Ferrocyanide Safety Program cyanide speciation studies. Final report

This report summarizes Pacific Northwest Laboratory's fiscal year (FY) 1995 progress toward developing and implementing methods to identify and quantify cyanide species in ferrocyanide tank waste. This work was conducted for Westinghouse Hanfbrd Company's (WHC's) Ferrocyanide Safety Program. Currently, there are 18 high-level waste storage tanks at the US Department of Energy's Hanford Site that are on a Ferrocyanide Tank Watchlist because they contain an estimated 1000 g-moles or more of precipitated ferrocyanide. In the presence of oxidizing material such as sodium nitrate or nitrite, ferrocyanide can be made to react exothermally by heating it to high temperatures or by applying an electrical spark of sufficient energy (Cady 1993). However, fuel, oxidizers, and temperature are all important parameters. If fuel, oxidizers, or high temperatures (initiators) are not present in sufficient amounts, then a runaway or propagating reaction cannot occur. To bound the safety concern, methods are needed to definitively measure and quantitate ferrocyanide concentration present within the actual waste. The target analyte concentration for cyanide in waste is approximately 0.1 to 15 wt % (as cyanide) in the original undiluted sample. After dissolution of the original sample and appropriate dilutions, the concentration range of interest in the analytical solutions can vary between 0.001 to 0.1 wt % (as cyanide). In FY 1992, 1993, and 1994, two solution (wet) methods were developed based on Fourier transform infrared (FTIR) spectroscopy and ion chromatography (IC); these methods were chosen for further development activities. The results of these activities are described