Automated radioanalytical system incorporating microwave-assisted sample preparation, chemical separation, and online radiometric detection for the monitoring of total 99Tc in nuclear waste processing streams.

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.

[1]  P. A. Smith,et al.  Volatility literature of chlorine, iodine, cesium, strontium, technetium, and rhenium; technetium and rhenium volatility testing , 1996 .

[2]  Jay W Grate,et al.  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. , 2004, Analytical chemistry.

[3]  Stephen Kiser,et al.  Automated flow injection system using extraction chromatography for the determination of plutonium in urine by inductively coupled plasma mass spectrometry , 2008 .

[4]  J. Grate,et al.  Sequential Injection Renewable Separation Column Instrument for Automated Sorbent Extraction Separations of Radionuclides , 1998 .

[5]  Kunjai Lee,et al.  Simultaneous analysis of 237Np and Pu isotopes in environmental samples by ICP-SF-MS coupled with automated sequential injection system , 2004 .

[6]  J. H. Kaye,et al.  Radiochemical determination of technetium-99 , 1982 .

[7]  E. Horwitz,et al.  Separation and preconcentration of actinides by extraction chromatography using a supported liquid anion exchanger : application to the characterization of high-level nuclear waste solutions , 1995 .

[8]  J. Grate,et al.  14 – AUTOMATED RADIOCHEMICAL SEPARATION, ANALYSIS, AND SENSING , 2003 .

[9]  Hill,et al.  Radiochemistry: inconvenient but indispensable , 2000, Applied radiation and isotopes : including data, instrumentation and methods for use in agriculture, industry and medicine.

[10]  W. Lukens,et al.  Identification of the non-pertechnetate species in Hanford waste tanks, Tc(I)--carbonyl complexes. , 2004, Environmental science & technology.

[11]  R. E. Eibling,et al.  Hanford Waste Simulants Created to Support the Research and Development on the River Protection Project - Waste Treatment Plant , 2001 .

[12]  E. Holm,et al.  Radiochemical measurements of99Tc: Sources and environmental levels , 1988 .

[13]  D. L. Blanchard,et al.  Technetium in alkaline, high-salt, radioactive tank waste supernate: Preliminary characterization and removal , 1997 .

[14]  L. A. Currie,et al.  LIMITS FOR QUALITATIVE DETECTION AND QUANTITATIVE DETERMINATION. APPLICATION TO RADIOCHEMISTRY. , 1968 .

[15]  J. Grate,et al.  Characterization and application of SuperLig® 620 solid phase extraction resin for automated process monitoring of 90Sr , 2009 .

[16]  Norman C. Schroeder,et al.  Feed Adjustment Chemistry for Hanford 101-SY and 103-SY Tank Waste: Attempts to Oxidize the Non-Pertechnetate Species , 2001 .

[17]  Jay W. Grate,et al.  Peer Reviewed: Automating Analytical Separations in Radiochemistry. , 1998 .

[18]  J. Grate,et al.  Sequential injection separation system with stopped-flow radiometric detection for automated analysis of (99)tc in nuclear waste. , 1998, Analytical Chemistry.

[19]  M. Hollenbach,et al.  Determination of technetium-99, thorium-230 and uranium-234 in soils by inductively coupled plasma mass spectrometry using flow injection preconcentration , 1994 .

[20]  Kunjai Lee,et al.  Rapid determination of Pu isotopes and atom ratios in small amounts of environmental samples by an on-line sample pre-treatment system and isotope dilution high resolution inductively coupled plasma mass spectrometry , 2000 .

[21]  Kunjai Lee,et al.  Determination of pu isotopes in seawater by an on-line sequential injection technique with sector field inductively coupled plasma mass spectrometry. , 2002, Analytical chemistry.

[23]  Jay W. Grate,et al.  AUTOMATED PROCESS MONITORING: APPLYING PROVEN AUTOMATION TECHNIQUES TO INTERNATIONAL SAFEGUARDS NEEDS , 2008 .

[24]  R. D. Evans,et al.  Rapid fingerprinting of 239Pu and 240Pu in environmental samples with high U levels using on-line ion chromatography coupled with high-sensitivity quadrupole ICP-MS detection , 2007 .