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SummaryOver several decades, site operations at what is now the U.S. Department of Energy's (DOE's) Idaho National Engineering and Environmental Laboratory have included nuclear reactor testing, reprocessing of spent nuclear fuel, and the storage, treatment, and disposal of the resultant radioactive and mixed wastes generated. Liquid, acidic, and radioactive high-level waste (HLW) and sodium bearing waste (SBW) from spent-fuel reprocessing operations have for the most part been calcined in the New Waste Calcining Facility (NWCF) and the earlier Waste Calcining Facility (WCF) to produce a dry granular waste form that is safer to store. However, about a million gallons of SBW remains uncalcined, and this liquid mixed waste, stored in tanks, does not meet current regulatory requirements for long-term storage and/or disposal. As a part of the Settlement Agreement between DOE and the State of Idaho, the tanks currently containing SBW are to be taken out of service by December 31, 2012, which requires the removal and treatment of the remaining SBW.Several potential options have been proposed for treating the SBW. Of those considered, vitrification received the highest weighted score against the criteria used. Beginning in fiscal year 2000, the INEEL HLW program embarked on a program for technology demonstration and development that would lead to conceptual design of a vitrification facility, based upon the liquid-fed melter technology, in the event that vitrification is the preferred alternative for SBW disposal. This program includes several separate activities that include, among others, waste-form development, process feed-stream design, and melter vitrification demonstration testing of the nonradioactive, surrogate SBW flowsheet. The first of the melter flowsheet tests conducted in support of INEEL's vitrification facility design is discussed below.The Pacific Northwest National Laboratory's (PNNL's) Research-Scale Melter (RSM) was used to conduct these initial melter-flowsheet evaluations. The RSM is a small (1/100-scale) joule-heated melter that is capable of processing melter feed on a continuous basis. This capability is key for:• developing/evaluating process flowsheets• characterizing relationships between feed composition and the properties of the final glass produced• establishing the fate and behavior of process effluent.This melter system's capability to produce glass in a continuous manner is also essential for estimating the behavior of a full-scale system. Moreover, the size of the RSM allows the impacts of process variables upon melter performance or glass quality to be quickly and efficiently evaluated without undue expense or waste generation.The experimental scope of this initial, 5-d, 120-h, SBW vitrification test was to evaluate the:• processing characteristics of the newly formulated SBW surrogate melter feed stream• acceptability of various SBW to glass-forming additive ratios• possible formation of a secondary sodium sulfate phase iv • effectiveness of sugar as a glass oxidation-state modifie...

A Class F fly ash was combined with a sodium aluminate slurry (3:1 Na:Al) in an attempt to synthesize zeolites from a highly alkaline waste stream. The reaction was studied as a function of composition (3:2, 1:1, and 1:2 fly ash:slurry), time (1, 3, and 7 days), and temperature (80°, 130°, and 180°C). X-ray diffraction analyses of the products indicated that the fly ash and sodium aluminate had combined to form Zeolite A at 80°C, and NaP1 (a gismondene-type) and an unnamed hydroxysodalite-type at 130°and 180°C. The fact that the pH of the reactants decreased from initial values in excess of 13 to near neutral (7-9) after reaction signifies that the bulk of the sodium had been incorporated into zeolitic phases. Because of the unique adsorptive and cation exchange capabilities of zeolites and the fact that some samples formed reasonably hard monoliths, zeolitic materials formed in this way might make excellent waste forms for ''mixed wastes'' which contain both radioactive and hazardous chemical species.

Radioactive waste generated during the reprocessing of fuel rods by the U.S. Department of Energy (DOE) is stored in underground tanks at Hanford, Savannah River and INEEL. The liquid fraction commonly referred to as sodium bearing waste (SBW), is a highly alkaline solution containing large amounts of sodium hydroxide, sodium nitrate and sodium nitrite. It has been shown that SBW can be mixed with a reducing agent and metakaolin and then calcined at 500• -700• C to form a calcine containing sodium aluminosilicate phases such as zeolite A, hydroxysodalite and/or cancrinite. Although calcination of the pretreated SBW produces a reasonable waste form in its own right, existing regulations require that granular calcines must be solidified before they can be shipped off site. It is possible to solidify the calcine in a number of ways. The calcine can be mixed with additional metakaolin and NaOH solution followed by mild curing (90• -200• C). The solid that forms (aka hydroceramic) has both strength and suitably low leachability. The current study examines the feasibility of using a more conventional Portland cement binder to solidify the calcine. Although strength was adequate, the leachabilities of the Portland cement solidified samples were higher than those of companion samples made with metakaolin. The zeolitic phases in the calcine acted like pozzolans and reacted with the Ca(OH) 2 in the Portland cement binder forming additional calcium silicate hydrate (C S H). Typically C S H is unable to host large amounts of sodium ions in its structure, thus a majority of the sodium present in the zeolites became concentrated in the pore solution present in the Portland cement binder and readily entered the leachant during PCT testing. In this instance metakaolin mixed with NaOH proved to be a superior binder for solidification purposes. C 2004 Kluwer Academic Publishers