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DOE OSTI2022

Relationship Between the Marginal Probability of Failure for a CPP Test and the Recommended Corrosion Control Requirements for Hanford Double Shell Waste Tanks

The Hanford Site in Washington State currently stores millions of gallons of radioactive waste in underground, carbon steel, double shell tanks (DSTs) that were constructed between 1968 and 1986. A chemistry control and monitoring program has been established mitigate corrosion in order to extend the service life for the DSTs. The current waste temperatures in the DSTs are at historical lows (i.e., typically less than 50 °C). The previous chemistry control requirements were determined for conditions at temperatures significantly higher. SRNL undertook a statistically based investigation of the role of nitrate and halide ion (i.e., chloride and fluoride) induced pitting corrosion. The objective was to develop a comprehensive waste chemistry envelope for the simultaneous minimization of the pitting and SCC risks caused by halide and nitrate ions at the lower temperature conditions. On the basis of these tests, new chemistry control requirements were proposed and have since been implemented for pitting corrosion control.

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DOE OSTI2026

Cathodic Protection Modeling for Hanford Underground Double-Shell Tank Farms

Hanford stores millions of gallons of radioactive and chemically hazardous waste from the production of weapon materials in tank farms consisting of underground carbon-steel storage tanks surrounded by reinforced concrete. Six of these Hanford tank farms use double-shell storage tanks (DSTs). The DST farms were constructed from 1968 to 1986 with a planned 40–50 year design life, so some are already operating beyond their initial life expectancy. Ultrasonic testing (UT) has indicated significant thinning on the bottom of the secondary (outer) liner of these tanks, believed to arise from groundwater intrusion driving concrete side corrosion. There is no direct access to the steel/concrete interface between the tank and the concrete pad, making it difficult to apply a chemical-based mitigation strategy or to conduct repairs, but cathodic protection (CP) is a possible method to inhibit further concrete-side corrosion. Hanford already uses CP to protect below grade steel piping within the tank farms and connected to the tanks, but this system was not designed to protect the tank bottoms. CP design must account for the structures surrounding the DSTs, including the steel reinforcing bars (rebar) within the concrete pad and vault, various process lines, and the existing CP system. In this study, finite element analysis (FEA) modeling was carried out to simulate CP protection of 1) a single tank and CP anode to develop options for modeling the rebar and to compare to a simpler circuit model and 2) the entire Hanford AN tank farm as a representative example consisting of seven tanks, associated piping, and both existing and new CP anodes. Both circuit and FEA models predict that significant protective current could be delivered to the bottoms of the tanks with the addition of tank-protection anodes below the depth of the tanks. Simulations with only the existing pipe-protection anodes active confirmed that only a very small current to the tank bottoms is predicted under present conditions. Multiple simplified representations of the dome and wall rebar were tested to reduce the computational complexity of the tank-farm simulations, resulting in modeling the rebar as edge elements with a prescribed effective circumference that matches the real rebar surface area. The geometry of the rebar is also simplified into horizontal hoops around the tank walls and radial rebar over the dome with increased effective circumference to retain the target surface area. This simplification was found to greatly reduce the complexity and solution time of the models without large changes in current distributions, especially to the tank bottom. A range of values were tested for model parameters such as soil and concrete resistivities and polarization resistance to investigate their impact on the current and electric potential distributions. Depending on the parameters used, FEA simulations predict some risk of overprotection, particularly on the piping system; since overprotection can also lead to surface damage associated with hydrogen gas generation at the interface (e.g. hydrogen embrittlement or damage to coatings), this needs to be considered when refining the design of the new CP system. Comparison between the FEA models and the circuit model representation demonstrated that the circuit model could not match the predicted FEA current distribution, even when using the exact same surface areas. This discrepancy appeared to be at least partly attributable to the impact of the relative positions of the tank components and anodes to each other and to the ground surface. The FEA model accounts for the relative positions since it solves the governing equations in three dimensions, but the circuit model cannot account for the positioning. In particular, the circuit model underpredicts the current to the tank bottom and overpredicts the current to the dome compared to FEA for the baseline geometry. The FEA models omitted the electrically isolated rebar in the bottom concrete slab. However, a circuit based stray current model estimated that only 2.1% of the total current through the slab would stray into the rebar, corresponding to ~0.21 A for a target current density of 2 mA/ft2 to the tank bottom. The estimated corrosion driven by this amount of stray current is predicted to yield a lifetime of >400 years for the minimum rebar diameter, assuming an acceptable cross-section area loss of 10%.

d'Entremont, Anna [Savannah River National Laborat↗
DOE OSTI2026

Determining Drying Conditions to Mitigate Hanford Double Shell Storage Tank Underside Corrosion — Phase 1

The Hanford Site in Washington State has legacy radiological waste that is being retrieved from single shell tanks (SSTs) and transferred to newer, double shell tanks (DSTs) for eventual closure of the SSTs. The waste is maintained in the DSTs until eventual immobilization can be performed at the Waste Treatment and Immobilization Plant (WTP), currently under construction. Until full immobilization is complete, extended service of the DSTs must be ensured by mitigating corrosion of the steel tank walls and buried steel pipelines. A Pit Air Supply System has been developed to mitigate corrosion of the leak detection pits connected to the concrete foundations of the DSTs. The objectives for the present study are: (i) to corrode steel specimens in an electrolytic simulant to form artificial pits with specific pit depths, and (ii) to determine the temperature and humidity levels that will mitigate further pit growth. Experimental work and results will be presented to evaluate conditions associated with the PASS system and predict corrosion rates when the PASS is operating.

Atmospheric Corrosion↗
DOE OSTI2023

Hanford Double Shell Waste Tank Corrosion Studies (Final Report)

For fiscal year (FY) 2022, the Savannah River National Laboratory (SRNL) focused on two experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of solids on the tanks' inner sidewalls and bottoms. The tank bottom solids contact corrosion testing focused on studying the effects of forming a dry adherent solids layer on a carbon steel substrate. Long-term exposure tests and electrochemical tests were performed to investigate the effect of drying (i.e., removing water) from the solids phase. The second task focused on corrosion of the exterior of the secondary liner. In previous years, vapor corrosion inhibitors (VCIs) were investigated as a means of mitigating corrosion of the exterior of the secondary liner. During FY22 the utilization of nitrogen was explored as a means of corrosion mitigation. The corrosion test results with nitrogen were compared with the corrosion mitigation performance of the VCIs.

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DOE OSTI2020

Hanford Double Shell Waste Tank Corrosion Studies (Final Report FY2019)

During fiscal year (FY) 2019, the Savannah River National Laboratory (SRNL) focused on four primary tasks for Hanford Double Shell Tanks (DSTs) corrosion studies. The first task, New Limits, was a continuation from the electrochemical work started in FY16, to expand electrochemical testing to elevated temperatures and elevated hydroxide concentrations and evaluate how these factors will influence pitting corrosion. Using the pitting factor (PF) equation, these new conditions were validated to provide a conservative estimate for the susceptibility of pitting corrosion on legacy carbon steel. The second task, Secondary Liner Corrosion, focused on Vapor Space Corrosion (VSC) and immersion testing studies using two commercially available vapor corrosion inhibitors (VCIs). For this FY, the VCI strategy was applied mid-experiment to determine performance on weathered coupons. The third task, Long-Term Open Circuit Potential (OCP) Drift, was performed using simplified simulated chemistries to evaluate change in pitting corrosion risk due to evolution of corrosion potential for mill-scale and freshly polished 600-grit surfaces. Finally, the fourth task, Microbiologically-Influenced Corrosion (MIC) studies, was focused on the study of leak detection pit (LDP) water sent from the Hanford tank farm for determination of bacteria that can be conducive to corrosion using commercially available kits: BART TM and MICkit® 5. In addition, this FY, a secondary task was added which was a continuation of the study of the Quartz-enhanced Photoacoustic Spectroscopy (QEPAS) system. Work was started but was ultimately not pursued. A summary of each task performed is presented below.

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DOE OSTI2024

Hanford Double Shell Waste Tank Corrosion Studies (Final Report FY2023)

For fiscal year (FY) 2023, the Savannah River National Laboratory (SRNL) focused on two experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of solids on the tanks’ inner sidewalls and bottoms. Differences in the conductivity between various layers of the tank (e.g., solids, liquid, etc.) could result in differences in the electrochemical potential of the tank metal at various locations. The electrochemical potential difference may result in a corrosion current between the coupled surfaces. In FY23, SRNL investigated test configurations and protocols that could evaluate the presence of a galvanic couple between the tank bottom and the tank wall.

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DOE OSTI2025

Hanford Double Shell Waste Tank Corrosion Studies- Final Report FY2024

For fiscal year (FY) 2024, the Savannah River National Laboratory (SRNL) focused on two experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of solids on the tanks’ inner sidewalls and bottoms. The objective of this task was to determine the effect of solid deposits on the corrosion risk to the tank bottom, and whether a combination of scale, saltcake and loose solids lead to under deposit corrosion. Electrochemical testing in a single cell arrangement was employed to determine a threshold inhibitor level for the interstitial liquid in the solids, above which carbon steel was not susceptible to corrosion beneath the solids. The inhibitor levels tested were based on the previously determined probability of failure for carbon steel in a simulated waste (i.e., Pitting Factor).

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DOE OSTI2021

Hanford Double Shell Waste Tank Corrosion Studies FY2020 (Final Report)

For fiscal year (FY) 2020, the Savannah River National Laboratory (SRNL) focused on three experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of deposits on the tanks’ inner sidewalls and bottoms. The second task studied vapor space corrosion (VSC) of the secondary liner using two commercially available vapor corrosion inhibitors (VCIs) at manufacturer recommended dosages. Finally, the third task investigated the long-term open circuit potential (OCP) drift for mill-scale coupons, coupons with polished surfaces, and partial mill-scale coupons that were exposed to tank waste simulants. Additional tests were performed to evaluate the OCP drift as a function of the quantity and composition of organic compounds added to the simulant. A test that was included in the matrix that established the new chemistry limits for tank corrosion, but was previously unreported, was presented and reviewed as well.

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DOE OSTI2022

Hanford Double Shell Waste Tank Corrosion Studies (Final Report FY2021)

For fiscal year (FY) 2021, the Savannah River National Laboratory (SRNL) focused on two experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of deposits on the tanks’ inner sidewalls and bottoms. The second task studied vapor space corrosion (VSC) inhibition of the secondary liner using vapor corrosion inhibitors (VCIs) at dosages less than the manufacturer recommended and a control test in which no VCIs were added.

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DOE OSTI2020

Developing and Implementing New Waste Chemistry Controls for Hanford's Double-Shell Tanks - 20041

Waste chemistry controls for the Hanford double-shell tanks (DSTs) were established in the 1980's in response to tank failures caused by stress corrosion cracking (SCC) at the Savannah River Site (SRS). The controls were established based on a combination of SRS chemistry limits and corrosion testing results. Conditions in the Hanford DSTs have changed over time, with the temperature in the majority of the DSTs dropping below 50 deg. C. Testing indicated that the original chemistry control specification and SCC testing performed in 2010 did not protect against pitting corrosion mechanisms - what is believed to have caused the failure of tank 241-AY-102. New waste chemistry controls are necessary to protect the DSTs from both SCC and pitting corrosion. Savannah River National Laboratory (SRNL), with input from the Tank Integrity Expert Panel (TIEP) Corrosion Subgroup (CSG), performed a statistically based investigation of nitrate and halide ion induced pitting corrosion. The investigation was intended to develop a comprehensive waste chemistry envelope that minimizes the risk of both SCC and pitting caused by halide and nitrate ions. The waste chemistry envelope needed to be robust enough to address future waste retrieval and process changes which could significantly change the waste composition of the DSTs. The experimental design allowed the statistically significant ions and their effect on pitting corrosion to be determined. SRNL developed the 'pitting factor' which is an empirical relationship between the statistically significant inhibitive species (hydroxide, and nitrite), and pitting inducing species (nitrate, chloride, and fluoride). The coefficients are weighted factors that show the degree of influence the species have on the propensity for pitting. New waste chemistry control limits were recommended by SRNL, and concurred with by the TIEP CSG, that incorporated the pitting factor along with other limits. The controls developed to reduce the risk of pitting corrosion were evaluated to determine if they also protected against SCC. Hundreds of test results were reviewed and compared against the proposed limits. With the exception of one test result, instances where cracking was observed corresponded to chemistry that was outside of the proposed limits - indicating that the chemistry controls developed for pitting also adequately addressed SCC concerns. Existing tank composition estimates were evaluated against the new chemistry controls - three current tank chemistries are suspect, and may not meet the new chemistry control requirements. These included the interstitial liquid (liquid associated with solids) of DSTs 241-AN-102, 241-AN-106, 241-AN-107, and 241-AY-101. Measures are ongoing to evaluate the tanks with the suspect chemistry. These include varying combinations of: performing additional evaluations (history of use, modeling); DST specific laboratory testing; and, pursuing core samples of the DSTs. (authors)

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DOE OSTI2026

Update on Integrity Monitoring, Prediction and Assessment, Corrosion Control, and Repair of the Hanford Storage Tanks

DOE has launched a multi-year research program with the focus of preserving and increasing available volume for waste storage at Hanford. The long-term availability and operability of the Hanford Double Shell Tanks (DST) is critical to the completion of the Hanford mission. Maintaining the integrity of the tank will involve having a technology for repair or refurbishment of a DST should the tank function be compromised by degradation, monitoring the tank for indications of accelerated degradation, developing a means for mitigating accelerated degradation, and evaluating options for increasing the storage capacity in the tank farm without constructing new tanks. The project work was started in the middle of 2024; significant progress has been made in the following four areas: (i) tank refurbishment using a high performance grout and an epoxy sealant layer system, (ii) developing a chemically and radiologically stable reference electrode, (iii) designing and implementing a cathodic protection system to mitigate underside corrosion of DST secondary shells, and (iv) exploring evaporation to increase waste storage capacity.

Shukla, Pavan [Savannah River National Laboratory ↗
DOE OSTI2026

Hanford Tank Waste Matrix Impact on Ion Exchange Performance Using Crystalline Silicotitanate

The removal of radiocesium from Hanford tank waste supernate is a critical step in preparing feed for low-activity waste immobilization. This study evaluated cesium ion exchange performance using crystalline silicotitanate (CST) media in a series of tests designed to evaluate the influence of waste matrix variability on capacity and kinetics. Tank waste supernate subsampled from five Hanford double-shell tanks encompassed a range of sodium, hydroxide, nitrate, and nitrite concentrations in order to assess the impact of feed variability on the performance of the ion exchange system. Both equilibrium and dynamic ion exchange tests were conducted to quantify cesium distribution coefficients and breakthrough behavior under prototypic operating conditions. Results indicated that effective cesium capacity varied by up to a factor of five across the matrices tested, with higher sodium concentrations significantly reducing uptake. Kinetic behavior was similarly matrix-dependent, with solution viscosity contributing to a twofold variation in mass-transfer rates. These results demonstrate the strong dependence of CST ion exchange performance on waste composition and must be incorporated into predictive models for future treatment system design and optimization.

Westesen, Amy M.↗
DOE OSTI2020

Double-Shell Tank Primary Bottom Visual Inspection Results - 20025

A pressing need for the Double-Shell Tank Integrity Program at Hanford is of the ability to inspect the bottom of the tanks. Though the DSTs' annulus spaces (the space between the internal and external tank walls) have been inspected visually since 1992 and with Ultrasonic Testing (UT) since 1996, inspections of the tank bottoms have been able to be conducted due to limitations of available technology, omitting about 40 percent of the tank surface below the maximum fill level from routine inspection. Visual inspections of the tank annulus have been conducted up to five times in some DSTs and portions of the annulus space for all of the DSTs has been inspected twice with UT. This region includes the walls of the primary tank and secondary liner along with accessible portions of the secondary liner bottom. Due to this lack of technology, the degradation of the primary tank bottom in Tank AY-102 was undetected until the tank leaked into its annulus space, confirmed in 2012. Since that time, WRPS has been working with the nondestructive examination community and the Pacific Northwest National Laboratory, to evaluate potential technologies to conduct these challenging remote inspections. Recent work has included the development, testing, and deployment of several remote visual inspection technologies to observe the condition of the primary tank bottom of the DSTs by leveraging air distribution slots in the refractory pad on which it rests. Robotic solutions to conduct this inspection were developed with a detailed understanding of the physical configuration and operational logistics. Understanding and subsequent communication of these details to vendors within the robotics and nondestructive examination community was a critical component to the successful production of these new tools. Throughout the FY16-FY18 years, vendors from nondestructive examination community were solicited for ideas to meet the tank bottom inspection challenge. Two tank bottom visual inspection solutions were then pursued to meet that challenge. Both tools were successfully deployed at Tank AP-107, and provided valuable visuals, never before obtained from the under tank environment of a double-shell tank. While there are minor opportunities for improvement identified with each system, general outcomes were overwhelmingly positive. Both systems were successfully able to navigate the refractory air slot pattern from the outer edge to the tank center and record video footage. The micro-crawler provided high quality and very stable footage through the air slot pattern, but took longer to deploy into the slots and traverse through them than the alternative system. The push-pull tethered camera was able to navigate all seven of its target air slots in a matter of a few hours, which included deployment, movement between slot entrances, and complete removal of the system from the annulus environment. Through these air slots, new information was gained about the tank bottom and refractory pad condition of tank AP-107, AP-106, AP-108, and AN-102. While some debris was noted in the air slots, including sand, chipped refractory, and construction materials, the refractory was found to be structurally stable and adequately supporting the primary tank bottom through the full diameter of the tank. Primary tank bottom steel exterior was found to be in good condition, free of ongoing or aggressive corrosion conditions. Looking toward the future, robotic access to and visual inspection of refractory air slots and the primary tank bottom steel has now proven viable. Incorporating periodic air slot inspections as a regular practice within the Double-Shell Tank Integrity Program is the next step, allowing trending of any changes in condition. As ultrasonic testing infrastructure was leveraged to complete the initial system deployments described in this report, it makes sense to adopt that same strategy for ongoing periodic examinations and deploy these primary tank bottom inspection tools alongside ultrasonic testing operations. Development of visual inspection tools to evaluate the primary tank bottom region of the double-shell tanks was planned as the first stage of inspection. Continued development of volumetric sensors and incorporation of these inspection tools into Hanford's ongoing Double-Shell Tank Integrity Program are the next steps, seeking to continuously expand understanding of asset integrity and remaining useful life. (authors)

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DOE OSTI2020

Repurposing Hanford Waste Tank AP-106 for Interim Storage of Treated Low-Activity Waste - 20044

Hanford Double-Shell Tank AP-106 is being repurposed to serve as the lag storage tank holding feed for the Direct Feed Low-Activity Waste (DFLAW) process at the Waste Treatment and Immobilization Plant (WTP). The repurposing process is the sequence of tank additions and transfers that will remove the Cs 137 inventory from AP-106. The repurposing process steps are designed to remove Cs-137 more effectively and efficiently as compared to regular supernatant transfers. The process steps are estimated to take 2-months to complete. (authors)

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