Chemical Reactivity and Recommended Remediation Strategy for Los Alamos Remediated Nitrate Salt (RNS) Wastes
Nitrate salt wastes were generated during historical processing operations to recover and purify plutonium at Los Alamos National Laboratory (LANL). These nitrate salts have the potential to behave as oxidizers, and to contain entrained liquids, both of which are prohibited in the Waste Isolation Pilot Plant (WIPP). A process was developed to remediate nitrate salts by mixing salts with an inorganic zeolite pet litter to absorb free liquids, and remove the oxidizing characteristic of the wastes. Process changes introduced instead an organic wheat--based pet litter along with organic neutralizers, generating a new waste form referred to as Remediated Nitrate Salt (RNS) waste. The February 2014 radiological release at the WIPP site was traced to a LANL RNS waste drum number 68660. Experimental and modeling studies performed at LANL indicate that mixtures of metal nitrate salts (oxidizer) with Swheat organic kitty litter (fuel) create the potential for exothermic chemical reactions. Even in the presence of triethanol--ammonium nitrate (TEAN) created during neutralization, relatively high temperatures, greater than approximately 160 °C (320 °F), are required for runaway exothermic reactions. Evaluation of Drum 68660 characteristics coupled with extensive chemical testing indicate that, in addition to the nitrate salt/Swheat organic kitty litter mixture, an additional trigger mechanism (or mechanisms) is likely required to raise the internal drum temperature high enough to initiate the nitrate salt/Swheat organic kitty litter reaction. A combination of chemical conditions were identified that may lower the temperature for reaction, including initial high acid concentration of free liquids; significant quantities (> 1 gal) of neutralized, absorbed free liquids; the presence of reactive or catalytic metals like magnesium, iron, or lead; the presence of bismuth containing glovebox gloves; and the presence of natural biological activity. Complex surrogate nitrate salt mixtures prepared to simulate wastes, particularly those containing iron and magnesium, can generate NOx gases that partially nitrate the organic Swheat kitty litter and form a more energetic fuel. These complex surrogate salt mixtures display exothermic behavior at temperatures as low as 60 °C (140 °F) which is still well above the ambient temperature conditions experience by a drum. Neutralization of free liquids, and sorption onto Swheat establishes conditions (moisture) with near-neutral pH) that will support natural biological activity. Spontaneous self-heating generated by low-level chemical reactions and/or the respiration of bacteria, molds, and microorganisms is potentially important in the early stages and may be sufficient to raise the temperature as high as 60 °C (140 °F), where the other exothermic chemical reactions can take place. Additional studies are being conducted to evaluate the role biological activity may have played in initiating the event. The use of Swheat absorbent in the processing of nitrate salt wastes can be pinpointed as the critical processing decision that led to the failure of drum 68660, regardless of the ii details of the thermal processes that enabled the drum to achieve temperatures sufficient to initiate the chemical reactions.