facilities for the timely detection of the removal of one significant quantity (SQ) of nuclear material. The SQ for Pu is currently defined as 8 Kg. 1 As the capacity and throughput of current and future nuclear reprocessing plants becomes larger, near-real time accountancy (NRTA) verification will become essential to ensure that safeguards officials can achieve their objectives of SQ detection within timeliness requirements. NRTA will likely require an even greater reliance on the Safeguards Analytical Laboratory (SAL) and On-Site Laboratories (OSLs) for performing more rapid, and likely more frequent, destructive assay (DA) measurements. Indeed, Yusuke Kuno et. al. recently published that Destructive Analysis (DA) as a state-of-the-art determination technique provides the highest possible measurement accuracy, and DA is the best approach for detecting bias defects, which arise when small amounts of nuclear material are diverted over a protracted length of time. 2 It is evident that a continued and growing dependence on laboratory-based DA techniques must be balanced with an increase in sample handling capacity and analytical throughput in the safeguards laboratory. Another major future safeguard objective is the development of new on-line assay techniques that can accurately measure, in near-real time, the content of U, Pu, and minor actinides in aqueous process liquors. Without such analytical techniques, NRTA (especially remote NRTA) becomes exceedingly difficult. 3 Non-destructive analysis (NDA) technologies (i.e., sensors) would be ideal for remote, on-line NRTA, yet current on-line NDA techniques cannot achieve levels of accuracy required to measure at the SQ. Advances in rapid at-line or near-line DA methods and instrumentation, therefore, may ultimately become necessary to provide the levels of precision and accuracy necessary for timely SQ-level measurements. Even where accuracy requirements are not unusually stringent, DA is frequently the only way to determine radionuclide content in complex nuclear solutions. As is well known, alpha and beta emitters must be separated from the sample matrix prior to radiometric detection. Gamma ray emitters may be detected nondestructively, but only if the sample does not contain interfering γ-emitters or a problematic Compton continuum. Mass spectrometric analysis is inherently a DA method, and chemical separations are frequently required to overcome isobaric (e.g., 241 Pu/ 241 Am), molecular (e.g., 238 U 1 H/ 239 Pu), and spectral ( 237 Np/ 238 U) interferences that 4 may bias the measurement. Given that sample preparation and chemical separation steps are highly labor intensive and time consuming, and typically cannot be avoided prior to detection of many radionuclides, various methods of automation have been developed and employed over recent years in order to streamline the radioanalytical process. Grate and Egorov summarized the use of sequential injection-based approaches to automate the separation and detection of fission products and actinides in various nuclear waste samples 5,6 and Egorov et. al. expanded this to include automation from groundwater monitoring to nuclear waste analysis. 7 In the 19 th edition of Solvent Extraction & Ion Exchange, the research team of Grate, O Hara, and Egorov provide a comprehensive review of modern automation approaches in the field of radioanalytical chemistry, which includes both fluidic and robotic methods. 8 The vast majority of existing automation efforts have been focused on column-based separations coupled with off- or on-line detection. The use of automated sample preparation / sample pretreatment steps involving wet chemical processes (e.g., sample dilution, acid adjustment, digestion, redox adjustment of analytes, matrix spiking) have been, unfortunately, conducted almost exclusively off-line. 2

3 In nuclear processing environments that require continuous or rapid analysis intervals, traditional manual wet chemical processes are difficult, slow and expensive. Radioanalytical systems capable of automating some or all of the steps in an assay would be highly beneficial tools, both in analytical laboratories and for near-real time DA-based process monitoring. In nuclear fuel reprocessing plants, for example, such systems could be utilized by both plant operators and safeguards officials to provide NRTA information of TRU element concentrations in various nuclear process streams. This paper focuses on some of the actinide DA techniques that have been automated at PNNL. Section 1 illustrates laboratory-based automated separation platforms. They exemplify how actinide separations can be automated and coupled to either on-line detection (Section 1.1) or fraction collection for off-line quantification (Section 1.2). Additionally, scientists at PNNL designed, developed and demonstrated a prototype radionuclide process monitoring system capable of a multitude of tasks that include sample pretreatment (sample acidification, digestion, valence state adjustment), column-based separation and selective elution of analyte, flowthrough detection, data analysis and reporting in less than 15 minute intervals. 9,10,11 The system was originally designed for the analysis of 99 Tc from nuclear tank waste process streams, and was later modified to perform analyses of 90 Sr from similar nuclear waste samples. 10,12 Section 2 of this paper briefly describes the overall design and performance of this more advanced system. The examples discussed in this paper are intended to illustrate how modern fluidic systems and separations can be developed to significantly streamline radiochemistry DA. These technologies could potentially enhance the analytical throughput of the SAL and OSLs without sacrificing essential precision and accuracy performance levels. More complex systems can be constructed that can perform fully automated analyses on nuclear process solutions in near-real time. We are confident that the demonstrated technology platforms could be configured to provide rapid radiochemical assay of U and Pu (or other minor actinides) in dissolved spent fuel and other down-stream reprocessing effluents to support safeguards as well as plant operations. EXPERIMENTAL Reagents, Standards, Simulants, and Tank Waste Samples All reagents were of analytical grade. Radiochemically pure actinide ( 230 Th, 233 U, 237 Np, 239 Pu, 241 Am) and fission product ( 99 Tc and 90 Sr) standards were prepared through an in-house standards laboratory. The activity of each standard was verified by ICP-MS or liquid scintillation counting. The nuclear waste sample for SI-ICP-MS analysis was derived from a vitrified solid waste glass that was first fused using KOH KNO 3 and then dissolved in acid. Solution was diluted 100-fold prior to actinide valence adjustment and system injection. Tank waste simulant (AN-105) and Hanford tank waste samples (from tanks AN-102, AN-107, AZ- 101 and AP-104) were used for method development and testing for 99 Tc process monitor. The tank waste solutions were normalized to ~5 M Na +, as they would be prepared in the Waste Treatment Plant. Next, the tank waste solutions were Cs decontaminated by an inorganic ion exchange process likewise being developed for the WTP. No other sample pretreatment was performed prior to system injection. Various separation media was used for the three analytical systems described in this paper: SI-ICP-MS system utilized TRU Resin, µm (Eichrom Technologies, Lisle, IL); the PNX system utilized weakly basic anion exchange resin, AG 1-X4, mesh (Eichrom); 3

4 and the 99 Tc process monitoring system utilized strongly basic anion exchange resin, AG MP- 1M, mesh (Bio-Rad Laboratories, Hercules, CA). Primary Hardware Components Sequential injection chromatography systems were constructed from a variety of Kloehn (Las Vegas, NV) syringe pumps and Valco Cheminert valves (Houston, TX). Fluidic lines were constructed typically from 0.03 ID Teflon FEP tubing with ¼-28 and fittings from Upchurch Scientific (Oak Harbor, WA). The columns for the SI-ICP-MS and 99 Tc process monitoring system were constructed of parts from the OmegaChrom column system (Upchurch Scientific) and frits from the Quick-Snap column system (IsoLab, Inc., Akron, OH). Columns and cartridges utilized in the PNX system were purchased from Eichrom Technologies, Inc. (Darien, IL) and consisted of 2 cc packed beds of AG 1-X4 anion exchange resin in 6 cc SPE column barrels. Luer-fitted caps from the Rezorian column system (Sigma-Aldrich, St. Louis, MO) were attached to the column barrels in order to connect to the fluidic system. Instrument Control Software All devices were controlled using RS-232 serial communications via laptop computer which was equipped with a serial port and running Windows 2000, NT, or XP operating systems (Microsoft, Redmond, WA). Control and data analysis software was developed using LabWindows / CVI (National Instruments, Austin, TX). RESULTS & DISCUSSION 1. Description of Laboratory-Based Radioanalytical Systems Sections 1.1 and 1.2 briefly illustrate two automated chemical separation systems developed at PNNL in previous years. Both systems were designed to streamline historically manual processes in the radiochemistry laboratory. They both perform chemical separation of actinides, yet the two are highly dissimilar in their layout and purpose. Section 1.1 describes a fully analytical system for separating and measuring actinide elements in near-real time (processing single samples in sequence). Section 1.2 likewise describes a system built to automatically separate actinides. However, the distinction here is that this system processes batches of six samples simultaneously. Additionally, directly coupled measurement instrumentation is not desired. Instead, fractions of purified actinides are collected for off-line analysis in a TIMS instrument. 1.1 Separation and Analysis of Actinides Using Extraction Chromatography and ICP-MS Compared to radiometric detection techniques, ICP-MS can potentially offer greater degrees of sensitivity for longer-lived radioisotopes, with much shorter analysis times (which can translate into greater laboratory throughput). However, isobaric, molecular, and spectral interferences described above can be problematic; therefore, radiochemical separations are frequently necessary for quantitative analysis of individual isotopes. This is especially the case for actinide elements that coexist in complex nuclear process solutions. 4

5 We developed a sequential injection (SI) chromatography system for the separation and analysis of Am, Pu, and Np isotopes. 13 The actinide separations were performed using TRU Resin (CMPO and TBP) as the stationary organic phase, which has high affinity and selectivity for actinides in oxidation states III, IV and VI in nitric acid media. The method was tested using a dissolved nuclear waste glass that contained high uranium, with minor concentrations of TRU elements. The fluidic system was coupled to an ICP-MS for virtually real-time detection of the TRU elements being eluted from the TRU Resin column. The ICP-MS instrument was designed for the analysis of highly radioactive solutions, and was integrated into a glove box containment unit. The analytical system was designed so that the majority of the fluidic hardware resided in the non-radioactive environment; only the sample injection valve, the separation column itself, and a diverter valve resided within the contamination zone (Figure 1). This configuration provided substantial ease of operator access for analysis set-up and system maintenance routines. Figure 1: Schematic diagram of the SI-ICP-MS instrument. Only the sample loop, separation column, and waste diversion valve of the SI system resides within the radiological zone of the glove box ICP-MS. The SI fluid handling module & electronics reside outside the radiological control zone. The column-based separation method was easily characterized using the on-line ICP-MS instrument. We developed a rapid separation protocol that allowed the actinides in the sample to be loaded onto the TRU column, the sample matrix to be washed from the column (directed to waste), followed by a two-reagent strip mixture that assured us that 1) isobaric, molecular and spectral interferences were eliminated during delivery of analyte to the ICP-MS and 2) that the high concentration of uranium present in the samples (ranging from ~ times the TRU element concentrations) was never allowed to be introduced into the ICP-MS. Ultimately, the performance of the newly-developed method was validated against a highly characterized nuclear waste sample. The analytical results for Am (241, 243), Pu ( ), and Np (237) were in excellent agreement with independent analyses. 1.2 Analysis of Actinides Using Anion Exchange w/ Off-Line Fraction Collection The automated fluidic system described in this section is designed to process batches of samples (up to six samples per batch) in parallel. The fluidic instrument is called the Pacific Northwest Extraction (PNX) system. It is a highly versatile and flexible laboratory workstation that can perform actinide separations using a wide variety of separation media (solid phase 5

6 extraction, extraction chromatography, and ion exchange) in a variety of column / cartridge sizes and configurations. The system consists of five modules, which are illustrated in Figure 2. Figure 2, left: PNX System to perform automated parallel column separations for TIMS sample preparation. Top is actual photo of system, with a schematic of the system below. General component list: A) Sample injection pump for sample delivery via disposable syringes, B) Custom pneumatically-driven fraction collection platform, C) Separation columns mounted in overhead rack, D) reagent handling module, and E) computer control station. The reagent handling module resides outside the radiological control zone. Right: multiple column & cartridge configurations that are compatible with the PNX. This instrument (prototype system shown in figure) was originally designed for the separation / purification of trace actinides from environmental samples. Analyte fractions processed in this system are measured off-line using thermal ionization mass spectrometry (TIMS), which requires highly rigorous chemical separations of actinides from the environmental matrix and from each other. A progressive method of analyte purification is required prior to analysis, which includes sequential sample treatments using extraction chromatography resin followed by two subsequent anion exchange separations. The overhead rack (Figure 2, C) can be loaded with either 2 cc cartridges, 6 cc columns or 1 cc columns (shown in Figure 2, right). The cartridges are for commercially packed extraction chromatography materials, while the 6 and 1 cc columns are for anion exchange resin beds. The PNX s overall platform makes it highly promising for utilization in highly radioactive or corrosive environments. Its modular design and use of pneumatics for platform movement and fluid control performed outside the containment zone would make it effective and robust in hot cell or glove box environments. 6

7 2 Description of Radiochemical Assay System for On-Line Process Monitoring 2.1 Background Recently, an on-line analytical method was required in order for the Waste Treatment Plant (WTP) at Hanford, WA to determine total 99 Tc in the effluent from technetium removal columns at the concentration required to comply with the immobilized low activity waste (LAW) 99 Tc is a pure beta emitter (E β = kev) with a half-life of 2.1 x 10 5 product specifications. 14 years. It s extremely long half-life and high degree of mobility in the environment (as TcO - 4 ) makes it a radionuclide of particular concern, as it will become one of the predominant radionuclides in permanent repositories long after most of the other fission products have decayed to stable isotopes. Analysis of 99 Tc in the WTP process stream immediately down-stream of the 99 Tc removal columns was necessary to determine when column break-through of 99 Tc was occurring. In order to ensure regulatory concentration goals were met, the process stream had to be analyzed for 99 Tc on a continuous basis at increments of least four times per hour. However, because 99 Tc is a pure low-energy beta emitter, NDA of the process line would not be possible. Rather, a complex DA method of direct sampling, sample preparation, chemical separation, and detection was necessary. These tasks have historically been performed manually in the wet radiochemistry laboratory / counting facility. However, the plant s demand for continuous measurements at incredibly short analysis intervals made manual techniques impossible. A system capable of continuous, unattended operation needed to be developed. In an attempt to fulfill this need, a prototype automated on-line radioanalytical system was devised, built, and tested by the research team of Egorov, O Hara and Grate at PNNL. Although the motivation for the development of such a system was for measuring a fission product in a stream of nuclear waste solution, the application of such technology to the field of reprocessing safeguards is obvious. 2.2 Fully automated DA Instrumentation Requirements An automated system expected to perform a complete radiochemical DA (regardless of the analyte being measured) must be able to perform the six essential functions that are employed by radioanalytical laboratories. These essential functions are 1) sampling, 2) sample pretreatment, 3) performance verification (i.e., addition of radiochemical yield tracers or calibration standards), 4) separation of analyte from matrix and interfering radionuclides, 5) detection of analyte, and 6) data analysis and reporting. Figure 3 illustrates the pathway a sample must follow over the course of its analysis. While the radioanalytical laboratory can have each of these steps performed in specialized locations within the lab, an automated system must be capable of performing all necessary steps within a small footprint, and steps 1 through 5 must be either fluidically or robotically interlinked. Additionally, the control software must be capable of computing the final analytical results, taking into account not only detector output, but all dilutions, spike yield recoveries, and efficiencies of the detector(s). 7

8 Performance Verification Sampling Sample Pretreatment Separations Detection Data Reporting Figure 3: Six essential functions required for on-line radiochemical assay of process streams. 2.3 Automated Sample Pretreatment One of the most unique features of the system is the automated sample pretreatment process. The determination of 99 Tc in the LAW samples posed a significant challenge for automated near-real-time analysis. Much of the 99 Tc in the waste stream existed either as reduced species or was bound in organometallic complexes. TRU elements can likewise exist in a multitude of valence states in reprocessing solutions. Before any analytical chemistry can be performed on these analytes, the valence state(s) must be assured (and likely manipulated). For these reasons, the sample pretreatment approach must be highly robust capable of 1) sample dilution (if necessary), 2) ph adjustment, 3) destruction of organic compounds (if present), and 4) oxidation / reduction of analyte or interfering analyte(s). To accomplish these varied steps with the currently described system, syringe pumps were programmed to add ph adjusting solutions (acid/base) and redox reagent solution to the sample, and open vessel microwave digestion was employed to apply rapid and controlled heating to the sample. This unique microwave-enhanced on-line digestion process was documented by Egorov, O Hara, and Grate. 9,15 The automated sample pretreatment system performs all the steps that would likewise be required in a manual wet prep laboratory. Yet the system performed this task in only a couple of minutes while consuming no staff resources and utilizing a very small laboratory footprint. 2.4 Final Prototype On-Line Process Monitoring Platform The system architecture for the 99 Tc process monitoring system is approximated by Figure 4. The essential components are five syringe pumps (with distribution valve heads), five valves, an atmospheric pressure microwave digestion instrument, a separation column, a flowscintillation spectrometer and a laptop computer. After performing the automated sample preparation described above, the sample is transferred automatically to an anion exchange column, purified, separated, and then finally quantified on-line. Although this was a prototype system, it was designed with an eye towards a production environment: All hardware components are commercially available; the instrument is highly modular, so replacement of failed equipment would require little down time; hardware is chemically compatible with samples and reagents used; vapors generated by the microwave are efficiently routed away from the instrument and scrubbed prior to release into ventilation system. The prototype instrument performance level was mandated by the funding client, and the down-selection of this technology for use in the WTP was a competitive process. Instrument 8

9 cost, operational costs, space utilization, and operational performance were all considered. Table 1 compares various client criteria with the final outcomes of the 99 Tc process monitor performance. All client criteria were exceeded or met, with the exception of the detection limit, which was calculated at 17% higher than mandated. However, the use of improved detector shielding would have dropped this value below the client threshold. Figure 4: Simplified schematic of the 99 Tc process monitoring system. Table 1: Summary of client criteria for 99 Tc process monitoring system and listing of the resulting accomplished performance. Final Demonstrated Performance Analytical Objectives Client Criteria Feed Stream a Treated Stream b,c Analysis Rate 4 per hour (+ hourly QA) Precision ± 10% ND ± 3.3% (n = 215) Accuracy ± 15% ± 6.6% (n = 5) ± 6.6% (n = 215) Detection Limit 1.0 μci/l 1.17 ± 0.07 μci/l d Final Demonstration 40 hours continuous 54 hours Continuous e a) Feed stream 99 Tc concentration ranged from ~50 to 450 µci/l b) Treated stream 99 Tc concentration ranged from ~10.5 to 18.6 µci/l c) AZ-102 tank sample diluted into AN-105 tank simulant (25x, 30x, 35x, 40x dilutions) d) Detection limit based on the integrated baseline counts under the 99 Tc elution peak from 215 analyzed samples e) 215 samples analyzed + 54 matrix spike additions performed 9

10 Ultimately, we envision an on-line DA monitoring system to be configured in one of two ways shown in Figure 5. Under scenario A, the method of sampling from the process stream can be directly via slip-stream (at-line application). Alternatively, such a system could be located remotely in an OSL, with samples delivered to the instrument (B, near-line application). In each configuration, analytical data is generated in near-real time, and computerized data processing means that final analytical results can be delivered to the safeguards organization within minutes of the sample acquisition. Figure 5: Conceptual schematics of on-line radiochemical assay instrumentation for monitoring nuclear process streams. Shown are at-line (A) and remote (near-line) (B) automated DA systems. Each scenario provides near-real time analytical results. DISCUSSION Destructive analysis techniques (ICP-MS, TIMS, alpha spectroscopy) for the assay of actinides in highly radioactive nuclear process solutions will likely be utilized in nuclear safeguards and plant operations for years or decades to come. These DA methods have unsurpassed levels of precision and accuracy. Unfortunately, they also require that samples be handled at a radioanalytical laboratory. Given the current safeguards reliance on DA techniques and the expansion of the use of nuclear power across the globe, safeguards analytical laboratories will likely have to develop the capability for significantly higher and faster sample throughputs. Classical radiochemical analysis principles, combined with developments in selective separation chemistries for TRU elements and modern computer-controlled fluidic instrumentation, has made the development of highly effective and reliable automated analytical systems feasible. Simple automated laboratory-based workstations, like those illustrated in Section 1, can introduce a great degree of laboratory efficiency, allow better use of existing personnel, and minimize chemical and radiological dose hazards to staff. Our research team has shown, however, that fluidic instrumentation can go well beyond automated separations. The automated near-real time monitoring approach described in Section 2 exemplifies how a complete sample analysis process, from initial sample preparation to final data reporting, is possible. Our technology has been thoroughly developed and tested for the determination of 99 Tc and in Hanford tank waste samples. In addition to automated separations and on-line detection, the system performed extensive sample preparation and computercontrolled matrix spike addition. These are tasks that until now have not been demonstrated for the on-line preparation and measurement of radioactive samples for near-real time assay. We believe that the modular fluidic architecture we have developed can be reconfigured for the analysis of targeted actinides in reprocessing solutions. The ability of such a system to 10

11 directly sample and analyze dissolved spent fuel or other down-stream reprocessing solutions could provide safeguards specialists with the earliest possible measurement of actinide concentrations in effluents at various locations in the reprocessing plant. Such a system would provide a tremendous time and efficiency advantage over current DA methods that may take days for analytical results to be returned. REFERENCES 1 International Atomic Energy Agency, IAEA Safeguards Glossary, 2001 Edition, (Vienna, Austria: International Atomic Energy Agency, 2002), p Yusuke, K., et. al., Increase in the role of destructive analysis for safeguards verification a strong measure against world concerns on nuclear proliferation, Proceedings of Global 2005, Paper #169. Safeguards Analytical Laboratory, IAEA, Vienna, Austria. 3 P.C. Durst, et. al., Advanced Safeguards Approaches for New Reprocessing Facilities, PNNL-16674, Pacific Northwest National Laboratory, Richland, WA. June, D. Lariviere, et. al., Radionuclide determination in environmental samples by inductively coupled plasma mass spectrometry (Review), Spectrochimica Acta, Part B. 61, Grate, J.W., O.B. Egorov, Automating Analytical Separations in Radiochemistry, Anal. Chem. 1998, 70, 779A- 788A. 6 Grate, J.W., O.B. Egorov, Automated radiochemical separation, analysis, and sensing, Handbook of Radioactivity Analysis, 2 nd Ed. Academic Press: San Diego, CA. 2003, Egorov, O.B., et. al Automation of radiochemical analysis: from groundwater monitoring to nuclear waste analysis. Radioanalytical methods in interdisciplinary research: fundamentals in cutting-edge applications (ACS Symposium Series 868), American Chemical Society, Washington, DC. Chp Grate JW, MJ O'Hara, and O Egorov "Automation of Extraction Chromatographic and Ion Exchange Separations for Radiochemical Analysis and Monitoring." In Ion Exchange and Solvent Extraction: A Series of Advances, CRC Press, Boca Raton, FL. Vol. 19 Chp Egorov, O.B., M.J. O Hara, Development and Testing of the Automated 99 Tc Monitor Final Report, PNWD- 3327; WTP-RPT-074. Pacific Northwest National Laboratory, Richland, WA. July M.J. O'Hara, et. al., "Automated process monitoring: applying proven automation techniques to international safeguards needs. In 49th Annual Meeting of the Institute of Nuclear Materials Management. Pacific Northwest National Laboratory, Richland, WA. 11 M.J. O Hara, et. al., Rapid Automated Radiochemical Analyzer for Determination of Targeted Radionuclides in Nuclear Process Streams 8th International Conference on Facility Operations-Safeguards Interface. PNNL-SA-59847, Pacific Northwest National Laboratory, Richland, WA. 12 Devol TA, JP Clements, AF Farawila, MJ O'Hara, O Egorov, and JW Grate "Characterization and Application of Superlig 620 Solid Phase Extraction Resin for Automated Process Monitoring of 90 Sr. J. Nucl. & Radiochem, 282(2), Egorov, O.B., et. al Extraction chromatographic separations and analysis of actinides using sequential injection techniques with on-line inductively coupled plasma mass spectrometry (ICP MS) detection The Analyst. 126, Waste Treatment Plant Contract No. DE-AC27-01RV14136, Dec. 2000, Specification Radionuclide Concentration Limitations, U.S. Department of Energy Office of River Protection, Richland, WA. 15 Egorov, O. B.; O'Hara, M. J.; Grate, J. W., Microwave-Assisted Sample Treatment in a Fully Automated Flow- Based Instrument: Oxidation of Reduced Technetium Species in the Analysis of Total Technetium-99 in Caustic Aged Nuclear Waste Samples, Anal. Chem. 2004, 76,