Double shell tanks (DST) chemistry control data quality objectives

The Tank Waste Remediation System (TWRS) has adopted a data quality objective (DQO) process to define informational needs required to address waste tank safety issues. This document, the Organic Solvent DQO, provides a process to resolve the Organic Solvent Safety Issue. Organic solvents in the presence of air (a source of oxidizer) in a waste tank headspace can combust when heated to the flash point of the solvent. Separable phase organic liquids can form a combustible situation by being present as a pool on the waste surface, or by collecting in sufficient concentration entrained in the waste solids to form a combustible mixture at the waste surface by capillary or wicking behavior. Organic solvent combustion would result in an increase in pressure and temperature of the gas in the waste tank headspace. A significant pressure increase could result in the release of radionuclides and toxic materials to the environment. The Organic Solvent DQO is based on several technical documents, summarized and referenced throughout, that provide the technical bases for threshold values (decision limits) used to develop decision rules that address the problem statement. Likewise, this DQO supports characterization documents, such as the tank sampling analysis plan (TSAP) and tank characterization plan (TCP). The threshold values are based upon approved technical documents. Any changes to these technical documents will be reflected in subsequent changes to this DQO. This DQO applies to static organic waste as presently stored in single-shell tanks (SSTs) and double-shell tanks (DSTs). Waste undergoing retrieval, pretreatment, and processing are outside the scope of this DQO.

There are 177 waste storage tanks containing over 210,000 m{sup 3} (55 million gal) of mixed waste at the Hanford Site. The River Protection Project (RPP) has adopted the data quality objective (DQO) process used by the U.S. Environmental Protection Agency (EPA) (EPA 1994a) and implemented by RPP internal procedure (Banning 1999a) to identify the information and data needed to address safety issues. This DQO document is based on several documents that provide the technical basis for inputs and decision/action levels used to develop the decision rules that evaluate the transfer of wastes. A number of these documents are presently in the process of being revised. This document will need to be revised if there are changes to the technical criteria in these supporting documents. This DQO process supports various documents, such as sampling and analysis plans and double-shell tank (DST) waste analysis plans. This document identifies the type, quality, and quantity of data needed to determine whether transfer of supernatant can be performed safely. The requirements in this document are designed to prevent the mixing of incompatible waste as defined in Washington Administrative Code (WAC) 173-303-040. Waste transfers which meet the requirements contained in this document and the Double-Shell Tank Waste Analysis Plan (Mulkey 1998) are considered to be compatible, and prevent the mixing of incompatible waste.

This report documents the evaluations was undertaken to establish the sampling and analysis requirements, for the Double-Shell Tank (DST) waste based on a review of the chemical composition of the waste mechanisms for chemistry change, and operations and waste transfers in the tanks. A sampling schedule, for the DST waste has been established previously and is documented in the Technical sampling Basis-Waste Information Requirements Document (TSB-WIRD). However, the TSB-WIRD was based on programmatic drivers for the collection of waste samples rather than on the specific needs of a chemistry control program. The focus of this evaluation is to ensure that the sampling requirements of the TSB-WIRD meet the needs of the DST chemistry control program defined in Tank Farms Technical Safety Requirements (TSR) Administrative Control (AC) 5.15, and to provide adjustments, if necessary, to those sampling requirements to account for known mechanisms for changes in chemistry of the tanks. DST waste composition data for nitrite, nitrate, and hydroxide was compiled from sample data and best basis liquid composition data extracted from the Tank Waste Information Network System (TWINS) database. Operations in the tanks up to January 1, 2001, were reviewed. Three free hydroxide depletion models were used to predict the future tank liquid hydroxide concentration over the next five year period and trend historical sample results where possible. This data was used as the method to provide priority to the sampling requirements provided in the TSB-WIRD. The effort looked at identifying those tanks that could become caustic deficient prior to the next scheduled tank specific sampling event, and recommended appropriate actions for those tanks that may not comply with the waste chemistry limits defined in AC 5.15.

The presence of organic chemicals regulated under the Resource Conservation and Recovery Act (RCRA) Land Disposal Restrictions (LDR) adds complexity to treating and disposing of the low activity fraction of Hanford tank waste if a low temperature treatment method such as grouting is used (SRNL-STI-2020-00228). The complexity arises from the fact that the baseline vitrification method is considered by the Washington State Department of Ecology (Ecology) as providing adequate thermal treatment for organics; a status not automatically extended to a lowtemperature process, such as solidifying the waste in a cementitious waste form. In addition, the Environmental Protection Agency (EPA) LDR program is intended to ensure that wastes are properly treated prior to disposal. Proper treatment makes hazardous waste less harmful to groundwater by reducing the mobility and/or toxicity of the hazardous constituents in the waste. EPA guidance indicates that stabilization/solidification of waste for organics could be considered impermissible dilution under the LDR dilution prohibition. In addition, waste storage activities at Hanford have required transferring and blending waste within the tank system and these activities have potentially altered the concentrations of the hazardous constituents. The LDR dilution prohibition found in 40 Code of Federal Regulations (CFR) 268.3 states that “… no generator, transporter, handler, or owner or operator of a treatment, storage, or disposal facility shall in any way dilute a restricted waste or the residual from treatment of a restricted waste as a substitute for adequate treatment …”. Hence, if LAW is to be treated using low temperature stabilization (such as cementation), then it is important to demonstrate both how past storage activities have contributed to the removal (by vacuum evaporation), or destruction (by in situ decomposition) of the LDR organics and how future retrieval and waste feed preparation will contribute to their removal (by filtration and ion exchange). Demonstrating these processes helps validate that cementation without additional organic treatment does not necessarily represent impermissible dilution. To aid in implementing cementitious solidification of Low Activity Waste (LAW), WRPS has been developing a regulatory and processing LDR treatment variance strategy termed “Sampleand-Send” that relies, in part, on demonstrating that in situ decomposition reactions along with historic evaporation of tank waste has destroyed or removed most of the LDR organics possibly associated with Hanford Tank Waste (SRNL-STI-2020-00582, SRNL-STI-2021-00453, SRNL-STI-2022-00391). Under the Sample-and-Send concept, Hanford tank waste would be retrieved, processed through a Tank-Side Cesium Removal-like system, and staged as a candidate feed that would then be sampled to confirm the waste acceptance criteria is met for solidification in an LAW cementitious treatment facility. If it can be shown that LDR organics are at concentrations below the waste acceptance criteria (WAC) for cementitious stabilization and have been sufficiently removed (by historic evaporation or by filtration and ion exchange during Cs removal), destroyed (by historic in situ decomposition), or are not soluble in LAW above the WAC then additional organic treatment is not needed prior to creating a cementitious final waste form and the concept of Sample-and-Send would be proposed to establish a non-rulemaking site-specific treatment variance using the specified method of treatment “STABL” to remove sampling requirements of the waste form after treatment. Waste not meeting the WAC could either be routed to the Hanford Waste Treatment and Immobilization Plant for LAW vitrification, or further processed by evaporation or chemical oxidation before solidifying in a cementitious waste form. A key component in implementing the Sample-and-Send strategy is identifying which of the 207 LDR organic compounds associated with the RCRA Part A permit application waste codes for the Double Shell Tanks (DSTs) and Single Shell Tanks (SSTs) and any applicable Underlying Hazardous Constituents (UHCs) from 40 CFR 268.48 should be considered as potentially present and thus subject to regulation. In addition, it is also necessary to understand the solubility volatility, and reactivity of these compounds in LAW to identify which of the potentially present LDR organic compounds are not soluble above regulatory levels or are likely to have been removed by historic evaporation or destroyed by in situ decomposition reactions. If there are potentially present LDR organic compounds that have not been removed or destroyed and are soluble above regulatorily significant concentrations then a treatability variance may be needed for these species to eliminate any concerns pertaining to impermissible dilution. The spreadsheet accompanying this calculation report contains the data and logic computations needed to screen the list of 207 LDR organics associated with Hanford tank waste to identify those potentially present and to indicate which compounds may need to be included in a treatability variance.

The US. Department of Energy, Richland Operations Office (DOE-RL) has initiated Phase 1 of a two-phase privatization strategy for treatment and immobilization of low-activity waste (LAW) currently being managed by the Hanford Tank Waste Remediation System (TWRS) Project. In this strategy, DOE will purchase services from a contractor-owned and operated facility under a fixed price. The Phase 1 TWRS privatization contract requires that the Project Hanford Management Contract (PHMC) contractors, on behalf of DOE, deliver LAW feed in specified quantities and composition to the Privatization Contractor in a timely manner (DOE-RL 1996). Additional requirements are imposed by the interface control document (ICD-19) for LAW feed (PHMC 1997). In response to these requirements, the Tank Waste Remediation System Operation and Utilization Plan (TWRSO and UP) (Kirkbride et al. 1997) was prepared by the PHMC. The TWRSO and UP, as updated by the Readiness-To-Proceed deliverable (Payne et al. 1998), establishes the baseline operating scenario for the delivery of LAW feed to the Privatization Contractor. The scenario specifies tanks from which LAW will be provided for each feed batch, the operational activities needed to prepare and deliver each batch, and the timing of these activities. The operating scenario was developed based on current knowledge of waste composition and chemistry, waste transfer methods, and operating constraints, such as tank farm logistics and availability of tank space. A project master baseline schedule (PMBS) has been developed to implement the operating scenario. The PMBS also includes activities aimed at reducing programmatic risks. One of the activities, ''Confirm Plans and Requirements,'' was identified to verify the basis used to develop the scenario. Additional data on waste quantity, physical and chemical characteristics, and transfer properties will be needed to support this activity. This document describes the data quality objective (DQO) process undertaken to assme appropriate data will be collected to support the activity, ''Confirm Tank Plans and Requirements.'' The DQO process was implemented in accordance with the TWRS DQO process (Banning 1997) with some modifications to accommodate project or tank-specific requirements and constraints.

During most of the year, it is assumed that the vapor in the 177 radioactive waste tanks on the Hanford Project site contain a uniform mixture of gases. Several of these waste tanks (currently twenty five, 6 Double Shell Tanks and 19 Single Shell Tanks) were identified as having the potential for the buildup of gases to a flammable level. An active ventilation system in the Double Shell Tanks and a passive ventilation system in the Single Shell Tanks provides a method of expelling gases from the tanks. A gas release from a tank causes a temporary rise in the tank pressure, and a potential for increased concentration of hydrogen gas in the vapor space. The gas is released via the ventilation systems until a uniform gas mixture in the vapor space is once again achieved. This document describes the design of the Standard-B Hydrogen Monitoring System, (SHMS) and its components as it differs from the original SHMS. The differences are derived from changes made to improve the system performance but not implemented in all the installed enclosures.

The Hanford Site is a 560-square-mile (1,450-km2) complex established by the U.S. government in 1943 to produce plutonium for nuclear weapons, ultimately bringing an end to World War II. Plutonium production activities continued after the war through 1991, at which point the site’s mission changed from plutonium production to environmental cleanup and restoration. Production activities at the site resulted in a broad range of contaminated materials and facilities, including 57 million gallons of high-level (i.e., highly radioactive) nuclear waste in liquid and solid forms. The high-level waste was stored as it was created, first in single-shell tanks built between 1943 and 1964, then in more robust double-shell tanks constructed between 1968 and 1986. Due to waste leakage in a small number of single-shell tanks and the potential for additional single-shell tank failures, all single-shell tanks were removed from service by 1980. All pumpable liquid has been transferred to sound double-shell tanks. The double-shell tanks have either exceeded or are expected to exceed their design life, and are managed under a comprehensive integrity management program. Key features of the program include the application and optimization of a waste chemistry specification designed to minimize corrosion in the double-shell tanks, laboratory studies, and the installation of double-shell tank corrosion monitoring systems to improve the understanding of waste corrosiveness, the development and application of an extensive non-destructive examination program to detect excessive corrosion or other forms of double-shell tank degradation should they occur, and the development and application of a comprehensive structural analysis program. Together, these programs help to ensure the continued availability of the site’s double-shell tanks for the balance of the cleanup mission.

A process for removing aluminum from tank waste simulants by adding lithium and precipitating Li-Al-dihydroxide (Lithiumhydrotalcite, [LiAl{sub 2}(OH){sub 6}]{sup +}X{sup -}) has been verified. The tests involved a double-shell tank (DST) simulant and a single-shell tank (SST) simulant. In the case of the DST simulant, the product was the anticipated Li-hydrotalcite. For the SST simulant, the product formed was primarily Li-phosphate. However, adding excess Li to the solution did result in the formation of traces of Li-hydrotalcite. The Li-hydrotalcite from the DST supernate was an easily filterable solid. After four water washes the filter cake was a fluffy white material made of < 100 {micro}m particles made of smaller spheres. These spheres are agglomerates of {approx} 5 {micro}m diameter platelets with < 1 {micro}m thickness. Chemical and mineralogical analyses of the filtrate, filter cake, and wash waters indicate a removal of 90+ wt% of the dissolved Al for the DST simulant. For the SST simulant, the main competing reaction to the formation of lithium hydrotalcite appears to be the formation of lithium phosphate. In case of the DST simulant, phosphorus co-precipitated with the hydrotalcite. This would imply the added benefit of the removal of phosphorus along with aluminum in the pre-treatment part of the waste treatment and immobilization plant (WTP). For this endeavor to be successful, a serious effort toward process parameter optimization is necessary. Among the major issues to be addressed are the dependency of the reaction yield on the solution chemistry, as well as residence times, temperatures, and an understanding of particle growth.

A Technical Safety Requirement (TSR) control level verification process was developed for the Tank Waste Remediation System (TWRS) TSRs at the Hanford Site in Richland, WA, at the direction of the US. Department of Energy, Richland Operations Office (RL). The objective of the effort was to develop a process to ensure that the TWRS TSR controls are designated and managed at the appropriate levels as Safety Limits (SLs), Limiting Control Settings (LCSs), Limiting Conditions for Operation (LCOs), Administrative Controls (ACs), or Design Features. The TSR control level verification process was developed and implemented by a team of contractor personnel with the participation of Fluor Daniel Hanford, Inc. (FDH), the Project Hanford Management Contract (PHMC) integrating contractor, and RL representatives. The team was composed of individuals with the following experience base: nuclear safety analysis; licensing; nuclear industry and DOE-complex TSR preparation/review experience; tank farm operations; FDH policy and compliance; and RL-TWRS oversight. Each TSR control level designation was completed utilizing TSR control logic diagrams and TSR criteria checklists based on DOE Orders, Standards, Contractor TSR policy, and other guidance. The control logic diagrams and criteria checklists were reviewed and modified by team members during team meetings. The TSR control level verification process was used to systematically evaluate 12 LCOs, 22 AC programs, and approximately 100 program key elements identified in the TWRS TSR document. The verification of each TSR control required a team consensus. Based on the results of the process, refinements were identified and the TWRS TSRs were modified as appropriate. A final report documenting key assumptions and the control level designation for each TSR control was prepared and is maintained on file for future reference. The results of the process were used as a reference in the RL review of the final TWRS TSRs and control suite. RL concluded that the TSR control level verification process is clear and logically based upon DOE Order 5480.22, Technical Safety Requirements, and other TSR control selection guidelines. The process provides a documented, traceable basis for TSR level decisions and is a valid reference for preparation of new TSRs.

The Hanford site contains approximately 55 million gallons of radioactive and chemically hazardous wastes stored in 177 carbon steel underground storage tanks, of which 149 are single-shell tanks (SSTs) and the remaining tanks are double-shell tanks (DSTs). This paper presents the results of ongoing studies on the effects of various waste chemistries on localized corrosion and SCC of one of the DSTs – 241 AY-102 (AY-102). This is the only DST to have experienced a leak of the primary tank liner. The chemistries of the waste in the annular space of AY-102 were simulated using various scenarios of evaporation and equilibration with atmospheric CO2. Additionally, the metallurgical treatments undergone by the tank during its installation were simulated. The resultant simulant chemistries and thermal treatments were used in localized corrosion and stress corrosion cracking (SCC) tests. A combination of cyclic potentiodynamic polarization and potential staircase methods indicate that the secondary tank liner is not likely to suffer from localized corrosion in simulants representing the waste present in the annular space. Similarly, crack growth rate tests do not indicate an immediate threat of SCC to the secondary tank liner.

The Tank Waste Remediation System (TWRS) is responsible for storing, processing, and immobilizing the Hanford Site tank wastes. Characterization information on the tank wastes is needed so that safety concerns can be addressed, and retrieval, pretreatment, and immobilization processes can be designed, permitted, and implemented. This document describes the near-term tank waste sampling and characterization needs of the Pretreatment, High-Level Waste (HLW) Disposal, and Low-Level Waste (LLW) Disposal Programs to support the TWRS disposal mission. The final DQO (Data Quality Objective) will define specific waste tanks to be sampled, sample timing requirements, an appropriate analytical scheme, and a list of required analytes. This interim DQO, however, focuses primarily on the required analytes since the tanks to be sampled in FY 1994 and early FY 1995 are being driven most heavily by other considerations, particularly safety. The major objective of this Interim DQO is to provide guidance for tank waste characterization requirements for samples taken before completion of the final DQO. The characterization data needs defined herein will support the final DQO to help perform the following: Support the TWRS technical strategy by identification of the chemical and physical composition of the waste in the tanks and Guide development efforts to define waste pretreatment processes, which will in turn define HLW and LLW feed to vitrification processes.

This Sampling and Analysis Plan (SAP) is written for the radiological environmental air surveillance program for the DOE-SC PNNL Site, Richland Washington. It provides the requirements for planning sampling events, and the requirements imposed on the analytical laboratory analyzing the air samples. The actual air sampling process is in procedure EPRP-AIR-029. The rationale for analyte selection, media, and sampling site location has been vetted through the data quality objectives (DQO) process (Barnett et al. 2010). The results from the DQO process have been reviewed and approved by the Washington State Department of Health. The DQO process (Barnett et al. 2010) identified seven specific radionuclides for analysis along with the need for gross alpha and gross beta radiological analyses. The analytes are {sup 241}Am, {sup 243}Am, {sup 244}Cm, {sup 60}Co, {sup 238}Pu, {sup 239}Pu, and {sup 233}U. The report also determined that air samples for particulates are the only sample matrix required for the monitoring program. These samples are collected on 47-mm glass-fiber filters.

The United States Environmental Protection Agency`s (EPA) Data Quality Objectives (DQO) process was applied to two environmental monitoring networks for the purpose of optimizing field quality control sampling to give the highest quality monitoring data with minimal impact on resources. The DQO process, developed primarily to aid in cleanup and restoration activities, is a systematic approach to designing sampling, and analysis programs with improved efficiency, cost savings, and measureable and traceable data quality. The two monitoring- networks studied had not been subjected to the systematic review and analysis of the DQO process defined by the EPA. The two monitoring networks studied had relied upon field duplicates or replicates as the main source of field quality control data. Sometimes, both duplicate and routine sample were analyzed by the same analytical laboratory; at other times they were analyzed by different laboratories. This study identified some potential inconsistencies between analytical data and reporting limits from two different laboratories. Application of the EPA DQO process resulted in recommendations for changes in the field quality control sampling program, allowed new insight into the monitoring data, and raised several issues that should be the subject of further investigation.

This report summarizes the predictive methods used to ensure that waste transfer operations in Hanford waste tanks do not create waste configurations that lead to unsafe gas release events. The gas release behavior of the waste in existing double-shell tanks has been well characterized, and the flammable gas safety issues associated with safe storage of waste in the current configuration are being formally resolved. However, waste is also being transferred between double-shell tanks and from single-shell tanks into double-shell tanks by saltwell pumping and sluicing that create new wastes and waste configurations that have not been studied as well. Additionally, planning is underway for various waste transfer scenarios to support waste feed delivery to the proposed vitrification plant. It is critical that such waste transfers do not create waste conditions with the potential for dangerous gas release events.

Since this report was originally issued in 2001, several options proposed for increasing double-shell tank (DST) storage space were implemented or are in the process of implementation. Changes to the single-shell tank (SST) waste retrieval schedule, completion of DST space saving options, and the DST space saving options in progress have delayed the projected shortfall of DST storage space from the 2007-2011 to the 2018-2025 timeframe (ORP-11242, River Protection Project System Plan). This report reevaluates options from Rev. 0 and includes evaluations of new options for alleviating projected restrictions on SST waste retrieval beginning in 2018 because of the lack of DST storage space.