Co - Ed : March - Two Step

https://digitalcommons.library.umaine.edu/mmb-ps/2445/thumbnail.jp

Swanee Rose

https://digitalcommons.library.umaine.edu/mmb-vp/2544/thumbnail.jp

As the Years Roll By

https://digitalcommons.library.umaine.edu/mmb-vp/1173/thumbnail.jp

DWPF simulant CPC studies for SB8

The Savannah River National Laboratory (SRNL) accepted a technical task request (TTR) from Waste Solidification Engineering to perform simulant tests to support the qualification of Sludge Batch 8 (SB8) and to develop the flowsheet for SB8 in the Defense Waste Processing Facility (DWPF). These efforts pertained to the DWPF Chemical Process Cell (CPC). Separate studies were conducted for frit development and glass properties (including REDOX). The SRNL CPC effort had two primary phases divided by the decision to drop Tank 12 from the SB8 constituents. This report focuses on the second phase with SB8 compositions that do not contain the Tank 12 piece. A separate report will document the initial phase of SB8 testing that included Tank 12. The second phase of SB8 studies consisted of two sets of CPC studies. The first study involved CPC testing of an SB8 simulant for Tank 51 to support the CPC demonstration of the washed Tank 51 qualification sample in the SRNL Shielded Cells facility. SB8-Tank 51 was a high iron-low aluminum waste with fairly high mercury and moderate noble metal concentrations. Tank 51 was ultimately washed to about 1.5 M sodium which is the highest wash endpoint since SB3-Tank 51. This study included three simulations of the DWPF Sludge Receipt and Adjustment Tank (SRAT) cycle and Slurry Mix Evaporator (SME) cycle with the sludge-only flowsheet at nominal DWPF processing conditions and three different acid stoichiometries. These runs produced a set of recommendations that were used to guide the successful SRNL qualification SRAT/SME demonstration with actual Tank 51 washed waste. The second study involved five SRAT/SME runs with SB8-Tank 40 simulant. Four of the runs were designed to define the acid requirements for sludge-only processing in DWPF with respect to nitrite destruction and hydrogen generation. The fifth run was an intermediate acid stoichiometry demonstration of the coupled flowsheet for SB8. These runs produced a set of processing recommendations for DWPF along with some data related to Safety Class documentation at DWPF. Some significant observations regarding SB8 follow: Reduced washing in Tank 51 led to an increase in the wt.% soluble solids of the DWPF feed. If wt.% total solids for the SRAT and SME product weren’t adjusted upward to maintain insoluble solids levels similar to past sludge batches, then the rheological properties of the slurry went below the low end of the DWPF design bases for the SRAT and SME. Much higher levels of dissolved manganese were found in the SRAT and SME products than in recent sludge batches. Closed crucible melts were more reduced than expected. The working hypothesis is that the soluble Mn is less oxidizing than assumed in the REDOX calculations. A change in the coefficient for Mn in the REDOX equation was recommended in a separate report. The DWPF (Hsu) stoichiometric acid equation was examined in detail to better evaluate how to control acid in DWPF. The existing DWPF equation can likely be improved without changing the required sample analyses through a paper study using existing data. The recommended acid stoichiometry for initial SB8 SRAT batches is 115-120% stoichiometry until some processing experience is gained. The conservative range (based on feed properties) of stoichiometric factors derived in this study was from 110-147%, but SRNL recommends using only the lower half of this range, 110-126% even after initial batches provide processing experience. The stoichiometric range for sludge-only processing appears to be suitable for coupled operation based on results from the run in the middle of the range. Catalytic hydrogen was detectable (>0.005 vol%) in all SRAT and SME cycles. Hydrogen reached 30-35% of the SRAT and SME limits at the mid-point of the stoichiometry window (bounding noble metals and acid demand)

EVALUATION OF ORGANIC VAPOR RELEASE FROM CEMENT-BASED WASTE FORMS

A cement based waste form was evaluated to determine the rates at which various organics were released during heating caused by the cementitious heat-of-hydration reaction. Saltstone is a cement-based waste form for the disposal of low-level salt solution. Samples were prepared with either Isopar{reg_sign} L, a long straight chained hydrocarbon, or (Cs,K) tetraphenylborate, a solid that, upon heating, decomposes to benzene and other aromatic compounds. The saltstone samples were heated over a range of temperatures. Periodically, sample headspaces were purged and the organic constituents were captured on carbon beds and analyzed. Isopar{reg_sign} L was released from the saltstone in a direct relationship to temperature. An equation was developed to correlate the release rate of Isopar{reg_sign} L from the saltstone to the temperature at which the samples were cured. The release of benzene was more complex and relied on both the decomposition of the tetraphenylborate as well as the transport of the manufactured benzene through the curing saltstone. Additional testing with saltstone prepared with different surface area/volume also was performed

Design, operation, and evaluation of the transportable vitrification system

The Transportable Vitrification System (TVS) is a transportable melter system designed to demonstrate the treatment of low-level and mixed hazardous and radioactive wastes such as wastewater treatment sludges, contaminated soils and incinerator ash. The TVS is a large-scale, fully integrated vitrification system consisting of melter feed preparation, melter, offgas, service, and control modules. The TVS was tested with surrogate waste at the Clemson University Environmental Systems Engineering Department`s (ESED) DOE/Industry Center for Vitrification Research prior to being shipped to the DOE Oak Ridge Reservation (ORR) K-25 site for treatment of mixed waste. This testing, along with additional testing at ORR, proved that the TVS would be able to successfully treat mixed waste. These surrogate tests consistently produced glass that met the EPA Toxicity Characteristic Leaching Procedure (TCLP). Performance of the system resulted in acceptable emissions of regulated metals from the offgas system. The TVS is scheduled to begin mixed waste operations at ORR in June 1997

DIRECT DISPOSAL OF A RADIOACTIVE ORGANIC WASTE IN A CEMENTITIOUS WASTE FORM

The disposition of {sup 137}Cs-containing tetraphenylborate (TPB) waste at the Savannah River Site (SRS) by immobilization in the cementitious waste form, or grout called ''saltstone'' was proposed as a straightforward, cost-effective method for disposal. Tests were performed to determine benzene release due to TPB decomposition in saltstone at several initial TPB concentrations and temperatures. The benzene release rates for simulants and radioactive samples were generally comparable at the same conditions. Saltstone monoliths with only the top surface exposed to air at 25 and 55 C at any tetraphenylborate concentration or at any temperature with 30 mg/L TPB gave insignificant releases of benzene. At higher TPB concentrations and 75 and 95 C, the benzene release could result in exceeding the Lower Flammable Limit in the saltstone vaults

ISOPAR L RELEASE FROM SALTSTONE CURED AT 55 C

The decontaminated salt solution waste stream from the Modular Caustic Side Solvent Extraction Unit and the Salt Waste Processing Facility is anticipated to contain entrained extraction solvent. The decontaminated salt solution is scheduled to be processed through Tank 50 into the Saltstone Production Facility. This study, among others, has been undertaken because the solvent concentration in the decontaminated salt solution may cause flammability issues within the Saltstone Disposal Facility that may need to be addressed prior to operation. Previous work at the Savannah River National Laboratory determined the release of Isopar{reg_sign} L from saltstone prepared with a simulated DSS with Isopar{reg_sign} L concentrations ranging from 50 to 200 {micro}g/g in the salt fraction and with test temperatures ranging from ambient to 95 C. The results from the curing of the saltstone showed that the Isopar{reg_sign} L release data can be treated as a percentage of initial concentration in the concentration range studied. The majority of the Isopar{reg_sign} L that was released over the test duration was released in the first few days. The release of Isopar{reg_sign} L begins immediately and the rate of release decreases over time. At higher temperatures the immediate release is larger than at lower temperatures. In this study, saltstone was prepared using a simulated decontaminated salt solution containing Isopar{reg_sign} L concentrations of 50 {micro}L/L (30 {micro}g/g) and 100 {micro}L/L (61 {micro}g/g) and cured at 55 C. The headspace of each sample was purged and the Isopar{reg_sign} L was trapped on a coconut shell carbon tube. The amount of Isopar{reg_sign} L captured was determined using NIOSH Method 1501. The percentage of Isopar{reg_sign} L released after 20 days was 1.4 - 3.7% for saltstone containing 50 {micro}L/L concentration and 2.1 - 4.3% for saltstone containing 100 {micro}L/L concentration. Given the measurement uncertainties in this work there is no clearly discernible relationship between percentage release and initial Isopar{reg_sign} L concentration

ISOPAR L RELEASE RATES FROM SALTSTONE USING SIMULATED SALT SOLUTIONS

The Modular Caustic-Side Solvent Extraction (CSSX) Unit (MCU) and the Salt Waste Processing Facility (SWPF) will produce a Decontaminated Salt Solution (DSS) that will go to the Saltstone Production Facility (SPF). Recent information indicates that solvent entrainment in the DSS is larger than expected. The main concern is with Isopar{reg_sign} L, the diluent in the solvent mixture, and its flammability in the saltstone vault. If it is assumed that all the Isopar{reg_sign} L is released instantaneously into the vault from the curing grout before each subsequent pour, the Isopar{reg_sign} L in the vault headspace is well mixed, and each pour displaces an equivalent volume of headspace, the maximum concentration of Isopar{reg_sign} L in the DSS to assure 25% of the lower flammable limit is not exceeded has been determined to be about 4 ppm. The amount allowed would be higher if the release from grout were significantly less. The Savannah River National Laboratory was tasked with determining the release of Isopar{reg_sign} L from saltstone prepared with a simulated DSS with Isopar{reg_sign} L concentrations ranging from 50 to 200 mg/L in the salt fraction and with test temperatures ranging from ambient to 95 C. The results from the curing of the saltstone showed that the amount of Isopar{reg_sign} L released versus time can be treated as a percentage of initial amount present; there was no statistically significant dependence of the release rate on the initial concentration. The majority of the Isopar{reg_sign} L that was released over the test duration was released in the first few days. The release of Isopar{reg_sign} L begins immediately and the rate of release decreases over time. At higher temperatures the immediate release rate is larger than at lower temperatures. Initial curing temperature was found to be very important as slight variations during the first few hours or days had a significant effect on the amount of Isopar{reg_sign} L released. Short scoping tests at 95 C with solvent containing all components (Isopar{reg_sign} L, suppressor trioctylamine (TOA), and modifier Cs-7SB) except the BOBCalixC6 extractant released less Isopar{reg_sign} L than the tests run with Isopar{reg_sign} L/TOA. Based on these scoping tests, the Isopar{reg_sign} L releases reported herein are conservative. Isopar{reg_sign} L release was studied for a two-month period and average cumulative release rates were determined from three sets of tests each at 95 and 75 C and at ambient conditions. The overall average releases at were estimated for each temperature. For the 95 and 75 C data, at a 5% significance level, the hypothesis that the three test sets at each temperature had the same average percent release can be rejected, suggesting that there was a statistically significant difference among the three averages seen in the three experimental tests conducted. An upper confidence limit on the mean percent release required incorporation of variation from two sources: test-to-test variation as well as the variation within a test. An analysis of variance that relies on a random effects model was used to estimate the two variance components. The test-to-test variance and the within test (or residual) variance were both calculated. There is no indication of a statistically significant linear correlation between the percent Isopar{reg_sign} L release and the Isopar{reg_sign} L initial concentration. From the analysis of variance, upper confidence limits at confidences of 80-95% were calculated for the data at 95 and 75 C. The mean Isopar{reg_sign} L percent releases were 67.33% and 13.17% at 95 and 75 C, respectively

Structure–activity relationships of dinucleotides: Potent and selective agonists of P2Y receptors

Dinucleoside polyphosphates act as agonists on purinergic P2Y receptors to mediate a variety of cellular processes. Symmetrical, naturally occurring purine dinucleotides are found in most living cells and their actions are generally known. Unsymmetrical purine dinucleotides and all pyrimidine containing dinucleotides, however, are not as common and therefore their actions are not well understood. To carry out a thorough examination of the activities and specificities of these dinucleotides, a robust method of synthesis was developed to allow manipulation of either nucleoside of the dinucleotide as well as the phosphate chain lengths. Adenosine containing dinucleotides exhibit some level of activity on P2Y1 while uridine containing dinucleotides have some level of agonist response on P2Y2 and P2Y6. The length of the linking phosphate chain determines a different specificity; diphosphates are most accurately mimicked by dinucleoside triphosphates and triphosphates most resemble dinucleoside tetraphosphates. The pharmacological activities and relative metabolic stabilities of these dinucleotides are reported with their potential therapeutic applications being discussed