Waste Chemistry Envelope for the Determination of Pitting Corrosion Susceptibility - 19554

Liquid radioactive wastes at the Hanford and Savannah River sites are stored in large underground carbon steel tanks. The high-level wastes are processed in several of the tanks and then transferred by piping to other site facilities for further processing before they are stabilized in a vitrified or grout waste form. Based on waste removal and processing schedules, many of the tanks, will be required to be in service for times exceeding the initial intended life (i.e., greater than 60 years). Until the waste is removed from storage, transferred, and processed, the materials and structures of the tanks must maintain a confinement function by providing a barrier to the environment and by maintaining acceptable structural stability during design basis events, which include loadings from both normal service and abnormal (e.g., earthquake) conditions. Administrative programs are in place to mitigate potential corrosion mechanisms and thereby maintain the structural and leak integrity functions of these waste tanks throughout their intended service life. Waste chemistry and temperature control are the means by which corrosion degradation of the waste tanks is minimized. Chemistry controls are based on in-situ coupon tests, waste tank experience, and laboratory testing. These requirements comprise the technical standards for corrosion control. The standards are utilized then as guidelines for operational procedures. The present waste chemistry controls for the Hanford DSTs were established in the 1980's in response to tank failures caused by stress corrosion cracking (SCC) at the DOE Savannah River Site (SRS). Portions of the SRS chemistry limits, which were developed at the Savannah River National Laboratory (SRNL) were coupled with corrosion testing results from Pacific Northwest National Laboratories (PNNL) and adopted for corrosion control of the double-shell tank (DST) waste at the Hanford Site. Since that time, the temperatures of the waste in the DSTs have decreased to less than 50 deg. C in most cases as the radioactive material has decayed. As a consequence, new chemistry controls were formulated for SCC in 2010. This testing however, did not address that potential for pitting in the supernatant and at the liquid-air interface. Indeed, initial tests indicated that the inhibitor requirements for SCC would be insufficient for the prevention of pitting. In addition to lower waste temperatures, future retrieval and process changes may impact the DST waste chemistry. Initial projections suggest that the waste chemistry of the DSTs may shift to a broader range of pH and higher aggressive anion concentrations (e.g., chloride, sulfate, etc.) than the wastes that are presently stored. Additionally, processes within the vitrification facility may result in streams that are returned to the tank farm for evaporation. These streams may also contain high concentrations of aggressive species. SRNL investigated the propensity for pitting of the carbon steel waste tanks at current and projected DST waste chemistries. A statistically designed series of tests provided a pitting factor that relates the ratio of the inhibitor species to the aggressive species and the probability of observing pitting. An acceptable pitting factor was determined and was utilized for the development of a new chemistry envelope. The new chemistry envelope was compared to the envelope that was established for SCC and was determined to be bounding. Validation of the new chemistry envelope was performed via model simulations and comparison with historical experimental results and approaches to establishing chemistry envelopes. The new chemistry envelope will eventually be part of an overall assessment of the condition of the tanks and any changes made to the overall structural integrity program for the Hanford DSTs. (authors)