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Quarterly report on the ferrocyanide safety program for the period ending June 30, 1996

Description: This quarterly report provides a status of activities underway on the Ferrocyanide Safety Issue at the Hanford Site, including actions in response to Defense Nuclear Facilities Safety Board (DNFSB) Recommendation 90-7 (FR 1990). In March 1991, a DNFSB implementation plan (Cash 1991) responding to the six parts of Recommendation 90-7 was prepared and sent to the DNFSB. A ferrocyanide safety program plan addressing the total Ferrocyanide Safety Program, including the six parts of DNFSB Recommendation 90-7, was released in October 1994 (DOE 1994b). Activities in the program plan are underway or are completed, and the status of each is described in Sections 2.0 and 3. 0 of this report.
Date: July 31, 1996
Creator: Dukelow, G.T., Westinghouse Hanford
Partner: UNT Libraries Government Documents Department

Dry-out and low temperature calcination of DST/SST waste blend high temperature melter feed

Description: The FY1994 DST/SST blend was prepared in accordance with the DST/SST blend feed specification. The laboratory preparation steps and observations were compared with an existing experience base to verify the acceptability of the feed specification for simulant make-up. The most significant test results included a variety of features. Ferrocyanide breaks down to NH{sub 3} plus formate, during the low-temperature calcining phase of the tests. Ferrocyanide displayed no redox reactivity with the nitrates and nitrites contained in the slurry in the absence of sugar. Sugar displays a redox reaction with the nitrates and nitrites in the blend similar to the redox. reaction observed in the LLW feed simulant. Boiling of a free flowing slurry occurs at temperatures below about 120{degrees}C. When about 45% of the total water loss has occurred, the feed slurry congeals and continues to lose water, shrinking and developing shrinkage cracks. Water stops coming off between 350{degrees}C and 400{degrees}C. Slurry shear strength and viscosity strongly increase as the weight percent solids increases from 20 wt% to 45 wt%. The 45 wt% solids corresponds to approximately a 40 % water loss. The principle beat sensitivity for this material is the exothermic reaction which is activated when the temperature exceeds about 250{degrees}C. The breakdown of ferrocyanide to ammonia and formate under strongly basic conditions may begin at temperatures less than 100{degrees}C, but the rate increased strongly with increasing temperature and appeared to be completed in the time of our tests. Differential thermal analysis (DTA) results on feed slurry without and with ferrocyanide showed only endothermic behavior. This is consistent with the dry out and low temperature calcine studies which did not indicate any exothermic behavior for the feed slurry with and without ferrocyanide.
Date: February 1, 1996
Creator: Smith, H.D. & Tracey, E.M.
Partner: UNT Libraries Government Documents Department

Functional design criteria for the self-installing liquid observation well

Description: This document presents the functional Design Criteria for installing liquid observation wells (LOWs) into single-shell tanks containing ferrocyanide and organic wastes. The LOWs will be designed to accommodate the deployment of gamma, neutron, and electromagnetic induction probes and to interface with the existing tank structure and environment.
Date: January 1, 1996
Creator: Parra, S.A.
Partner: UNT Libraries Government Documents Department

Tank characterization report for single-shell tank 241-T-107

Description: This document summarizes the information on the historical uses, present status, and the sampling and analysis results of waste stored in Tank 241-T-107. This tank is listed on the Ferrocyanide Watch List. This report supports the requirements of the Tri-Party Agreement Milestone M-44-05.
Date: May 1, 1997
Creator: Sasaki, L.M.
Partner: UNT Libraries Government Documents Department

Assessment of the potential for ferrocyanide propagating reaction accidents

Description: This report contains safety criteria for the storage of ferrocyanide bearing waste sludges in Hanford underground waste storage tanks. In addition, the tank wastes are categorized with this criteria into SAFE, CONDITIONALLY SAFE, and UNSAFE categories based on available historical records and sample information. Fourteen (14) tanks are classified as CONDITIONALLY SAFE, while four (4) C-Farm tanks are categorized as SAFE. This report therefore provides a technical basis to resolve the ferrocyanide safety issue for these four tanks and supports their removal from the Watch List. The 14 CONDITIONALLY SAFE tanks will be re-evaluated in a future revision to this report as representative sample data becomes available. It is anticipated that the 14 tanks will be re-categorized as SAFE at that time.
Date: January 1, 1996
Creator: Meacham, J.E.; Cash, R.J. & Dickinson, D.R.
Partner: UNT Libraries Government Documents Department

Quarterly report on the ferrocyanide safety program for the period ending March 31, 1996

Description: This is the twentieth quarterly report on the progress of activities addressing the Ferrocyanide Safety Issue associated with Hanford Site high-level radioactive waste tanks. Progress in the Ferrocyanide Safety Program is reviewed, including work addressing the six parts of Defense Nuclear Facilities Safety Board Recommendation 90-7 (FR 1990). All work activities are described in the revised program plan (DOE 1994b), and this report follows the same fomzat presented there. A summary of the key events occurring this quarter is presented in Section 1. 2. More detailed discussions of progress are located in Sections 2. 0 through 4. 0.
Date: May 8, 1996
Creator: Meacham, J.E.
Partner: UNT Libraries Government Documents Department

Surface moisture measurement system operation and maintenance manual

Description: The purpose of this manual is to provide detailed operating instructions for the Surface Moisture Measurement System (SMMS).In addition, operating instructions for the Liquid Observation Well Moisture Measurement System (LOWMMS) are included. These systems were developed primarily in support of Tank Waste Remediation System (TWRS) Safety Programs for moisture measurement in organic and ferrocyanide watch list tanks.
Date: June 11, 1996
Creator: Vargo, G.F., Westinghouse Hanford
Partner: UNT Libraries Government Documents Department

Electromagnetic induction moisture measurement system acceptance test plan

Description: The purpose of this acceptance test plan (ATP) is to verify that the mechanical, electrical and software features of the ElectroMagnetic Induction (EMI) probe are operating as designed,and that the unit is ready for field service. The accepted EMI and Surface Moisture Measurement Systems (SMMS) will be used primarily in support of Tank Waste Remediation System (TWRS) Safety Programs for moisture measurement of organic and ferrocyanide watch list tanks.
Date: August 1, 1996
Creator: Vargo, G.F., Westinghouse Hanford
Partner: UNT Libraries Government Documents Department

Assessment of the potential for ferrocyanide propagating reaction accidents

Description: The risk posed by the continued storage of ferrocyanide wastes in Hanford Site underground storage tanks has been studied extensively using theoretical analyses, laboratory experiments,tank monitoring, and waste sampling. This report provides an assessment of this hazard and provides the technical basis to resolve the Ferrocyanide Safety Issue for the 18 tanks, and supports the removal of these tanks from the Watch List. Based on the assessment provided in this report, the ferrocyanide waste in all 18 of the current ferrocyanide Watch List tanks, is categorized as safe and cannot burn or explode.
Date: July 3, 1996
Creator: Meacham, J.E., Westinghouse Hanford
Partner: UNT Libraries Government Documents Department

Electrically switched cesium ion exchange. FY 1997 annual report

Description: This paper describes the Electrically Switched Ion Exchange (ESIX) separation technology being developed as an alternative to ion exchange for removing radionuclides from high-level waste. Progress in FY 1997 for specific applications of ESIX is also outlined. The ESIX technology, which combines ion exchange and electrochemistry, is geared toward producing electroactive films that are highly selective, regenerable, and long lasting. During the process, ion uptake and elution can be controlled directly by modulating the potential of an ion exchange film that has been electrochemically deposited onto a high surface area electrode. This method adds little sodium to the waste stream and minimizes the secondary wastes associated with traditional ion exchange techniques. Development of the ESIX process is well underway for cesium removal using ferrocyanides as the electroactive films. Films having selectivity for perrhenate (a pertechnetate surrogate) over nitrate also have been deposited and tested. Based on the ferrocyanide film capacity, stability, rate of uptake, and selectivity shown during performance testing, it appears possible to retain a consistent rate of removal and elute cesium into the same elution solution over several load/unload cycles. In batch experiments, metal hexacyanoferrate films showed high selectivities for cesium in concentrated sodium solutions. Cesium uptake was unaffected by Na/Cs molar ratios of up to 2 x 10{sup 4} , and reached equilibrium within 18 hours. During engineering design tests using 60 pores per inch, high surface area nickel electrodes, nickel ferrocyanide films displayed continued durability. losing less than 20% of their capacity after 1500 load/unload cycles. Bench-scale flow system studies showed no change in capacity or performance of the ESIX films at a flow rate up to 13 BV/h, the maximum flow rate tested, and breakthrough curves further supported once-through waste processing. 9 refs., 24 figs.
Date: September 1, 1997
Creator: Lilga, M.A.; Orth, R.J. & Sukamto, J.P.H.
Partner: UNT Libraries Government Documents Department

Data requirements for the Ferrocyanide Safety Issue developed through the data quality objectives process. Revision 1

Description: This document provides the requirements for obtaining tank characterization information to support resolution of the Ferrocyanide Safety Issue at the Hanford Site by applying the data quality objectives (DQO) process. A strategy describing the overall approach to safe storage and disposal of the waste in the ferrocyanide tanks identifies the problems and decisions that require characterization data. The DQO process is applied to each decision or group of related decisions to specify data requirements.
Date: April 28, 1995
Creator: Meacham, J.E. & Cash, R.J.
Partner: UNT Libraries Government Documents Department

Surface moisture measurement system hardware acceptance test report

Description: This document summarizes the results of the hardware acceptance test for the Surface Moisture Measurement System (SMMS). This test verified that the mechanical and electrical features of the SMMS functioned as designed and that the unit is ready for field service. The bulk of hardware testing was performed at the 306E Facility in the 300 Area and the Fuels and Materials Examination Facility in the 400 Area. The SMMS was developed primarily in support of Tank Waste Remediation System (TWRS) Safety Programs for moisture measurement in organic and ferrocyanide watch list tanks.
Date: May 28, 1996
Creator: Ritter, G. A.
Partner: UNT Libraries Government Documents Department

Ferrocyanide safety program: Final report on adiabatic calorimetry and tube propagation tests with synthetic ferrocyanide materials

Description: Based on Fauske and Associates, Inc. Reactive System Screening Tool tests, the onset or initiation temperature for a ferrocyanide-nitrate propagating reaction is about 250 degrees Celcius. This is at about 200 degrees Celcius higher than current waste temperatures in the highest temperature ferrocyanide tanks. Furthermore, for current ambient waste temperatures, the tube propagation tests show that a ferrocyanide concentration of 15.5 wt% or more is required to sustain a propagation reaction in the complete absence of free water. Ignoring the presence of free water, this finding rules out propagating reactions for all the Hanford flowsheet materials with the exception of the ferrocyanide waste produced by the original In Farm flowsheet
Date: September 29, 1995
Creator: Fauske, H.F.; Meacham, J.E. & Cash, R.J.
Partner: UNT Libraries Government Documents Department

Ferrocyanide tank safety program: Cesium uptake capacity of simulated ferrocyanide tank waste. Final report

Description: The objective of this project is to determine the capacity for {sup 137}Cs uptake by mixed metal ferrocyanides present in Hanford Site waste tanks, and to assess the potential for aggregation of these {sup 137}Cs-exchanged materials to form ``hot-spots`` in the tanks. This research, performed at Pacific Northwest Laboratory (PNL) for Westinghouse Hanford Company, stems from concerns regarding possible localized radiolytic heating within the tanks. After ferrocyanide was added to 18 high-level waste tanks in the 1950s, some of the ferrocyanide tanks received considerable quantities of saltcake waste that was rich in {sup 137}Cs. If radioactive cesium was exchanged and concentrated by the nickel ferrocyanide present in the tanks, the associated heating could cause tank temperatures to rise above the safety limits specified for the ferrocyanide-containing tanks, especially if the supernate in the tanks is pumped out and the waste becomes drier.
Date: July 1, 1995
Creator: Burgeson, I.E. & Bryan, S.A.
Partner: UNT Libraries Government Documents Department

Scanning electron microscopic analyses of Ferrocyanide tank wastes for the Ferrocyanide safety program

Description: This is Fiscal Year 1995 Annual Report on the progress of activities relating to the application of scanning electron microscopy in addressing the Ferrocyanide Safety Issue associated with Hanford Site high-level radioactive waste tanks. The status of the FY 1995 activities directed towards establishing facilities capable of providing SEM based micro-characterization of ferrocyanide tank wastes is described. A summary of key events in the SEM task over FY 1995 and target activities in FY 1996 are presented. A brief overview of the potential applications of computer controlled SEM analytical data in light of analyses of ferrocyanide simulants performed by an independent contractor is also presented
Date: September 1, 1995
Creator: Callaway, W.S.
Partner: UNT Libraries Government Documents Department

Functional design criteria for the self-installing liquid observation well. Revision 2

Description: This document presents the functional design criteria for installing liquid observation wells (LOWs) into single-shell tanks containing ferrocyanide or organic wastes. The LOWs will be designed to accommodate the deployment of gamma, neutron, and electromagnetic induction probes and to interface with the existing tank structure and environment.
Date: December 4, 1995
Creator: Parra, S.A.
Partner: UNT Libraries Government Documents Department

Modeling water retention of sludge simulants and actual saltcake tank wastes

Description: The Ferrocyanide Tanks Safety Program managed by Westinghouse hanford Company has been concerned with the potential combustion hazard of dry tank wastes containing ferrocyanide chemical in combination with nitrate salts. Pervious studies have shown that tank waste containing greater than 20 percent of weight as water could not be accidentally ignited. Moreover, a sustained combustion could not be propagated in such a wet waste even if it contained enough ferrocyanide to burn. Because moisture content is a key critical factor determining the safety of ferrocyanide-containing tank wastes, physical modeling was performed by Pacific Northwest National laboratory to evaluate the moisture-retaining behavior of typical tank wastes. The physical modeling reported here has quantified the mechanisms by which two main types of tank waste, sludge and saltcake, retain moisture in a tank profile under static conditions. Static conditions usually prevail after a tank profile has been stabilized by pumping out any excess interstitial liquid, which is not naturally retained by the waste as a result of physical forces such as capillarity.
Date: July 1, 1996
Creator: Simmons, C.S.
Partner: UNT Libraries Government Documents Department

Ferrocyanide Safety Project: Comparison of actual and simulated ferrocyanide waste properties

Description: In the 1950s, additional high-level radioactive waste storage capacity was needed to accommodate the wastes that would result from the production of recovery of additional nuclear defense materials. To provide this additional waste storage capacity, the Hanford Site operating contractor developed a process to decontaminate aqueous wastes by precipitating radiocesium as an alkali nickel ferrocyanide; this process allowed disposal of the aqueous waste. The radiocesium scavenging process as developed was used to decontaminate (1) first-cycle bismuth phosphate (BiPO{sub 4}) wastes, (2) acidic wastes resulting from uranium recovery operations, and (3) the supernate from neutralized uranium recovery wastes. The radiocesium scavenging process was often coupled with other scavenging processes to remove radiostrontium and radiocobalt. Because all defense materials recovery processes used nitric acid solutions, all of the wastes contained nitrate, which is a strong oxidizer. The variety of wastes treated, and the occasional coupling of radiostrontium and radiocobalt scavenging processes with the radiocesium scavenging process, resulted in ferrocyanide-bearing wastes having many different compositions. In this report, we compare selected physical, chemical, and radiochemical properties measured for Tanks C-109 and C-112 wastes and selected physical and chemical properties of simulated ferrocyanide wastes to assess the representativeness of stimulants prepared by WHC.
Date: September 1, 1994
Creator: Scheele, R.D.; Burger, L.L.; Sell, R.L.; Bredt, P.R. & Barrington, R.J.
Partner: UNT Libraries Government Documents Department

Tank 241-BY-103 Tank Characterization Plan. Revision 1

Description: This document is a plan which serves as the contractual agreement between the Characterization Program, Sampling Operations and WHC 222-S Laboratory. The scope of this plan is to provide guidance for the sampling and analysis of samples for tank 241-BY-103.
Date: February 27, 1995
Creator: Schreiber, R.D.
Partner: UNT Libraries Government Documents Department

Characterization report for the ferrocyanide safety issue

Description: Recently PNNL was tasked by DOE to develop and demonstrate a risk-based strategic approach to characterizing Hanford`s Nuclear Waste Tanks. This strategic approach was documented in a report entitled ``A Risk-Based Focused Decision-Management Approach for Justifying Characterization of Hanford Tank Waste``. In support of the general approach, a specific strategy for addressing each of the several safety issues associated with the tanks was developed. This report documents the approach for the Ferrocyanide Safety Issue. The purpose of this report is to describe a structured logic diagram (SLD) for determining the risk associated with the ferrocyanide tank safety issue and provide the supporting information for the SLD. The SLD addresses the resolution of risks resulting from the presence of ferrocyanide layers within the Hanford tanks. The informational requirements for determining risk from any reaction stemming from ferrocyanide are outlined in the SLD. This report will describe the potential paths to a successful resolution of the ferrocyanide safety issue. Complete development of the intervention pathway is outside the scope of this current activity. General descriptions of the approach, key components of the SLD, and conclusions are provided in the body of this report. The complete SLD, descriptions of each box shown in the SLD, a discussion on how to fill data needs, and a list of contributors is provided in the appendices.
Date: June 1, 1997
Creator: Pulsipher, B.A.; Burger, L.L.; Liebetrau, A.M. & Scheele, R.D.
Partner: UNT Libraries Government Documents Department

Surface Moisture Measurement System Operation and Maintenance Manual

Description: This operations and maintenance manual addresses deployment, equipment and field hazards, operating instructions, calibration verification, removal, maintenance, and other pertinent information necessary to safely operate and store the Surface Moisture Measurement System (SMMS) and Liquid Observation Well Moisture Measurement System (LOWMMS). These systems were developed primarily in support of Tank Waste Remediation System (TWRS) Safety Programs for moisture measurement in organic and ferrocyanide watch list tanks.
Date: December 1, 1995
Creator: Ritter, G.A.; Pearce, K.L. & Stokes, T.L.
Partner: UNT Libraries Government Documents Department

Quarterly report on the Ferrocyanide Safety Program for the period ending, March 31, 1995

Description: This quarterly report provides a status of the activities underway on the Ferrocyanide Safety Issue at the Hanford Site, including actions in response to Defense Nuclear Facilities Safety Board (DNFSB) Recommendation 90-7 (FR 1990). In March 1991, a DNFSB implementation plan (Cash 1991) responding to the six parts of Recommendation 90-7 was prepared and sent to the DNFSB. A Ferrocyanide Safety Program Plan addressing the total Ferrocyanide Safety Program, including the six parts of DNFSB Recommendation 90-7, was released in October 1994 (DOE 1994b). Activities in the program plan are underway or have been completed, and the status of each is described in Sections 2.0 and 3.0 of this report.
Date: April 1, 1995
Creator: Cash, R.J.; Meacham, J.E. & Dukelow, G.T.
Partner: UNT Libraries Government Documents Department