Summary report of FY 1995 Raman spectroscopy technology development

US DOE is sponsoring development of remote, fiber-optic Raman spectroscopy for rapid chemical characterization of Hanford high-level radioactive tank waste. Deployment targets for this technology are analytical hot cells and, via the Light-Duty Utility Arm and cone penetrometer, the waste tanks themselves. Perceived benefits of fiber-optic Raman spectroscopy are (1) rapid generation of tank-waste safety-related data, (2) reduced personnel exposure to highly radioactive waste, (3) reduced tank-waste sampling and analysis costs, and (4) reduced radioactive analytical waste. This document presents the results from the investigation of two dispersive, transmission-grating Raman systems and four fiber-optic Raman probe designs with non-radioactive tank waste simulants. One Raman system used a 532-nm, 400 mW, solid-state laser; the other used a 785-nm, 500 mW, solid-state diode laser. We found (1) the transmission-grating systems had better wavelength stability than previously tried Czerny-Turner-Based systems and (2) the 785-nm system`s specie detection limits in the spectral fingerprint regiion were at least as good as those for the 532-nm system. Based on these results, and the fact that some tank wastes luminesce with 514.5nm excitation, we selected the 785-nm system for hot-cell use. Of the four probes tested, three had a ``six-around-on`` fiber probe design; the fourth probe was a one-fiber-in-one-fiber-out, diffuse-relectance design. Comparison of the four probes` signal-to-noise rations, rations, transmission/collection efficiencies, and probe-silica Raman backgrounds showed that the best probe for use with Hanford-Site tank waste should (1) be filtered as close to the probe tip as possible to reduce the probe-silica Raman background and (2) have multiple collection fibers. The responses of all the probes tested showed a strong dependence on probe-sample distance, and the presence of a probe window appeared to increase the probe`s silica Raman background