This report describes laboratory development and process plant applications of Raman spectroscopy for detection of hydrogen isotopes in the Tritium Facilities at the Savannah River Site (SRS), a U.S. Department of Energy complex. Raman spectroscopy provides a lower-cost, in situ alternative to mass spectrometry techniques currently employed at SRS. Using conventional Raman and fiber optics, we have measured, in the production facility glove boxes, process mixtures of protium and deuterium at various compositions and total pressures ranging from 1000 -4000 torr, with detection limits ranging from 1-2% for as low as 3-second integration times. We are currently investigating fabrication techniques for SERS surfaces in order to measure trace (0.01-0.1%) amounts of one isotope in the presence of the other. These efforts have concentrated on surfaces containing palladium, which promotes hydrogen dissociation and forms metal hydride bonds, essentially providing a chemical enhancement mechanism.

This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. This report has been reproduced directly from the best available copy.

EXECUTIVE SUMMARYThe problem of the aging mass spectrometers coupled with lack of vendor support and no viable commercially available replacement presents risks for process control and monitoring in the Tritium Facilities. Therefore, several technologies were evaluated to maintain and, if possible, to enhance the current analytical capabilities provided by the existing mass spectrometers. These technologies included potential replacement/complement mass spectrometers as well as on-line sensors. Based on the results of this evaluation, the Savannah River National Laboratory (SRNL) makes the following recommendations.• Work should begin on implementation of the Quantra Fourier Transform-Ion CyclotronResonance (FT-ICR) as a complement to the existing mass spectrometers or as an on-line process analyzer. In its current configuration, the instrument can measure masses 12 or greater, with a resolution of 30,000 at mass 28, and 100 part per million detection limit using ion ejection of major ions. Thus, the 16-24 mass region that is not so easily separated by the existing Tritium Facility mass spectrometers could be resolved and measured using the FT-ICR. For the FT-ICR (Quantra) to be of even more benefit to the Tritium Facilities, it should be reengineered to provide analysis of masses 2-1000 in a single scan as well as other hardware and software improvements identified during our evaluation (i.e. long term stability, quantitative analysis of mixtures, etc.). In collaboration, SRS, LANL, and Y12 have secured funding for this project and the re-engineering effort will begin in FY06. Once the re-engineering effort is complete, funding will be required for performance testing and implementation in a tritiated environment as well as validation with the design agency.• The bench top magnetic sector mass spectrometer (GCMATE) technology closely matches that of the existing mass spectrometers in the Tritium Facilities. The initial work with the GCMATE indicates that its resolution and sensitivity meet the requirements of a replacement mass spectrometer for the Tritium Facilities. Although this instrument appears to be the most promising as a replacement for the existing mass spectrometers, delayed funding in FY05 precluded a complete evaluation. Therefore, evaluation of this instrument should continue in FY06.• Fiber optic Raman Spectroscopy has been demonstrated as a useful on-line technology for measurement of hydrogen isotopes at a concentration of greater than 1%. The method should be demonstrated on a process containing tritium. Upon successful demonstration in a tritium process, the method should then be implemented on the Hydrogen-Tritium Thermal Cycling Adsorption Process (HT-TCAP) and other processes that would require a detection limit of 1% or greater. Research and development to improve the detection limit of the fiber optic Raman method should continue as this would allow on-line analysis of other process points (i.e. HT-TCAP product and raffinate, Tritium Process Stripper, etc.).• The on-line vapochromic sens...

No abstract

No abstract