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Fondeur, F.

Publications and source records attributed to Fondeur, F..

At least 19 records

Solvent hold tank sample results for MCU-17-150-152 (July 2017) and MCU-17-153-155 (August 2017): Quarterly report

A trend summary that includes the last two Solvent Hold Tank (SHT) monthly samples is shown; MCU- 17-150-152 (July SHT) and MCU-17-153-155 (August SHT). Since the last SHT sample sent for analysis was the August sample the chemical state of the solvent is best approximated by the chemical analysis of the August SHT sample (MCU-17-153-155). This report mainly focused on the chemical analysis of the August SHT sample. The analysis data from the July SHT sample are presented in the “trend” plots of this report. Analysis of the August SHT sample (MCU-17-153-155) indicated that the modifier (CS-7SB) was 2% below but the extractant (MaxCalix) concentration was at its nominal recommended level (169,000 mg/L and 46,400 mg/L respectively). The suppressor (TiDG) level has decreased since the last measurement taken while the Modular Caustic-Side Solvent Extraction unit (MCU) was operating in January 2017, but has remained steady in the range of 666 (observed in April) to 715 mg/L (observed in the August 2017 sample) since February 2017, well above the minimum recommended level (479 mg/L), but below the nominal level. The “flat” trends observed in the TiDG, MaxCalix, modifier, and Gamma measurement are consistent with the solvent being idle since January 10, 2017. A strong correlation between density and modifier concentration in the solvent continues to be observed in the SHT samples. This analysis confirms the Isopar™L addition to the solvent in January 2017. This analysis also indicates the solvent did not require further additions. Based on the current monthly sample, the levels of TiDG, Isopar™L, MaxCalix, and modifier are sufficient for continuing operation but are expected to decrease with time if the Modular Caustic-Side Solvent Extraction Unit (MCU) returns to processing radioactive liquid waste. Otherwise, the levels of these components will remain steady. A future Isopar™L trimming addition to the solvent is recommended when MCU resumes processing waste. Two unknown impurities related to the modifier (but not sec-butyl phenol: a modifier degradation product observed before) at the 290 and 110 mg/L levels were observed in the August SHT sample by the Gas - Chromatography-Mass Spectrometry (GC-MS) method. They were observed in a second GC-MS re-run with a new column. Their identification can’t be ascertained at this time. No impurities were observed in the Hydrogen Nuclear Magnetic Resonance (HNMR). Another impurity observed in the samples was mercury. Based on the August SHT sample, up to 23 ± 5 micrograms of mercury per mL of solvent was detected (the average of the Cold Vapor-Atomic Adsorption [CV-AA] and X-Ray Fluorescence [XRF] methods). The higher mercury concentration in the solvent (as determined in the last three-monthly samples) is possibly due to either a higher mercury concentration in Salt Batches 8 and 9 (Tank 49H) . The gamma level (~ 2.0E4 dpm/mL) measured in the August SHT samples was one order of magnitude lower than the gamma levels observed in the December 2016 and January 2017 SHT samples. A similar level was observed in the July SHT sample (MCU-SHT-150-152). The gamma level has remained consistently steady since January 10, 2017 when MCU stopped processing radioactive liquid waste. The laboratory will continue to monitor the quality of the solvent in particularly for any new impurities or degradation of the solvent components.

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Solvent hold tank sample results for MCU-17-122-124 (March 2017), MCU-17-130-132 (April 2017), MCU-17-133-135 (May 2017), and MCU-17-141-149 (June 2017): Quarterly Report

A trend summary of four Solvent Hold Tank (SHT) monthly samples; MCU-16-122-124 (March 2017), MCU-17-130-132 (April 2017), MCU-17-133-135 (May 2017), and MCU-17-141-149 (June 2017) are reported. Analyses of the June SHT sample (MCU-17-141-149) indicated that the modifier (CS-7SB) and the extractant (MaxCalix) concentrations were slightly below (4% each) their nominal recommended levels (169,000 mg/L and 46,400 mg/L respectively). The suppressor (TiDG) level has decreased since the January 2017 measurement but has remained steady in the range of 666 to 705 mg/L, well above the minimum recommended level (479 mg/L), but below the nominal level. The “flat” trends observed in the TiDG, MaxCalix, modifier, and Gamma measurement are consistent with the solvent being idle since January 10, 2017.

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Solvent Hold Tank Sample Results for MCU-16-991-992-993: July 2016 Monthly sample and MCU-16-1033-1034-1035: July 2016 Superwashed Sample

SRNL received one set of SHT samples (MCU-16-991, MCU-16-992 and MCU-16-993), pulled on 07/13/2016 and another set of SHT samples (MCU-16-1033, MCU-16-1034, and MCU-16-1035) that were pulled on 07/24/2016 after the solvent was superwashed with 300 mM sodium hydroxide for analysis. Samples MCU-16-991, MCU-16-992, and MCU-16-993 were combined into one sample (MCU-16-991-992-993) and samples MCU-16-1033, MCU-16-1034, and MCU-16-1035 were combined into one sample (MCU-16-1033-1034-1035). Of the two composite samples MCU-16-1033-1034-1035 represents the current chemical state of the solvent at MCU. All analytical conclusions are based on the chemical analysis of MCU-16-1033-1034-1035. There were no chemical differences between MCU-16- 991-992-993 and superwashed MCU-16-1033-1034-1035.

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Characterization of solids deposited on the modular caustic-side solvent extraction unit (MCU) coalescer media removed in October 2014

In February 2015, Savannah River National Laboratory (SRNL) received a Strip Effluent (SE) coalescer (FLT-304) from MCU. That coalescer was first installed at MCU in July 2014 and removed in October 2014. While processing approximately 31,400 gallons of strip solution, the pressure drop steadily increased from 1 psi to beyond the administrative limit of 20 psi. The physical and chemical analysis was conducted on this coalescer to determine the mechanism that led to the plugging of this coalescer. Characterization of this coalescer revealed the adsorption of organic containing amines as well as MCU modifier. The amines are probably from the decomposition of the suppressor (TiDG) as well as from bacteria. This adsorption may have changed the surface energetics (characteristics) of the coalescer fibers and therefore, their wetting behavior. A very small amount of inorganic solids were found to have deposited on this coalescer (possibly an artifact of cleaning the coalescer with Boric acid. However, we believe that inorganic precipitation, as has been seen in the past, did not play a role in the high pressure drop rise of this coalescer. With regards to the current practice of reducing the radioactive content of the SE coalescer, it is recommended that future SE coalescer should be flushed with 10 mM boric acid which is currently used at MCU. Plugging of the SE coalescer was most likely due to the formation and accumulation of a water-in-oil emulsion that reduced the overall porosity of the coalescer. There is also evidence that a bimodal oil particle distribution may have entered and deposited in the coalescer and caused the initial increase in pressure drop.

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Solvent Hold Tank Sample Results For MCU-15-710-711-712: June 2015 Monthly Sample

Savannah River National Laboratory (SRNL) received one set of Solvent Hold Tank (SHT) samples (MCU-15-710, MCU-15-711, and MCU-15-712), pulled on 06/15/2015 for analysis. The samples were combined and analyzed for composition. Analysis of the composite sample MCU-15-710-711-712 indicated a low concentration (~ 55 % of nominal) of the suppressor (TiDG) and concentrations of the extractant (MaxCalix), and of the modifier (Cs-7SB) in the solvent that were slightly lower than nominal. This analysis confirms the addition of TiDG, MaxCalix, and modifier (92 % of nominal) to the solvent in February 2015. Based on the current monthly sample, the levels of TiDG, MaxCalix, and modifier were sufficient when this solvent sample was collected from MCU. A higher cesium concentration (9.3 E6 dpm/mL) was observed in this sample relative to recent samples. In the past, this level of cesium appeared to correlate with upsets in the MCU operation. It is not known at this time the reason for the higher cesium level in this solvent. No impurities above the 1000 ppm level were found in this solvent by the Semi-Volatile Organic Analysis (SVOA). In addition, the sample contains up to 10.4 micrograms of mercury per gram of solvent (or 8.7 µg/mL). A relatively large cesium concentration (9.3 E 6 dpm/mL) was measured in this solvent and it may indicate poor cesium stripping. The laboratory will continue to monitor the quality of the solvent in particular for any new impurities or degradation of the solvent components.

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Solvent Hold Tank Sample Results For MCU-15-750-751-752-: June Monthly Sample

Savannah River National Laboratory (SRNL) received one set of Solvent Hold Tank (SHT) samples (MCU-15-750, MCU-15-751, and MCU-15-752), pulled on 06/22/2015 for analysis. The samples were combined and analyzed for composition. Analysis of the composite sample MCU-15-750-751-752 indicated a low concentration (~ 49 % of nominal) of the suppressor (TiDG) and slightly lower than nominal concentrations of the extractant (MaxCalix), and of the modifier (Cs-7SB) in the solvent. This analysis confirms the addition of TiDG, MaxCalix, and modifier to the solvent in February 2015. Based on the current monthly sample, the levels of TiDG, MaxCalix, and modifier are sufficient for continuing operation without adding a trim at this time but it is recommended that an addition of TiDG, modifier and Isopar™L should be made in the near future. No impurities above the 1000 ppm level were found in this solvent by the Semi-Volatile Organic Analysis (SVOA). No impurities were observed in the Hydrogen Nuclear Magnetic Resonance (HNMR). In addition, up to 13.9 micrograms of mercury per gram of solvent (or 11.5 µg/mL) was detected in this sample. The laboratory will continue to monitor the quality of the solvent in particular for any new impurities or degradation of the solvent components.

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Solvent Hold Tank Sample Results for MCU-15-556-557-558: March 2015 Monthly Sample

Savannah River National Laboratory (SRNL) received one set of Solvent Hold Tank (SHT) samples (MCU-15-556, MCU-15-557, and MCU-15-558), pulled on 03/16/2015 for analysis. The samples were combined and analyzed for composition. Analysis of the composite sample MCU-15-556-557-558 indicated a low concentration (~ 78 % of nominal) of the suppressor (TiDG) and concentrations of the extractant (MaxCalix), and of the modifier (CS-7SB) in the solvent that were slightly lower than nominal. This analysis confirms the addition of TiDG, MaxCalix, and modifier to the solvent in February 2015. Based on the current monthly sample, the levels of TiDG, MaxCalix, and modifier are sufficient for continuing operation without adding a trim at this time. No impurities above the 1000 ppm level were found in this solvent by the Semi-Volatile Organic Analysis (SVOA). However, the p-nut vials that delivered the samples contained small (1 mm) droplets of oxidized modifier and amides (as detected by the FTIR analysis). In addition, up to 21 microgram of mercury per gram of solvent (or 17.4 µg/mL) was detected in this sample. The laboratory will continue to monitor the quality of the solvent in particular for any new impurities or degradation of the solvent components.

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Solvent Hold Tank Sample Results for MCU-15-389-390 and MCU-15-439-440-441. February 2015 Monthly Samples

Savannah River National Laboratory (SRNL) received two sets of Solvent Hold Tank (SHT) samples (MCU-15-389 and MCU-15-390 pulled on February 23, 2015 and MCU-15-439, MCU-15-440, and MCU-15-441 pulled on February 28, 2015) for analysis. The samples in each set were combined and analyzed for composition. Analysis of the composite samples MCU-15-389-390 and MCU-15-439-440- 441 indicated a low concentration (~ 92 to 93 % of nominal) of the suppressor (TiDG) and slightly below nominal concentrations of the extractant (MaxCalix), but nominal levels of the modifier (CS-7SB) and of the Isopar™ L. This analysis confirms the addition of TiDG, MaxCalix, and modifier to the solvent on February 22, 2015. Despite that the values are below the target component levels, the current levels of TiDG and MaxCalix are sufficient for continuing operation without adding a trim at this time. No impurities above the 1000 ppm level were found in this solvent. However, the p-nut vials that delivered the samples contained small (1 mm) droplets of oxidized modifier and amides. The laboratory will continue to monitor the quality of the solvent in particular for any new impurity or degradation of the solvent components.

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Solvent hold tank sample results for MCU-14-943 and MCU-14-1061: November 2014 monthly samples

SRNL received two sets of SHT samples (MCU-14-943, pulled 11/28/2014 and MCU-14-1061, pulled on 12/03/2014) for analysis. The samples were combined and analyzed for composition. Analysis of the combined sample (MCU-14-943-1061) indicated low concentrations of the suppressor (TiDG) and modifier (CS-7SB) despite the addition of TiDG to the solvent in October 26, 2014. However, the TiDG level in this sample is within recommended operating parameters. The solvent’s density is at nominal value despite the low modifier level. No impurities were observed in the solvent at this time. The laboratory will continue to monitor the quality of the solvent in particular for any new impurity or degradation of the solvent components.

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Solvent hold tank sample results for MCU-14-913 and MCU-14-986/987: October 2014 monthly

SRNL received two sets of SHT samples (MCU-14-913, pulled 10/7/2014 and MCU-14-986/987, pulled on 10/27/2014) for analysis. The samples were analyzed for composition. Analysis of sample MCU-14- 913 indicated low concentrations of the suppressor (TiDG) and of the modifier (CS-7SB) in the solvent. The addition of suppressor and modifier to the solvent on October 26, 2014 restored the concentration of these components to nominal levels as confirmed with the analysis of sample MCU-14-986/987. The laboratory will continue to monitor the quality of the solvent in particular for any new impurity or degradation of the solvent components.

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SOLVENT HOLD TANK SAMPLE RESULTS FOR MCU-14-667-672 AND MCU-14-846-847: AUGUST AND SEPTEMBER 2014 MONTHLY SAMPLES

SRNL received two sets of SHT samples (MCU-14-667-672, pulled 8/27/2014 and MCU-14-846-847, pulled on 9/22/2014) for analysis. The samples were analyzed for composition. It is recommended that the solvent receives Isopar® L and TiDG trimming at this time. Analysis of sample MCU-14-846-847 indicates the solvent has evaporated Isopar®L and has lost TiDG to a level below the recommended minimum 1 mM level. Since the addition of MaxCalix to the SHT in early July 2014, the MaxCalix concentration in the solvent has reached nominal values. The laboratory will continue to monitor the quality of the solvent in particular for any new impurity or degradation of the solvent components.

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SOLVENT HOLD TANK SAMPLE RESULTS FOR MCU-14-259/260/261 AND MCU-14-315/316/317: APRIL AND MAY 2014 MONTHLY SAMPLES

SRNL received two sets of SHT samples (MCU-14-259/260/261 in April 2014 and MCU-14- 315/316/317 in May 2014) for analysis. The samples were analyzed for composition. Both samples have similar chemical composition. As with the previous solvent sample results, these analyses indicate that the solvent does not require Isopar® L trimming at this time. Since an addition of TiDG and MaxCalix to the SHT was added in early July 2014, the solvent does not require TiDG addition at this time. The current TiDG level (1.5 mM) is above the minimum recommended operating level of 1 mM.

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Characterization of Solids in Fouled Modular Caustic Side Solvent Extraction Unit (MCU) Prefilter/Coalescer Media

Prefilters and coalescers utilized during the Modular Caustic Side Solvent Extraction Unit (MCU) processing of Salt Batches 5 and 6 were sampled and submitted to SRNL for characterization, for the purpose of identifying solid phase constituents potentially fouling the pores. Specifically, three samples were received and characterized: 1) a decontaminated salt solution (DSS) prefilter (PF) sample; 2) a DSS coalescer sample; and 3) a strip effluent (SE) coalescer sample. Aliquots of the samples were analyzed by X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR) Spectroscopy, and Scanning Electron Microscopy (SEM)/Energy Dispersive Spectroscopy (EDS). Other aliquots of the samples were leached in acid solution, and the leachates were analyzed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). In addition, modeling was performed to provide a basis for comparison of the analytical results.

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THE USE OF POLYMERS IN RADIOACTIVE WASTE PROCESSING SYSTEMS

The Savannah River Site (SRS), one of the largest U.S. Department of Energy (DOE) sites, has operated since the early 1950s. The early mission of the site was to produce critical nuclear materials for national defense. Many facilities have been constructed at the SRS over the years to process, stabilize and/or store radioactive waste and related materials. The primary materials of construction used in such facilities are inorganic (metals, concrete), but polymeric materials are inevitably used in various applications. The effects of aging, radiation, chemicals, heat and other environmental variables must therefore be understood to maximize service life of polymeric components. In particular, the potential for dose rate effects and synergistic effects on polymeric materials in multivariable environments can complicate compatibility reviews and life predictions. The selection and performance of polymeric materials in radioactive waste processing systems at the SRS are discussed.

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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.

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NEXT GENERATION SOLVENT MATERIALS COMPATIBILITY WITH POLYMER COMPONENTS WITHIN MODULAR CAUSTIC-SIDE SOLVENT EXTRACTION UNIT

The Office of Waste Processing, within the Office of Technology Innovation and Development, is funding the development of an enhanced solvent for deployment at the Savannah River Site for removal of cesium from High Level Waste. The technical effort is collaboration between Oak Ridge National Laboratory (ORNL), Savannah River National Laboratory (SRNL), and Argonne National Laboratory. The first deployment target for the technology is within the Modular Caustic-Side Solvent Extraction Unit (MCU). Deployment of a new chemical within an existing facility requires verification that the 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 facility. This report provides the data from exposing these polymers to the Next Generation Solvent (NGS). The test was conducted over six months. An assessment of the dimensional stability of polymers present in MCU (i.e., PEEK, Grafoil{reg_sign}, Tefzel{reg_sign} and Isolast{reg_sign}) in the modified NGS (where the concentration of the guanidine suppressor and MaxCalix was varied systematically) showed that guanidine (LIX{reg_sign}79) selectively affected Tefzel{reg_sign} (by an increase in size and lowering its density). The copolymer structure of Tefzel{reg_sign} and possibly its porosity allows for the easier diffusion of guanidine. Tefzel{reg_sign} is used as the seat material in some of the valves at MCU. Long term exposure to guanidine, may make the valves hard to operate over time due to the seat material (Tefzel{reg_sign}) increasing in size. However, since the physical changes of Tefzel{reg_sign} in the improved solvent are comparable to the changes in the CSSX baseline solvent, no design changes are needed with respect to the Tefzel{reg_sign} seating material. PEEK, Grafoil{reg_sign} and Isolast{reg_sign} were not affected by guanidine and MaxCalix within six months of exposure. The initial rapid weight gain observed in every polymer is assigned to the finite and limited uptake of Isopar{reg_sign} L/Modifier by the polymers probably due to the polymers porosity and rough surfaces. Spectroscopic data on the organic liquid and the polymer surfaces showed no preferential adsorption of any component in the NGS to the polymers and no leachate was observed in the NGS from any of the polymers studied.

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