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At least 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2010

Evaluation of Potential Eluants for Non-Acid Elution of Cesium From Resorcinol-Formaldehyde Resin

Small-column ion exchange (SCIX) units installed in high-level waste tanks to remove Cs-137 from highly alkaline salt solutions are among the waste treatment plans in the DOE-complex. Spherical Resorcinol-Formaldehyde (sRF) is the ion exchange resin selected for use in the Hanford Waste Treatment and Immobilization Plant (WTP). It is also the primary ion exchange material under consideration for SCIX at the Hanford site. The elution step of the multi-step ion exchange process is typically done with 0.5 M nitric acid. An acid eluant is a potential hazard in the event of a spill, leak, etc. because the high-level waste tanks are made of carbon steel. Corrosion and associated structural damage may ensue. A study has been conducted to explore non-acid elution as an alternative. Batch contact sorption equilibrium screening tests have been conducted with 36 potential non-acid eluants. The sorption tests involve equilibrating each cesium-containing eluant solution with the sRF resin for 48 hours at 25 C in a shaker oven. In the sorption tests, an eluant is deemed to have a high cesium elution potential if it minimizes cesium sorption onto the sRF resin. The top candidates (based on lowest cesium sorption distribution coefficients) include ammonium carbonate, ammonium carbonate/ammonium hydroxide, ammonium bicarbonate, rubidium carbonate, ammonium acetate, ammonium acetate/ammonium hydroxide, ammonium bicarbonate/ammonium hydroxide, calcium chloride, and magnesium chloride. A select few of the top candidate eluants from the screening tests were subjected to actual sorption (loading) and elution tests to confirm their elution ability. The actual sorption (loading) and elution tests mimicked the typical sRF-cesium ion exchange process (i.e., sorption or loading, caustic wash, water rinse, and elution) via batch contact sorption and quasi column caustic wash/water rinse/elution. The eluants tested included ammonium carbonate, ammonium acetate, calcium acetate, magnesium acetate, and nitric acid. Calcium acetate and magnesium acetate were substitutes for calcium chloride and magnesium chloride respectively due to corrosion concerns. Nitric acid was selected for benchmarking since it is the baseline cesium eluant for sRF resin. The cesium elution performance of ammonium carbonate and ammonium acetate was approximately the same as the benchmark eluant, nitric acid. Ninety-seven (97), 94, and 100% percent of the cesium sorbed or loaded were eluted by ammonium carbonate, ammonium acetate, and nitric acid was respectively. The performance of calcium acetate and magnesium acetate, on the other hand, was mediocre. Percent elution was 16 and 8 respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Use of tamarisk as a potential feedstock for biofuel production.

This study assesses the energy and water use of saltcedar (or tamarisk) as biomass for biofuel production in a hypothetical sub-region in New Mexico. The baseline scenario consists of a rural stretch of the Middle Rio Grande River with 25% coverage of mature saltcedar that is removed and converted to biofuels. A manufacturing system life cycle consisting of harvesting, transportation, pyrolysis, and purification is constructed for calculating energy and water balances. On a dry short ton woody biomass basis, the total energy input is approximately 8.21 mmBTU/st. There is potential for 18.82 mmBTU/st of energy output from the baseline system. Of the extractable energy, approximately 61.1% consists of bio-oil, 20.3% bio-char, and 18.6% biogas. Water consumptive use by removal of tamarisk will not impact the existing rate of evapotranspiration. However, approximately 195 gal of water is needed per short ton of woody biomass for the conversion of biomass to biocrude, three-quarters of which is cooling water that can be recovered and recycled. The impact of salt presence is briefly assessed. Not accounted for in the baseline are high concentrations of Calcium, Sodium, and Sulfur ions in saltcedar woody biomass that can potentially shift the relative quantities of bio-char and bio-oil. This can be alleviated by a pre-wash step prior to the conversion step. More study is needed to account for the impact of salt presence on the overall energy and water balance.

03 NATURAL GAS↗
DOE OSTI2011

Corrective Action Decision Document/Closure Report for Corrective Action Unit 372: Area 20 Cabriolet/Palanquin Unit Craters, Nevada National Security Site, Nevada, Revision 0 with ROTC 1

This Corrective Action Decision Document (CADD)/Closure Report (CR) has been prepared for Corrective Action Unit (CAU) 372, Area 20 Cabriolet/Palanquin Unit Craters, located within Areas 18 and 20 at the Nevada National Security Site, Nevada, in accordance with the Federal Facility Agreement and Consent Order (FFACO). Corrective Action Unit 372 comprises four corrective action sites (CASs): • 18-45-02, Little Feller I Surface Crater • 18-45-03, Little Feller II Surface Crater • 20-23-01, U-20k Contamination Area • 20-45-01, U-20L Crater (Cabriolet) The purpose of this CADD/CR is to provide justification and documentation supporting the recommendation that no further corrective action is needed for CAU 372 based on the implementation of the corrective action of closure in place with administrative controls at all CASs. Corrective action investigation (CAI) activities were performed from November 9, 2009, through December 10, 2010, as set forth in the Corrective Action Investigation Plan for Corrective Action Unit 372: Area 20 Cabriolet/Palanquin Unit Craters. The approach for the CAI was divided into two facets: investigation of the primary release of radionuclides and investigation of other releases (migration in washes and chemical releases). The purpose of the CAI was to fulfill data needs as defined during the data quality objective (DQO) process. The CAU 372 dataset of investigation results was evaluated based on a data quality assessment. This assessment demonstrated the dataset is acceptable for use in fulfilling the DQO data needs. Investigation results were evaluated against final action levels (FALs) established in this document. A radiological dose FAL was established of 25 millirem per year based on the Remote Work Area exposure scenario (336 hours of annual exposure). Radiological doses exceeding the FAL were found to be present at all four CASs. It is assumed that radionuclide levels present within the Little Feller I and Cabriolet high contamination areas and within the craters at Palanquin and Cabriolet exceed the FAL. It is also assumed that potential source material in the form of lead bricks at Little Feller I and lead-acid batteries at Palanquin and Cabriolet exceed the FAL. Therefore, corrective actions were undertaken that consist of removing potential source material, where present, and implementing a use restriction and posting warning signs at each CAS. These use restrictions were recorded in the FFACO database; the U.S. Department of Energy, National Nuclear Security Administration Nevada Site Office (NNSA/NSO) Facility Information Management System; and the NNSA/NSO CAU/CAS files. Therefore, NNSA/NSO provides the following recommendations: • No further corrective actions are necessary for CAU 372. • A Notice of Completion to NNSA/NSO is requested from the Nevada Division of Environmental Protection for closure of CAU 372. • Corrective Action Unit 372 should be moved from Appendix III to Appendix IV of the FFACO.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2010

Guidelines for Estimating Unmetered Industrial Water Use

The document provides a methodology to estimate unmetered industrial water use for evaporative cooling systems, steam generating boiler systems, batch process applications, and wash systems. For each category standard mathematical relationships are summarized and provided in a single resource to assist Federal agencies in developing an initial estimate of their industrial water use. The approach incorporates industry norms, general rules of thumb, and industry survey information to provide methodologies for each section.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2011

GLYCOLIC-FORMIC ACID FLOWSHEET SLUDGE MATRIX STUDY

Testing was completed to demonstrate the viability of the newly developed glycolic acid/formic acid flowsheet on processing in the Defense Waste Processing Facility's (DWPF) Chemical Process Cell (CPC). The Savannah River National Laboratory (SRNL) initiated a sludge matrix study to evaluate the impact of changing insoluble solid composition on the processing characteristics of slurries in DWPF. Four sludge simulants were prepared to cover two compositional ranges in the waste. The first was high iron/low aluminum versus low iron/high aluminum (referred to as HiFe or LoFe in this report). The second was high calcium-manganese/low nickel, chromium, and magnesium versus low calcium-manganese/high nickel, chromium, and magnesium (referred to as HiMn or LoMn in this report). These two options can be combined to form four distinct sludge compositions. The sludge matrix study called for testing each of these four simulants near the minimum acid required for nitrite destruction (100% acid stoichiometry) and at a second acid level that produced significant hydrogen by noble metal catalyzed decomposition of formic acid (150% acid stoichiometry). Four simulants were prepared based on the four possible combinations of the Al/Fe and Mn-Ca/Mg-Ni-Cr options. Preliminary simulant preparation work has already been documented. The four simulants were used for high and low acid testing. Eight planned experiments (GF26 to GF33) were completed to demonstrate the viability of the glycolic-formic flowsheet. Composition and physical property measurements were made on the SRAT product. Composition measurements were made on the condensate from the Mercury Water Wash Tank (MWWT), Formic Acid Vent Condenser (FAVC), ammonia scrubber and on SRAT samples pulled throughout the SRAT cycle. Updated values for formate loss and nitrite-tonitrate conversion were found that can be used in the acid calculations for future sludge matrix process simulations with the glycolic acid/formic acid flowsheet. Preliminary results of the initial testing indicate: (1) Hydrogen generation rate was very low throughout all SRAT cycles. (2) The mercury concentration of the SRAT product was below the 0.8 wt% limit in all runs. (3) Nitrite in the SRAT product was <100 mg/kg for all runs. (4) Foaminess was not an issue using the nominal antifoam addition strategy in these tests. (5) The high aluminum sludges (LoFe, HM type sludges) were much more viscous than the Hi Fe sludges. At 100% acid stoichiometry, the SRAT products from the high aluminum sludges were very viscous but at 150% acid stoichiometry, the SRAT products from the high aluminum sludges were very thin. This makes the glycolic acid/formic acid flowsheet an improvement for processing more viscous sludges. (6) The pH of the SRAT products was from 2.7-3.1 for the 150% acid stoichiometry runs and 5.1-6.1 for the 100% acid stoichiometry runs, significantly lower than is typical of the baseline nitric acid/formic acid flowsheet.

08 HYDROGEN↗
DOE OSTI2011

Corrective Action Decision Document/Closure Report for Corrective Action Unit 367: Area 10 Sedan, Ess and Uncle Unit Craters Nevada National Security Site, Nevada, Revision 0 with ROTC 1

Corrective Action Unit 367 comprises four corrective action sites (CASs): • 10-09-03, Mud Pit • 10-45-01, U-10h Crater (Sedan) • 10-45-02, Ess Crater Site • 10-45-03, Uncle Crater Site The purpose of this Corrective Action Decision Document/Closure Report is to provide justification and documentation of the corrective actions and site closure activities implemented at CAU 367. A corrective action of closure in place with use restrictions was completed at each of the three crater CASs (10-45-01, 10-45-02, and 10-45-03); corrective actions were not required at CAS 10-09-03. In addition, a limited soil removal corrective action was conducted at the location of a potential source material release. Based on completion of these correction actions, no additional corrective action is required at CAU 367, and site closure is considered complete. Corrective action investigation (CAI) activities were performed from February 2010 through March 2011, as set forth in the Corrective Action Investigation Plan for Corrective Action Unit 367: Area 10 Sedan, Ess and Uncle Unit Craters, Nevada Test Site, Nevada. The approach for the CAI was divided into two facets: investigation of the primary release of radionuclides, and investigation of non-test or other releases (e.g., migration in washes and potential source material). Based on the proximity of the Uncle, Ess, and Sedan craters, the impact of the Sedan test on the fallout deposited from the two earlier tests, and aerial radiological surveys, the CAU 367 investigation was designed to study the releases from the three crater CASs as one combined release (primary release). Corrective Action Site 10-09-03, Mud Pit, consists of two mud pits identified at CAU 367. The mud pits are considered non-test releases or other releases and were investigated independent of the three crater CASs. The purpose of the CAI was to fulfill data needs as defined during the data quality objective (DQO) process. The CAU 367 dataset of investigation results was evaluated based on a data quality assessment. This assessment demonstrated the dataset is complete and acceptable for use in fulfilling the DQO data needs. Analytes detected during the CAI were evaluated against final action levels (FALs) established in this document. For the primary release, radiological doses exceeding the FAL of 25 millirem per year were not found to be present in the surface or shallow subsurface soil outside the default contamination boundary. However, it was assumed that radionuclides are present in subsurface media within each of the three craters (Sedan, Ess, and Uncle) due to prompt injection of radionuclides from the tests. Based on the assumption of radiological dose exceeding the FAL, corrective actions were undertaken that consisted of implementing a use restriction and posting warning signs at each crater CAS. These use restrictions were recorded in the FFACO database; the U.S. Department of Energy, National Nuclear Security Administration Nevada Site Office (NNSA/NSO) Facility Information Management System; and the NNSA/NSO CAU/CAS files. With regard to other releases, no contaminants of concern were identified at the mud pits or any of the other release locations, with one exception. Potential source material in the form of lead was found at one location. A corrective action of clean closure was implemented at this location, and verification samples indicated that no further action is necessary. Therefore, NNSA/NSO provides the following recommendations: • A Notice of Completion to NNSA/NSO is requested from the Nevada Division of Environmental Protection for closure of CAU 367. • Corrective Action Unit 367 should be promoted from Appendix III to Appendix IV of the FFACO.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2011

Secondary waste form testing : ceramicrete phosphate bonded ceramics.

The cleanup activities of the Hanford tank wastes require stabilization and solidification of the secondary waste streams generated from the processing of the tank wastes. The treatment of these tank wastes to produce glass waste forms will generate secondary wastes, including routine solid wastes and liquid process effluents. Liquid wastes may include process condensates and scrubber/off-gas treatment liquids from the thermal waste treatment. The current baseline for solidification of the secondary wastes is a cement-based waste form. However, alternative secondary waste forms are being considered. In this regard, Ceramicrete technology, developed at Argonne National Laboratory, is being explored as an option to solidify and stabilize the secondary wastes. The Ceramicrete process has been demonstrated on four secondary waste formulations: baseline, cluster 1, cluster 2, and mixed waste streams. Based on the recipes provided by Pacific Northwest National Laboratory, the four waste simulants were prepared in-house. Waste forms were fabricated with three filler materials: Class C fly ash, CaSiO{sub 3}, and Class C fly ash + slag. Optimum waste loadings were as high as 20 wt.% for the fly ash and CaSiO{sub 3}, and 15 wt.% for fly ash + slag filler. Waste forms for physical characterizations were fabricated with no additives, hazardous contaminants, and radionuclide surrogates. Physical property characterizations (density, compressive strength, and 90-day water immersion test) showed that the waste forms were stable and durable. Compressive strengths were >2,500 psi, and the strengths remained high after the 90-day water immersion test. Fly ash and CaSiO{sub 3} filler waste forms appeared to be superior to the waste forms with fly ash + slag as a filler. Waste form weight loss was {approx}5-14 wt.% over the 90-day immersion test. The majority of the weight loss occurred during the initial phase of the immersion test, indicative of washing off of residual unreacted binder components from the waste form surface. Waste forms for ANS 16.1 leach testing contained appropriate amounts of rhenium and iodine as radionuclide surrogates, along with the additives silver-loaded zeolite and tin chloride. The leachability index for Re was found to range from 7.9 to 9.0 for all the samples evaluated. Iodine was below detection limit (5 ppb) for all the leachate samples. Further, leaching of sodium was low, as indicated by the leachability index ranging from 7.6-10.4, indicative of chemical binding of the various chemical species. Target leachability indices for Re, I, and Na were 9, 11, and 6, respectively. Degradation was observed in some of the samples post 90-day ANS 16.1 tests. Toxicity characteristic leaching procedure (TCLP) results showed that all the hazardous contaminants were contained in the waste, and the hazardous metal concentrations were below the Universal Treatment Standard limits. Preliminary scale-up (2-gal waste forms) was conducted to demonstrate the scalability of the Ceramicrete process. Use of minimal amounts of boric acid as a set retarder was used to control the working time for the slurry. Flexibility in treating waste streams with wide ranging compositional make-ups and ease of process scale-up are attractive attributes of Ceramicrete technology.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

ANNUAL RADIOACTIVE WASTE TANK INSPECTION PROGRAM 2010

Aqueous radioactive wastes from Savannah River Site (SRS) separations and vitrification processes are contained in large underground carbon steel tanks. Inspections made during 2010 to evaluate these vessels and other waste handling facilities along with evaluations based on data from previous inspections are the subject of this report. The 2010 inspection program revealed that the structural integrity and waste confinement capability of the Savannah River Site waste tanks were maintained. All inspections scheduled per SRR-LWE-2009-00138, HLW Tank Farm Inspection Plan for 2010, were completed. Ultrasonic measurements (UT) performed in 2010 met the requirements of C-ESG-00006, In-Service Inspection Program for High Level Waste Tanks, Rev. 3, and WSRC-TR-2002-00061, Rev.6. UT inspections were performed on Tanks 30, 31 and 32 and the findings are documented in SRNL-STI-2010-00533, Tank Inspection NDE Results for Fiscal Year 2010, Waste Tanks 30, 31 and 32. A total of 5824 photographs were made and 1087 visual and video inspections were performed during 2010. Ten new leaksites at Tank 5 were identified in 2010. The locations of these leaksites are documented in C-ESR-G-00003, SRS High Level Waste Tank Leaksite Information, Rev.5. Ten leaksites at Tank 5 were documented during tank wall/annulus cleaning activities. None of these new leaksites resulted in a release to the environment. The leaksites were documented during wall cleaning activities and the waste nodules associated with the leaksites were washed away. Previously documented leaksites were reactivated at Tank 12 during waste removal activities.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

DNA Extraction by Isotachophoresis in a Microfluidic Channel

Biological assays have many applications. For example, forensics personnel and medical professionals use these tests to diagnose diseases and track their progression or identify pathogens and the host response to them. One limitation of these tests, however, is that most of them target only one piece of the sample - such as bacterial DNA - and other components (e.g. host genomic DNA) get in the way, even though they may be useful for different tests. To address this problem, it would be useful to extract several different substances from a complex biological sample - such as blood - in an inexpensive and efficient manner. This summer, I worked with Maxim Shusteff at Lawrence Livermore National Lab on the Rapid Automated Sample Prep project. The goal of the project is to solve the aforementioned problem by creating a system that uses a series of different extraction methods to extract cells, bacteria, and DNA from a complex biological sample. Biological assays can then be run on purified output samples. In this device, an operator could input a complex sample such as blood or saliva, and would receive separate outputs of cells, bacteria, viruses, and DNA. I had the opportunity to work this summer with isotachophoresis (ITP), a technique that can be used to extract nucleic acids from a sample. This technique is intended to be the last stage of the purification device. Isotachophoresis separates particles based on different electrophoretic mobilities. This technique is convenient for out application because free solution DNA mobility is approximately equal for DNA longer than 300 base pairs in length. The sample of interest - in our case DNA - is fed into the chip with streams of leading electrolyte (LE) and trailing electrolyte (TE). When an electric field is applied, the species migrate based on their electrophoretic mobilities. Because the ions in the leading electrolyte have a high electrophoretic mobility, they race ahead of the slower sample and trailing electrolyte ions. Conversely, the trailing electrolyte ions have a slow electrophoretic mobility, so they lag behind the sample, thus trapping the species of interest between the LE and TE streams. In a typical isotachophoresis configuration, the electric field is applied in a direction parallel to the direction of flow. The species then form bands that stretch across the width of the channel. A major limitation of that approach is that only a finite amount of sample can be processed at once, and the sample must be processed in batches. For our purposes, a form of free-flow isotachophoresis is more convenient, where the DNA forms a band parallel to the edges of the channel. To achieve this, in our chip, the electric field is applied transversely. This creates a force perpendicular to the direction of flow, which causes the different ions to migrate across the flow direction. Because the mobility of the DNA is between the mobility of the leading and the trailing electrolyte, the DNA is focused in a tight band near the center of the channel. The stream of DNA can then be directed to a different output to produce a highly concentrated outlet stream without batch processing. One hurdle that must be overcome for successful ITP is isolating the electrochemical reactions that result from the application of high voltage for the actual process of isotachophoresis. The electrochemical reactions that occur around metal electrodes produce bubbles and pH changes that are detrimental to successful ITP. The design of the chips we use incorporates polyacrylamide gels to serve as electrodes along the central channel. For our design, the metal electrodes are located away from the chip, and high conductivity buffer streams carry the potential to the chip, functioning as a 'liquid electrode.' The stream then runs alongside a gel barrier. The gel electrode permits ion transfer while simultaneously isolating the separation chamber from any contaminants in the outer, 'liquid electrode' streams. The difference in potential from one side of the chip to the other creates an electric field. This field traverses the inner, separation channel, containing the leading electrolyte, the trailing electrolyte, and the sample of interest (DNA). To increase the ease of use of the chips, a newer chip design has been fabricated. This design has wire electrodes integrated on the chip, rather than elsewhere. To keep the pH changes and bubbling isolated from the separation channel, the chip contains deeper wells near the electrodes so that the flowing buffer can wash away any gases that form around the electrode. This design is significantly more compact because it eliminates the cumbersome electrode boxes. Eliminating the electrode boxes also decreases the required voltage, making the experiments safer. This happens because when the 'liquid electrode' streams travel through small diameter tubing, they lose much of their voltage due to the electrical resistance of the fluid in the tubing.

42 ENGINEERING↗
DOE OSTI2011

Corrective Action Decision Document/Closure Report for Corrective Action Unit 374: Area 20 Schooner Unit Crater, Nevada National Security Site, Nevada with ROTC 1 and 2, Revision 0 with ROTCs 1,2, and 3

Corrective Action Unit 374 comprises five corrective action sites (CASs): • 18-22-05, Drum • 18-22-06, Drums (20) • 18-22-08, Drum • 18-23-01, Danny Boy Contamination Area • 20-45-03, U-20u Crater (Schooner) The purpose of this Corrective Action Decision Document/Closure Report is to provide justification and documentation supporting the recommendation that no further corrective action is needed for CAU 374 based on the implementation of corrective actions. The corrective action of closure in place with administrative controls was implemented at CASs 18-23-01 and 20-45-03, and a corrective action of removing potential source material (PSM) was conducted at CAS 20-45-03. The other CASs require no further action; however, best management practices of removing PSM and drums at CAS 18-22-06, and removing drums at CAS 18-22-08 were performed. Corrective action investigation (CAI) activities were performed from May 4 through October 6, 2010, as set forth in the Corrective Action Investigation Plan for Corrective Action Unit 374: Area 20 Schooner Unit Crater, Nevada Test Site, Nevada. The approach for the CAI was divided into two facets: investigating the primary release of radionuclides and investigating other releases (migration in washes and chemical releases). The purpose of the CAI was to fulfill data needs as defined during the data quality objective (DQO) process. The CAU 374 dataset of investigation results was evaluated based on the data quality indicator parameters. This evaluation demonstrated the dataset is acceptable for use in fulfilling the DQO data needs. Analytes detected during the CAI were evaluated against final action levels (FALs) established in this document. Radiological doses exceeding the FAL of 25 millirem per year were found to be present in the surface soil that was sampled. It is assumed that radionuclide levels present in subsurface media within the craters and ejecta fields (default contamination boundaries) at the Danny Boy and Schooner sites exceed the FAL. It is also assumed that PSM in the form of lead-acid batteries at Schooner exceeds the FAL. Therefore, corrective actions were undertaken that consist of removing PSM, where present, and implementing a use restriction and posting warning signs at the Danny Boy and Schooner sites. These use restrictions were recorded in the FFACO database; the U.S. Department of Energy, National Nuclear Security Administration Nevada Site Office (NNSA/NSO) Facility Information Management System; and the NNSA/NSO CAU/CAS files. Therefore, NNSA/NSO provides the following recommendations: • No further corrective actions are necessary for CAU 374. • A Notice of Completion to NNSA/NSO is requested from the Nevada Division of Environmental Protection for closure of CAU 374. • Corrective Action Unit 374 should be moved from Appendix III to Appendix IV of the FFACO.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2011

LITERATURE REVIEW OF BORIC ACID SOLUBILITY DATA

A new solvent system is being evaluated for use in the Modular Caustic-Side Solvent Extraction Unit (MCU) and in the Salt Waste Processing Facility (SWPF). The new system replaces the current dilute nitric acid strip solution with 0.01 M boric acid. This literature study is performed to determine if there is a potential for boric acid to crystallize in the lines with emphasis on the transfer lines to the Defense Waste Processing Facility. This report focuses on the aqueous phase chemistry of boric acid under conditions relevant to MCU and SWPF. Operating and transfer conditions examined for the purpose of this review include temperatures between 13 C (McLeskey, 2008) and 45 C (Fondeur, 2007) and concentrations from 0 to 3M in nitric acid as well as exposure of small amounts of entrained boric acid in the organic phase to the sodium hydroxide caustic wash stream. Experiments were also conducted to observe any chemical reactions and off-gas generation that could occur when 0.01 M boric acid solution mixes with 3 M nitric acid solution and vice versa. Based on the low concentration (0.01M) of boric acid in the MCU/SWPF strip acid and the moderate operating temperatures (13 C to 45 C), it is unlikely that crystallization of boric acid will occur in the acid strip solution under process or transfer conditions. Mixing experiments of boric and nitric acid show no measurable gas generation (< 1 cc of gas per liter of solution) under similar process conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

SUPPLEMENTAL ANALYSES FOR SOLVENT HOLD TANK SAMPLES MCU-11-314, MCU-11-315, MCU-11-316, MCU-11-317, MCU-11-318 AND MCU-11-319

Savannah River National Laboratory (SRNL) periodically analyses 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-11-314, MCU-11-315, MCU-11-316, MCU-11-317, MCU-11-318 and MCU-11-319 have been previously reported. MCU has experienced a modest decline in cesium removal efficiency while processing the current feed, 'Macrobatch 3'. While the target decontamination factor (DF) is 200, the fiscal year 2011 DF average is 161. The results of the prior solvent analysis report did not identify a specific factor that would correlate with the poor cesium decontamination beyond a low concentration of the suppressor, trioctylamine. New analyses of the quarterly sample are reported in this document, as well as a cross-check of {sup 137}Cs measurements for SRNL and F/H lab. Furthermore, in an attempt to discover the reason for the decline in DF at MCU, SRNL was tasked with analyzing numerous Caustic Wash Tank (CWT) and chemical feed samples.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2011

ENHANCED CHEMICAL CLEANING OF SRS WASTE TANKS TO IMPROVE ACTINIDE SOLUBILITY

Processes for the removal of residual sludge from SRS waste tanks have historically used solutions containing up to 0.9 M oxalic acid to dissolve the remaining material following sludge removal. The selection of this process was based on a comparison of a number of studies performed to evaluate the dissolution of residual sludge. In contrast, the dissolution of the actinide mass, which represents a very small fraction of the waste, has not been extensively studied. The Pu, Np, and Am in the sludge is reported to be present as hydrated and crystalline oxides. To identify aqueous solutions which have the potential to increase the solubility of the actinides, the alkaline and mildly acidic test solutions shown below were selected as candidates for use in a series of solubility experiments. The efficiency of the solutions in solubilizing the actinides was evaluated using a simulated sludge prepared by neutralizing a HNO{sub 3} solution containing Pu, Np, and Am. The hydroxide concentration was adjusted to a 1.2 M excess and the solids were allowed to age for several weeks prior to starting the experiments. The sludge was washed with 0.01 M NaOH to prepare the solids for use. Following the addition of an equal portion of the solids to each test solution, the concentrations of Pu, Np, and Am were measured as a function of time over a 792 h (33 day) period to provide a direct comparison of the efficiency of each solution in solubilizing the actinide elements. Although the composition of the sludge was limited to the hydrated actinide oxides (and did not contain other components of demonstrated importance), the results of the study provides guidance for the selection of solutions which should be evaluated in subsequent tests with a more realistic surrogate sludge and actual tank waste.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2011

Corrective Action Decision Document/Closure Report for Corrective Action Unit 375: Area 30 Buggy Unit Craters, Nevada National Security Site, Nevada, Revision 0 with ROTC 1

Corrective Action Unit 375 comprises three corrective action sites (CASs): (1) 25-23-22, Contaminated Soils Site; (2) 25-34-06, Test Cell A Bunker; and (3) 30-45-01, U-30a, b, c, d, e Craters. The purpose of this CADD/CR is to provide justification and documentation supporting the recommendation that no further corrective action is needed for CAU 375 based on the implementation of corrective action of closure in place with administrative controls at CAS 25-23-22, no further action at CAS 25-34-06, and closure in place with administrative controls and removal of potential source material (PSM) at CAS 30-45-01. Corrective action investigation (CAI) activities were performed from July 28, 2010, through April 4, 2011, as set forth in the Corrective Action Investigation Plan for Corrective Action Unit 375: Area 30 Buggy Unit Craters. The approach for the CAI was divided into two facets: investigation of the primary release of radionuclides, and investigation of other releases (migration in washes and chemical releases). The purpose of the CAI was to fulfill data needs as defined during the data quality objective (DQO) process. The CAU 375 dataset of investigation results was evaluated based on the data quality assessment. This assessment demonstrated the dataset is acceptable for use in fulfilling the DQO data needs. Investigation results were evaluated against final action levels (FALs) established in this document. A radiological dose FAL of 25 millirem per year was established based on the Remote Work Area exposure scenario (336 hours of annual exposure). Radiological doses exceeding the FAL were assumed to be present within the default contamination boundaries at CASs 25-23-22 and 30-45-01. No contaminants were identified at CAS 25-34-06, and no corrective action is necessary. Potential source material in the form of lead plate, lead-acid batteries, and oil within an abandoned transformer were identified at CAS 30-45-01, and corrective actions were undertaken that consisted of removing the PSM. Use restrictions and warning signs were implemented for the remaining radiological contamination at CASs 25-23-22 and 30-45-01. These use restrictions were recorded in the FFACO database; the U.S. Department of Energy, National Nuclear Security Administration Nevada Site Office (NNSA/NSO) Facility Information Management System; and the NNSA/NSO CAU/CAS files. Therefore, NNSA/NSO provides the following recommendations: (1) No further corrective actions are necessary for CAU 375; (2) A Notice of Completion to NNSA/NSO is requested from the Nevada Division of Environmental Protection for closure of CAU 375; and (3) Move CAU 375 from Appendix III to Appendix IV of the FFACO.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2011

Estimated United States Residential Energy Use in 2005

A flow chart depicting energy flow in the residential sector of the United States economy in 2005 has been constructed from publicly available data and estimates of national energy use patterns. Approximately 11,000 trillion British Thermal Units (trBTUs) of electricity and fuels were used throughout the United States residential sector in lighting, electronics, air conditioning, space heating, water heating, washing appliances, cooking appliances, refrigerators, and other appliances. The residential sector is powered mainly by electricity and natural gas. Other fuels used include petroleum products (fuel oil, liquefied petroleum gas and kerosene), biomass (wood), and on-premises solar, wind, and geothermal energy. The flow patterns represent a comprehensive systems view of energy used within the residential sector.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2012

Energy Efficiency Upgrades

The energy efficiency upgrades project at Hardin County General Hospital did not include research nor was it a demonstration project. The project enabled the hospital to replace outdated systems with modern efficient models. Hardin County General Hospital is a 501c3, nonprofit hospital and the sole community provider for Hardin and Pope Counties of Illinois. This project provided much needed equipment and facility upgrades that would not have been possible through locally generated funding. Task 1 was a reroofing of the hospital. The hospital architect designed the replacement to increase the energy efficiency of the hospital roof/ceiling structure. Task 2 was replacement and installation of a new more efficient CT scanner for the hospital. Included in the project was replacement of HVAC equipment for the entire radiological suite. Task 5 was a replacement and installation of a new higher capacity diesel-fueled emergency generator for the hospital replacing a 50+ year old gas-fired generator. Task 7 was the replacement of 50+ year-old walk-in cooler/freezer with a newer, energy efficient model. Task 8 was the replacement of 10+ year-old washing machines in the hospital laundry with higher capacity, energy efficient models. Task 9 was replacement of 50-year old single pane curtain window system with double-pane insulated windows. Additionally, insulation was added around ventilation systems and the curtain wall system.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2012

Solar Grade Silicon from Agricultural By-Products

In this project, Mayaterials developed a low cost, low energy and low temperature method of purifying rice hull ash to high purity (5-6Ns) and converting it by carbothermal reduction to solar grade quality silicon (Si pv ) using a self-designed and built electric arc furnace (EAF). Outside evaluation of our process by an independent engineering firm confirms that our technology greatly lowers estimated operating expenses (OPEX) to $\$$5/kg and capital expenses (CAPEX) to $\$$24/kg for Si pv production, which is well below best-in-class plants using a Siemens process approach (OPEX of ≈$\$$14/kg and CAPEX of $\$$87/kg, respectively). The primary limiting factor in the widespread use of photovoltaic (PV) cells is the high cost of manufacturing, compared to more traditional sources to reach 6 g Si pv /watt (with averages closer to 8+g/watt). In 2008, the spot price of Si pv rose to $\$$450/kg. While prices have since dropped to a more reasonable $\$$25/kg; this low price level is not sustainable, meaning the longer-term price will likely return to $\$$35/kg. The 6-8 g Si/watt implies that the Si pv used in a module will cost $\$$0.21-0.28/watt for the best producers (45% of the cost of a traditional solar panel), a major improvement from the cost/wafer driven by the $\$$50/kg Si costs of early 2011, but still a major hindrance in fulfilling DOE goal of lowering the cost of solar energy below $\$$1/watt. The solar cell industry has grown by 40% yearly for the past eight years, increasing the demand for Si pv . As such, future solar silicon price spikes are expected in the next few years. Although industry has invested billions of dollars to meet this ever-increasing demand, the technology to produce Si pv remains largely unchanged requiring the energy intensive, and chlorine dependent Siemens process or variations thereof. While huge improvements have been made, current state-of-the-art industrial plant still use 65 kWh/kg of silicon purified. Our technology offers a key distinction to other technologies as it starts one step upstream from all other Si pv production efforts. Our process starts by producing high purity SiO 2 /C feedstocks from which Si pv can be produced in a single, chlorine free, final EAF step. Specifically, our unique technology, and the resultant SiO 2 /C product can serve as high purity feedstocks to existing metallurgical silicon (Si met ) producers, allowing them to generate Si pv with existing US manufacturing infrastructure, reducing the overall capital and commissioning schedule. Our low energy, low CAPEX and OPEX process purifies the silica and carbon present in rice hull ash (RHA) at low temperatures (< 200°C) to produce high purity (5-6 Ns) feedstock for production of Si pv using furnaces similar to those used to produce Si met . During the course of this project we partnered with Wadham Energy LP (Wadham), who burns 220k ton of rice hulls (RH)/yr generating 200 GWh of electricity/yr and >30k ton/yr RHA. The power generation step produces much more energy (42 kWh/kg of final silicon produced) than required to purify the RHA (5 kWh/kg of Si pv , compared to 65 kWh/kg noted above. Biogenic silica offers three very important foundations for producing high purity silicon. First, wastes from silica accumulating plants, such as rice, corn, many grasses, algae and grains, contain very reactive, amorphous silica from which impurities are easily removed. Second, plants take up only a limited set of, and minimal quantities of the heavy metals present in nature, meaning fewer minerals must be removed. Third, biomass combustion generates a product with intrinsic residual carbon, mixed at nanometer length scales with the SiO 2 . RHA is 80-90 wt% high surface area (20 m 2 /g), amorphous SiO 2 with some simple mineral content mixed intimately with 5-15 wt% carbon. The mineral content is easily removed by low cost, acid washes using Mayaterials IP, leading to purified rice hull ash (RHAclean) at up to 6N purity. This highly reactive silica is partially extracted from RHAclean at 200 C in an environmentally benign process to adjust SiO 2 :C ratios to those needed in EAF processing to Si pv . EAF processing with silica depleted rice hull ash (RHASD), with nanometer scale carbon/silica mixing, reacts up to 10x faster than in traditional EAF processing because the physical distances over which the reactions occur are measured in nm vs cm. We have focused on demonstrating the efficiency in existing furnace technologies, meaning our success offers the potential to convert some portion of existing US furnace infrastructure (for Si met ) to high purity silicon production. The linkage of our process to the existing infrastructure of the U.S. silicon manufacturing industry, already a world leader, is unique compared to all other initiatives trying to produce Si pv . Purifying the silica/carbon mixture before EAF conversion to Si pv greatly reduces CAPEX and OPEX costs, reducing the final solar energy cost by $\$$0.18-0.24/watt.

09 BIOMASS FUELS↗
DOE OSTI2012

Fast Pyrolysis Oil Stabilization: An Integrated Catalytic and Membrane Approach for Improved Bio-oils. Final Report

This University of Massachusetts, Amherst project, "Fast Pyrolysis Oil Stabilization: An Integrated Catalytic and Membrane Approach for Improved Bio-oils" started on 1st February 2009 and finished on August 31st 2011. The project consisted following tasks: Task 1.0: Char Removal by Membrane Separation Technology The presence of char particles in the bio-oil causes problems in storage and end-use. Currently there is no well-established technology to remove char particles less than 10 micron in size. This study focused on the application of a liquid-phase microfiltration process to remove char particles from bio-oil down to slightly sub-micron levels. Tubular ceramic membranes of nominal pore sizes 0.5 and 0.8m were employed to carry out the microfiltration, which was conducted in the cross-flow mode at temperatures ranging from 38 to 45 C and at three different trans-membrane pressures varying from 1 to 3 bars. The results demonstrated the removal of the major quantity of char particles with a significant reduction in overall ash content of the bio-oil. The results clearly showed that the cake formation mechanism of fouling is predominant in this process. Task 2.0 Acid Removal by Membrane Separation Technology The feasibility of removing small organic acids from the aqueous fraction of fast pyrolysis bio-oils using nanofiltration (NF) and reverse osmosis (RO) membranes was studied. Experiments were carried out with a single solute solutions of acetic acid and glucose, binary solute solutions containing both acetic acid and glucose, and a model aqueous fraction of bio-oil (AFBO). Retention factors above 90% for glucose and below 0% for acetic acid were observed at feed pressures near 40 bar for single and binary solutions, so that their separation in the model AFBO was expected to be feasible. However, all of the membranes were irreversibly damaged when experiments were conducted with the model AFBO due to the presence of guaiacol in the feed solution. Experiments with model AFBO excluding guaiacol were also conducted. NF membranes showed retention factors of glucose greater than 80% and of acetic acid less than 15% when operated at transmembrane pressures near 60 bar. Task 3.0 Acid Removal by Catalytic Processing It was found that the TAN reduction in bio-oil was very difficult using low temperature hydrogenation in flow and batch reactors. Acetic acid is very resilient to hydrogenation and we could only achieve about 16% conversion for acetic acid. Although it was observed that acetic acid was not responsible for instability of aqueous fraction of bio-oil during ageing studies (described in task 5). The bimetallic catalyst PtRe/ceria-zirconia was found to be best catalyst because its ability to convert the acid functionality with low conversion to gas phase carbon. Hydrogenation of the whole bio-oil was carried out at 125°C, 1450 psi over Ru/C catalyst in a flow reactor. Again, negligible acetic acid conversion was obtained in low temperature hydrogenation. Hydrogenation experiments with whole bio-oil were difficult to perform because of difficulty to pumping the high viscosity oil and reactor clogging. Task 4.0 Acid Removal using Ion Exchange Resins DOWEX M43 resin was used to carry out the neutralization of bio-oil using a packed bed column. The pH of the bio-oil increased from 2.43 to 3.7. The GC analysis of the samples showed that acetic acid was removed from the bio-oil during the neutralization and recovered in the methanol washing. But it was concluded that process would not be economical at large scale as it is extremely difficult to regenerate the resin once the bio-oil is passed over it. Task 5.0 Characterization of Upgraded Bio-oils We investigated the viscosity, microstructure, and chemical composition of bio-oils prepared by a fast pyrolysis approach, upon aging these fuels at 90ºC for periods of several days. Our results suggest that the viscosity increase is not correlated with the acids or char present in the bio-oils. The viscosity increase is due to formation of high molecular weight polymeric species over time. Our work also suggests that hydrogenation of the samples is beneficial in eliminating the viscosity increase. Task 6.0 Commercialization Assessment Renewable Oil International LLC (ROI) was responsible for Task 6.0, Commercialization Assessment. As part of this effort ROI focused on methods to reduce char carryover in the vapor stream from the fast pyrolysis reactor and residence time of the vapor in the reactor. Changes were made in the bio-oil recovery methodology and a reactor sweep gas used to reduce vapor residence time. Cyclones were placed in the vapor stream to reduce char particulate carryover. Microfiltration of the bio-oil was also researched to remove char particulate from the bio-oil. The capital cost for these improvements would be less than 2% of the total plant capital cost.

09 BIOMASS FUELS↗