SOLVENT HOLD TANK SAMPLE RESULTS FOR MCU-13-1403/1404/1405/1406/1407/1408: QUARTERLY SAMPLE FROM SEPTEMBER 2013

Savannah River National Laboratory (SRNL) analyzed solvent samples from the Modular Caustic-Side Solvent Extraction Unit (MCU) in support of continuing operations. A quarterly analysis of the solvent is required to maintain solvent composition within specifications. Analytical results of the analyses of Solvent Hold Tank (SHT) samples MCU-13-1403, MCU-13-1404, MCU-13-1405, MCU-13-1406, MCU-13-1407, and MCU-13-1408 received on September 17, 2013 are reported. This sample was taken after the addition of the Next Generation Solvent (NGS) cocktail to produce a NGS-MCU blended solvent. The results show that the solvent contains a slight excess of Isopar� L and a deficit concentration of modifier and TiDG when compared to the target composition. Addition of TiDG trim is recommended. SRNL also analyzed the SHT sample for {sup 137}Cs content and determined the measured value is within tolerance and that the value has returned to levels observed in 2011. In contrast to what was observed in the heel prior to adding the NGS cocktail, no organic impurities were detected in these solvent samples

Gamma radiation stability studies of mercury fulminate

Mercury fulminate completely decomposed in a gamma source (0.86 Mrad/h) after a dose of 208 Mrad. This exposure equates to approximately 2.4 years in Tank 15H and 4 years in Tank 12H, one of the vessels of concern. Since the tanks lost the supernatant cover layer more than a decade ago, this study suggests that any mercury fulminate or closely related energetic species decomposed long ago if ever formed

Miscibility Evaluation Of The Next Generation Solvent With Polymers Currently Used At DWPF, MCU, And Saltstone

The Office of Waste Processing, within the Office of Technology Innovation and Development, funded the development of an enhanced Caustic-Side Solvent Extraction (CSSX) solvent for deployment at the Savannah River Site for removal of cesium from High Level Waste. This effort lead to the development of the Next Generation Solvent (NGS) with Tris (3,7-dimethyl octyl) guanidine (TiDG). The first deployment target for the NGS solvent is within the Modular CSSX Unit (MCU). Deployment of a new chemical within an existing facility requires verification that the new chemical components are compatible with the installed equipment. In the instance of a new organic solvent, the primary focus is on compatibility of the solvent with organic polymers used in the affected facility. This report provides the calculated data from exposing these polymers to the Next Generation Solvent. An assessment of the dimensional stability of polymers known to be used or present in the MCU, Defense Waste Processing Facility (DWPF), and Saltstone facilities that will be exposed to the NGS showed that TiDG could selectively affect the elastomers and some thermoplastics to varying extents, but the typical use of these polymers in a confined geometry will likely prevent the NGS from impacting component performance. The polymers identified as of primary concern include Grafoil® (flexible graphite), Tefzel®, Isolast®, ethylene-propylene-diene monomer (EPDM) rubber, nitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), ultra high molecular weight polyethylene (UHMWPE), and fluorocarbon rubber (FKM). Certain polymers like NBR and EPDM were found to interact mildly with NGS but their calculated swelling and the confined geometry will impede interaction with NGS. In addition, it was found that Vellumoid (cellulose fibers-reinforced glycerin and protein) may leach protein and Polyvinyl Chloride (PVC) may leach plasticizer (such as Bis-Ethylhexyl-Phthalates) into the NGS solvent. Either case will not impact decontamination or immobilization operations at Savannah River Site (SRS). Some applications have zero tolerance for dimensional changes such as the operation of valves while other applications a finite dimensional change improves the function of the application such as seals and gaskets. Additional considerations are required before using the conclusions from this work to judge outcomes in field applications. Decane, a component of IsoparL that is most likely to interact with the polymers, mildly interacted with the elastomers and the propylene based polymers but their degree of swelling is at most 10% and the confined geometry that they are typically placed in indicate this is not significant. In addition, it was found that Vellumoid may leach protein into the NGS solvent. Since Vellumoid is used at the mixer in Saltstone where it sees minimum quantities of solvent, this leaching has no effect on the extraction process at MCU or the immobilization process at saltstone. No significant interaction is expected between MaxCalix and the polymers and elastomers used at MCU, DWPF, and Saltstone. Overall, minimal and insignificant interactions are expected on extraction and immobilization operations when MCU switches from CSSX to NGS solvent. It is expected that contacting NGS will not accelerate the aging rate of polymers and elastomers under radiation and heat. This is due to the minimal interaction between NGS and the polymers and the confined geometries for these polymers. SRNL recommends the use of the HSP method (for screening) and some testing to evaluate the impact of other organic such as alcohols, glycolate, and their byproducts on the polymers used throughout the site

Kinetics and Equilibrium Sorption Models: Fitting Plutonium, Strontium, Uranium and Neptunium Loading on Monosodium Titanate (MST)

The Dubinin-Astashov (DA) isotherm parameters for U, Pu, Sr and Np have been updated to include additional data obtained since the original derivation. The DA isotherms were modified to include a kinetic function derived by Rahn to describe sorbate loading from the beginning of sorption up to steady state. The final functions describe both kinetic and thermodynamic sorption

Solvent hold tank sample results for MCU-13-143, MCU-13-144, MCU-13-145, MCU-13-146, MCU-13-147 AND MCU-13-148: quarterly sample from January 2013

Savannah River National Laboratory (SRNL) analyzed solvent samples from Modular Caustic-Side Solvent Extraction Unit (MCU) in support of continuing operations. A quarterly analysis of the solvent is required to maintain solvent composition within specifications. Analytical results of the analyses of Solvent Hold Tank (SHT) samples MCU-13-143, MCU-13-144, MCU-13-145, MCU-13-146, MCU-13-147 and MCU-13-148 received 29 January 2012 are reported. The results show that the solvent at MCU does not require an Isopar® L addition, but it will require addition of trioctylamine. SRNL also analyzed the SHT sample for {sup 137}Cs content and determined the measured value is within tolerance and the value has returned to levels observed in 2012

CHARACTERIZATION AND EVALUATION OF CAUSTIC WASH TANK AND SOLVENT HOLD TANK SAMPLES FROM MCU FROM AUGUST TO SEPTEMBER 2011

During processing of Salt Batches 3 and 4 in the Modular Caustic-Side Solvent Extraction Unit (MCU), the decontamination efficiency for cesium declined from historical values and from expectations based on laboratory testing. This report documents efforts to analyze samples of solvent and process solutions from MCU in an attempt to understand the cause of the reduced performance and to recommend mitigations. CWT Solutions from MCU from the time period of variable decontamination factor (DF) performance which covers from April 2011 to September 2011 (during processing of Salt Batch 4) were examined for impurities using chromatography and spectroscopy. The results indicate that impurities were found to be of two types: aromatic containing impurities most likely from Modifier degradation and aliphatic type impurities most likely from Isopar{reg_sign} L and tri-n-octylamine (TOA) degradation. Caustic washing the Solvent Hold Tank (SHT) solution with 1M NaOH improved its extraction ability as determined from {sup 22}Na uptake tests. Evidence from this work showed that pH variance in the aqueous solutions within the range of 1M nitric acid to 1.91M NaOH that contacted the solvent samples does not influence the analytical determination of the TOA concentration by GC-MS

SOLVENT HOLD TANK SAMPLE RESULTS FOR MCU-13-189, MCU-13-190, AND MCU-13-191: QUARTERLY SAMPLE FROM SEPTEMBER 2013

Savannah River National Laboratory (SRNL) analyzed solvent samples from Modular Caustic-Side Solvent Extraction Unit (MCU) in support of continuing operations. A quarterly analysis of the solvent is required to maintain solvent composition within specifications. Analytical results of the analyses of Solvent Hold Tank (SHT) samples MCU-13-189, MCU-13-190, and MCU-13-191 received on September 4, 2013 are reported. The results show that the solvent (remaining heel in the SHT tank) at MCU contains excess Isopar� L and a deficit concentration of modifier and trioctylamine when compared to the standard MCU solvent. As with the previous solvent sample results, these analyses indicate that the solvent does not require Isopar� L trimming at this time. Since MCU is switching to NGS, there is no need to add TOA nor modifier. SRNL also analyzed the SHT sample for {{sup 137}Cs content and determined the measured value is within tolerance and the value has returned to levels observed in 2011

THERMAL AND SPECTROSCOPIC ANALYSES OF NEXT GENERATION CAUSTIC SIDE SOLVENT EXTRACTION SOLVENT CONTACTED WITH 3, 8, AND 16 MOLAR NITRIC ACID

A new solvent system referred to as Next Generation Solvent or NGS, has been developed at Oak Ridge National Laboratory for the removal of cesium from alkaline solutions in the Caustic Side Solvent Extraction process. NGS is proposed for deployment at MCU and at the Salt Waste Processing Facility. This work investigated the chemical compatibility between NGS and 16 M, 8 M, and 3 M nitric acid from contact that may occur in handling of analytical samples from MCU or, for 3 M acid, which may occur during contactor cleaning operations at MCU. This work shows that reactions occurred between NGS components and the high molarity nitric acid. In the case of 16 M and 8 M nitric acid, initially organo-nitrate groups are generated and attach to the modifier and that with time oxidation reactions convert the modifier into a tarry substance with gases (NO{sub x} and possibly CO) evolving. Calorimetric analysis of the organonitrate revealed the reaction products are not explosive nor will they deflagrate. NGS exposure to 3 M nitric acid resulted in much slower reaction kinetics and that the generated products were not energetic. We recommended conducting Accelerated Rate calorimetry on the materials generated in the 16 M and 8 M nitric acid test. Also, we recommend continue monitoring of the samples contacting NGS with 3 M nitric acid

Thermal And Spectroscopic Analyses Of Next Generation Caustic Side Solvent Extraction Solvent Contacted With 3, 8, And 16 Molar Nitric Acid

A new solvent system referred to as Next Generation Solvent or NGS, has been developed at Oak Ridge National Laboratory for the removal of cesium from alkaline solutions in the Caustic Side Solvent Extraction process. The NGS is proposed for deployment at MCU{sup a} and at the Salt Waste Processing Facility. This work investigated the chemical compatibility between NGS and 16 M, 8 M, and 3 M nitric acid from contact that may occur in handling of analytical samples from MCU or, for 3 M acid, which may occur during contactor cleaning operations at MCU. This work shows that reactions occurred between NGS components and the high molarity nitric acid. Reaction rates are much faster in 8 M and 16 M nitric acid than in 3 M nitric acid. In the case of 16 M and 8 M nitric acid, the nitric acid reacts with the extractant to produce initially organo-nitrate species. The reaction also releases soluble fluorinated alcohols such as tetrafluoropropanol. With longer contact time, the modifier reacts to produce a tarry substance with evolved gases (NO{sub x} and possibly CO). Calorimetric analysis of the reaction product mixtures revealed that the organo-nitrates reaction products are not explosive and will not deflagrate

Solvent hold tank sample results for MCU-13-143, MCU-13-144, MCU-13-145, MCU-13-146, MCU-13-147 AND MCU-13-148: quarterly sample from January 2013

Savannah River National Laboratory (SRNL) analyzed solvent samples from Modular Caustic-Side Solvent Extraction Unit (MCU) in support of continuing operations. A quarterly analysis of the solvent is required to maintain solvent composition within specifications. Analytical results of the analyses of Solvent Hold Tank (SHT) samples MCU-13-143, MCU-13-144, MCU-13-145, MCU-13-146, MCU-13-147 and MCU-13-148 received 29 January 2012 are reported. The results show that the solvent at MCU does not require an Isopar® L addition, but it will require addition of trioctylamine. SRNL also analyzed the SHT sample for {sup 137}Cs content and determined the measured value is within tolerance and the value has returned to levels observed in 2012