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Polar Bear™ – Innovative Capture of Storage Tank Vapors

Polar Bear™ is a patented technology developed by the Energy & Environmental Research Center (EERC) to capture storage tank vapors and eliminate methane emissions from upstream oil- and gas-producing facilities. Sparked by early commercial investment, the EERC licensed the technology and extended the intellectual property to storage tanks. Polar Bear™ is uniquely engineered and adapted to individual lower-producing facilities where there is otherwise no economic alternative for capturing tank vapors. A high number of small producing oil and gas wells are distributed across the country. The aggregate contributes to a significant volume of emissions. Because of the lack of economy of scale, gas volumes from these facilities are typically not recovered and contribute to methane emissions. Polar Bear™ provides a fit-for-purpose compression solution that addresses cost by reducing complexity with respect to conventional vapor recovery units and eliminating oil changes. Unique to Polar Bear™ is the capability to separate oxygenated gas from storage tank vapors. Storage tanks are designed to “breathe,” allowing gas to enter and escape during internal level and temperature changes. This infiltration of air into the tank headspace imparts undesirable oxygen content with respect to pipeline gathering. Polar Bear™ separates the vapor stream, allowing oxygen-rich gas to be used as fuel on-site while recovering the liquids-rich portion of the gas where oxygen content is minimized. A prototype system was tested to verify process models, evaluate operational performance, and advance the technology readiness level from 5 to 6. Results provide a good match between experimental measurements and process models, indicating the models are useful for future scale-up and field design. Various mixtures of nitrogen and liquefied petroleum gas were tested to understand the mass balance of nitrogen and how it relates to the potential control of oxygen content. Findings indicate that less than 2000 ppm of oxygen is likely to remain in the liquid portion of the gas in field applications. The research and development prepare the technology for field implementation to eliminate routine and fugitive methane emissions from storage tanks.

02 PETROLEUM↗

Hanford Tank Vapors in Worker Breathing Zones - Source, Dispersion, and Receptor Data - 20373

A wide range of organic and inorganic chemicals from historical Hanford Site processes are now stored in 177 underground storage tanks at the Hanford tank farms. Workers at the Hanford tank farms have expressed concerns about chemical vapor exposures for many years. During the spring of 2014, worker reports of chemical odors and/or symptoms prompted the development of the Savannah River National Laboratory Hanford Tank Vapor Assessment Team (TVAT) and their resulting independent assessment and recommendations concerning tank farm worker reports of vapors. The Tank Vapor Assessment report included a hypothesis that 'vapors coming out of tanks in high concentration (bolus) plumes sporadically intersected with the breathing zones of workers, resulting in brief but intense exposures to some workers.' The focus of this effort is to present current knowledge to describe the mechanisms by which workers may experience short duration vapor concentrations above background in the tank farms environment. The TVAT hypothesis that workers have experienced concentrations approaching 80% of the tank headspace up to 3 meters (10 feet) from tank sources is not supported by sampling data or modeling results. Modeling indicates that concentrations are quickly reduced from the source, and that the upper end of predicted concentrations at worker breathing zones are a factor of 10 or more lower than source concentrations. Area measurements corroborate the fact that worker breathing zone concentrations are 10 to 100 times lower than source concentrations, and events with elevated concentrations are rare. These reduced vapor concentration levels may result in detectable odors or irritation, depending on a worker's specific odor threshold and sensitivity to the chemical species. Short-duration vapor events may be mitigated by evaluating daily atmospheric conditions in conjunction with planned tank farm activities. Monitoring changing conditions related to tank vapors concentrations at the source and within worker breathing zone is also an important step to protect workers from short duration elevated concentration events. (authors)

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Hanford Tank Farm Vapors Abatement Technology and Vendor Proposals Assessment

Suspected chemical vapor releases from the Hanford nuclear waste tank system pose concerns for worker exposure. Washington River Protection Solutions (WRPS) contracted the Savannah River National Laboratory (SRNL) to explore abatement technologies and strategies to remediate the vapors emitted through the ventilation system. In response, SRNL conducted an evaluation of technologies to abate, or reduce, vapor emissions to below 10% of the recognized occupational exposure limits (OELs). The evaluation included a review of published literature and a broadly communicated Request for Information to commercial vendors through a Federal Business Opportunities (Fed Biz Opps) web posting. In addition, SRNL conducted a workshop and post-workshop conference calls with interested suppliers (vendors) to assess proposals of relevant technologies. This report reviews applicable technologies and summarizes the approaches proposed by the vendors who participated in the workshop and teleconference interviews. In addition, the report evaluates the estimated performance of the individual technologies for the various classes of chemical compounds present in the Hanford Chemicals of Potential Concern (COPCs) list. Similarly, the report provides a relative evaluation of the vendor proposed approaches against criteria of: technical feasibility (and maturity), design features, operational considerations, secondary waste generation, safety/regulatory, and cost / schedule. These rough order-of-magnitude (ROM) cost estimates are intended to provide a comparison basis between technologies and are not intended to be actual project estimates.

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Vapor Space Corrosion Testing Simulating The Environment Of Hanford Double Shell Tanks

As part of an integrated program to better understand corrosion in the high level waste tanks, Hanford has been investigating corrosion at the liquid/air interface (LAI) and at higher areas in the tank vapor space. This current research evaluated localized corrosion in the vapor space over Hanford double shell tank simulants to assess the impact of ammonia and new minimum nitrite concentration limits, which are part of the broader corrosion chemistry limits. The findings from this study showed that the presence of ammonia gas (550 ppm) in the vapor space is sufficient to reduce corrosion over the short-term (i.e. four months) for a Hanford waste chemistry (SY102 High Nitrate). These findings are in agreement with previous studies at both Hanford and SRS which showed ammonia gas in the vapor space to be inhibitive. The presence of ammonia in electrochemical test solution, however, was insufficient to inhibit against pitting corrosion. The effect of the ammonia appears to be a function of the waste chemistry and may have more significant effects in waste with low nitrite concentrations. Since high levels of ammonia were found beneficial in previous studies, additional testing is recommended to assess the necessary minimum concentration for protection of carbon steel. The new minimum R value of 0.15 was found to be insufficient to prevent pitting corrosion in the vapor space. The pitting that occurred, however, did not progress over the four-month test. Pits appeared to stop growing, which would indicate that pitting might not progress through wall.

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Separation and Speciation of Mercury from Hanford 241-AP-107 Tank Waste Supernatant

Mercuric nitrate, Hg(NO 3 ) 2 , was introduced into the Hanford flowsheet when it was used to catalyze nitric acid dissolution of certain aluminum alloy fuels and to suppress radioiodine volatilization during nitric acid dissolution of short-cooled uranium metal fuel. Inventory estimates, based primarily on Hanford process-knowledge, suggest a total mercury inventory of 2,100 kg 1 in the Hanford Tank Farms. Aside from the obvious human exposure concerns via tank vapors, mercury species in the tank waste liquid and solid fraction pose risk to the implementation and execution of the River Protection Project mission due to mercury limits imposed under waste acceptance criteria, toxicity characteristic leaching procedure restrictions for secondary waste disposal, and air emission permits. Although there is currently no processing of tank waste at Hanford, waste processing is imminent and representative mercury inventory tracking will be important to anticipate and mitigate stack emissions and secondary liquid waste disposal issues like those experienced at the Savannah River Site.

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BY-110 Headspace Sampling Comparison Test: Volume 1

The Hanford Tank Operations Contractor, Washington River Protection Solutions, conducted comparison tests of two Hanford Waste tank vapor sampling systems to determine the relative differences in quantifying Chemicals of Potential Concern (COPC) while sampling the same waste tank. The systems are the traditional in situ, inline headspace sampling (HS) method and the recently developed slipstream sampling unit for testing respirator chemical cartridges known as the cartridge test (CT) rig. The comparison test was performed to determine if results obtained using the CT rig are similar to results obtained using the traditional HS method. Using the CT rig would provide efficiencies in headspace vapors sampling such as applying ALARA principles, minimizing worker entries to the tank farms, and eliminating the physical strain of manually lowering the headspace sampling bundles into the waste tanks. Six sampling events were conducted during January and February 2018 to collect headspace vapor samples from Hanford tank BY-110 with the two systems. Pacific Northwest National Laboratory was tasked with conducting an analysis of the analytical results to assess the comparability of the sampling methods and make recommendations on future testing or deployment of the CT method.

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BY-110 Headspace Sampling Comparison Test: Volume 2: Raw Data

The Hanford Tank Operations Contractor, Washington River Protection Solutions, conducted comparison tests of two Hanford Waste tank vapor sampling systems to determine the relative differences in quantifying Chemicals of Potential Concern (COPC) while sampling the same waste tank. The systems are the traditional in situ, inline headspace sampling (HS) method and the recently developed slipstream sampling unit for testing respirator chemical cartridges known as the cartridge test (CT) rig. The comparison test was performed to determine if results obtained using the CT rig are similar to results obtained using the traditional HS method. Using the CT rig would provide efficiencies in headspace vapors sampling such as applying ALARA principles, minimizing worker entries to the tank farms, and eliminating the physical strain of manually lowering the headspace sampling bundles into the waste tanks. Six sampling events were conducted during January and February 2018 to collect headspace vapor samples from Hanford tank BY-110 with the two systems. Pacific Northwest National Laboratory was tasked with conducting an analysis of the analytical results to assess the comparability of the sampling methods and make recommendations on future testing or deployment of the CT method.

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Respirator Cartridge Performance on Mixed Vapors from Hanford Tank Headspaces and Exhausters - 20427

Between 2016 and 2018, the Hanford Tank Operations Contractor - Washington River Protection Solutions (WRPS) - conducted a series of tests of air-purifying respirator (APR) chemical cartridges commonly used at Hanford tank farms to determine the period of time for which the cartridges would provide adequate performance when used in APRs and powered-air-purifying respirators (PAPRs) to protect workers when exposed to a mixture of vapors exiting tank headspaces. Although cartridge manufacturers provide service life estimating tools for individual chemical compounds, the projected performance of these cartridges on complex vapor mixtures is not available, and the adequacy of APRs for tank farm applications represents an important workforce concern. The Occupational Safety and Health Administration identifies cartridge testing as a valid approach for establishing cartridge service life. The primary function of the WRPS Cartridge Test Program was to obtain objective data to determine service lives for the APR and PAPR cartridges used at Hanford tank farms. WRPS contracted with Pacific Northwest National Laboratory to analyze the test data and offer an independent analysis of and recommendations based on respirator cartridge performance. A total of 28 APR and 10 PAPR cartridge tests were conducted between 2016 and 2018 on 12 different tank headspaces and tank farm exhauster slipstreams. Two APR cartridges from SCOTT (now 3M) and two PAPR cartridges from MSA Safety, Inc. and 3M were evaluated using a cartridge testing system specifically designed to measure and monitor test conditions and sample cartridge inlet and outlet vapor streams for important chemical compounds. Testing focused on analysis of approximately 61 tank vapor chemicals of potential concern (COPCs) that have been previously detected in tank vapors at levels above 10% of their occupational exposure limits (OELs). Each test was conducted over 16 hours of run time. Evidence of chemical breakthrough was assessed by comparing inlet and outlet COPC concentrations over the duration of each test. The breakthrough threshold was normally defined as exceeding 10% of the compounds OEL at the cartridge outlet. Ammonia breakthrough was observed in a majority of the cartridge tests and occurred earlier than breakthrough of any other chemical compound. Several other COPCs did exhibit breakthrough behavior, including mercury, 1,3-butadiene, furan, 2,5 dihydrofuran, and N-nitrosodimethylamine (NDMA), but only in a very limited number of cartridge tests and only after ammonia breakthrough had occurred. In addition, tests results suggest that breakthrough of some of these COPCs may have been affected by competition with and breakthrough of other non-COPC organics, such as ethanol and acetone, with substantially lower toxicological hazard. Comparison of cartridge manufacturers' service life estimates with the experimentally derived breakthrough times indicates that manufacturers' estimates are generally conservative, even in the presence of the complex mixed vapor streams experienced in these tests. With consideration of appropriate safety margins, these results provide valuable insights on cartridge performance to inform industrial hygiene professionals in establishing appropriate cartridge change-out schedules for APR and PAPR use in the Hanford tank farms. (authors)

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Integrating Commercial Ready Autonomous Robotic Platforms to Enhance Worker Safety and Efficiency - 20053

This paper will explore the challenges and triumphs of implementing advanced robotic systems and the supporting technology for the waste management industry. Deployment-ready solutions for autonomous robotic platforms are new to the radioactive waste management industry and have been slow to implement across the complex. Specifically, it will explore Hanford Tank Operations Contractor's implementation of ground-based autonomous robotic platforms to enhance workforce safety and efficiency. The first objective of the project is to demonstrate safe operation of autonomous instrumented robots, followed by a scaling up of capabilities for the platform to meet any additional requests of internal stakeholders. Autonomous robotics platforms offer a fantastic range of capabilities that will aid in decreasing long-term liability of radioactive waste management industry by enhancing clean-up efforts and worker safety. Over the past five years, deployment-ready solutions for autonomous robotic platforms have come a long way. Autonomous robotic platforms are increasingly available to purchase from many vendors, often for prices under $100,000. Additionally, the vendors who produce these products are efficient in accommodating customized solutions to unique challenges, such as those often found in the radioactive waste management industry. However, the newness of this technology to the radioactive waste management industry and has resulted in a slow implementation across the complex. This paper will explore the challenges and triumphs of implementing advanced robotic systems and supporting technology for the waste management industry. Specifically, it will explore Hanford Tank Operations Contractor's implementation of ground based autonomous robotic platforms to enhance workforce safety and efficiency. While the company has utilized robots in many parts of the tank farms mission, this was first attempted in the deployment of an autonomous platform that required no operator with only minor maintenance and created challenges not yet encountered. These challenges included stakeholder buy-in, operational safety, procurement uncertainties, adaption of 'off the shelf products, overcoming the 'Fukushima complexity' perception, security concerns, and the initial criteria down select. Hanford Tank Operations Contractor's management identified the need for a workforce protecting low cost robotics solution in the fall of 2017. The project scope generated was part of the response to the Tank Vapor Assessment Team recommendation to enhance the safety of the workforce by utilizing new technology. Since the projects inception, it has been incorporated into the Tank Stewardship Plan. This project was unique to Hanford Tank Operations Contractor, as the company does not frequently incorporate advanced technology for field deployment quickly. The project was also progressive to the Hanford Tank Operations Contractor as it functions as a partnership project with a local university. The first objective of the project is to demonstrate safe operations of autonomous instrumented robotics, monitoring and collecting data, and the wireless transmission of data to a central computing system. Following the completion of this first objective, the project will scale up capabilities of the platform to meet the requests of additional internal stakeholders throughout the tank farms - including completion of specific in-field tasks. (authors)

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A Design Document: Custom Analytical Tools and Automation for the Industrial Hygienist

This report outlines an approach for developing a modular and scalable web-based application suite, Internal Data Access and Visualization (I-DAV), that would be developed to meet the specific analytic requirements for Industrial Hygienist (IH) analysts and tank vapors Subject Matter Expert’s (SME) at the Hanford site. Through interviews and requirements elicitation with IH analyst, and on-site in depth review of workflow patterns and expected outcomes, PNNL has developed a framework for proposed collection of interdependent goal oriented software applications. Commercial off the shelf applications, which require only minimal custom code, were deployed this year as a mechanism of rapid prototyping and providing proof of concept. This report describes these efforts and accomplishments to date, as well as concepts for future applications and general enhancement of the DAV and core concepts for the I-DAV. Additional content was integrated into this report as of March 2019. Updated content was added to reflect the inclusion of I-DAV concepts and ideas, and refined versions of original concepts set forth as the work commenced and continued through the first half of FY19. New and refined concepts have been the product of ongoing weekly meetings, outreach, and elicitation with WRPS.

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A Design Document: Custom Analytical Tools and Automation for the Industrial Hygienist

This report outlines an approach for developing a modular and scalable web-based application suite, Internal Data Access and Visualization (I-DAV), that would be developed to meet the specific analytic requirements for Industrial Hygienist (IH) analysts and tank vapors Subject Matter Expert’s (SME) at the Hanford site. Through interviews and requirements elicitation with IH analyst, and on-site in depth review of workflow patterns and expected outcomes, PNNL has developed a framework for proposed collection of interdependent goal oriented software applications. Commercial off the shelf applications, which require only minimal custom code, were deployed this year as a mechanism of rapid prototyping and providing proof of concept. This report describes these efforts and accomplishments to date, as well as concepts for future applications and general enhancement of the DAV and core concepts for the I-DAV. Additional content was integrated into this report as of March 2019. Updated content was added to reflect the inclusion of I-DAV concepts and ideas, and refined versions of original concepts set forth as the work commenced and continued through the first half of FY19. New and refined concepts have been the product of ongoing weekly meetings, outreach, and elicitation with WRPS.

97 MATHEMATICS AND COMPUTING↗

NUCON Vapor Abatement Unit Performance on Hanford Tank Farm Chemicals of Potential Concern

This report provided the results and methods used in the NUCON Vapor Abatement Unit performance testing. The purpose of the Pacific Northwest National Laboratory (PNNL) testing was to assess the performance of the NUCON International, Inc., Vapor Abatement Unit (VAU) prototype for the reduction of Hanford Tank Farm vapors associated chemicals of potential concern (COPC). The testing was conducted in compliance with the PNNL Assessment of NUCON Vapor Abatement Unit for Single-Shell Tank (SST) Farm Off-Gas Chemicals of Potential Concern (COPCs) test plan. Performance testing started on May 4, 2018 and continued through June 13, 2018. Eleven (11) COPCs were chosen for testing out of the 61 identified COPCs. The COPCs were chosen either due to the importance of that COPC measured in Hanford high-level waste single-shell tank (SST) vapor emissions, as a surrogate to represent a class of COPC compounds, or both. Results of the performance tests are included.

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Application of Vapor Corrosion Inhibitors for Tank Bottom Plate Corrosion Control

Soil-side corrosion of aboveground storage tank (AST) bottoms is a great challenge. ASTs usually include active cathodic protection (CP) systems to mitigate soil-side corrosion of the bottoms. CP systems could fail leading to unprotected tank bottoms, and sometime corrosion could occur even with active CP. A study was conducted to determine efficacy of the vapor corrosion inhibitor (VCI) technology in mitigating corrosion. VCIs were discovered to be effective in mitigating corrosion when recommended dosages are used, and could also be used in combination with impressed current CP systems. Overall, VCI technology was found to be a viable corrosion control measure.

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Progress in Addressing Workers' Concerns Related to Chemical Vapors at the Hanford Site - 19054

Washington River Protections Solutions, LLC (WRPS) is the prime contractor for the Department of Energy (DOE) Tank Farm Operations at the Hanford Site, and is responsible for the management and retrieval of millions of gallons of radioactive and chemical wastes, stored in 177 underground tanks; a legacy of decades of production activities at the Site. The potential for workforce exposure to the chemical vapors from the tanks has long been a concern for the workforce and for DOE and its tank contractors; concerns about tank vapors is an issue that pre-dates WRPS's incumbency as the Tank Operations Contractor. In response to an increase in the number of tank vapor events reported by workers at the Hanford Site in 2014, WRPS commissioned the Savannah River National Laboratory with establishing and overseeing a panel of external, independent experts (Tank Vapor Assessment Team (TVAT)) to examine chemical vapor management and related worker-protection measures at the Hanford Tank Farms. The TVAT released the Hanford Tank Vapor Assessment Report (SRNL-RP-2014-00791) in late 2014, which included several recommendations to reduce the potential for chemical vapor exposures. From 2015- 2018, governmental and external groups conducted additional assessments to review the progress made in implementing the TVAT recommendations, and the overall Industrial Hygiene (IH) program. All of these assessments specifically recommended WRPS take action to improve communications with the workforce around the subject of tank vapors. Some further recommended assessing the effectiveness of vapors-related communications. In fiscal year 2016, WRPS and DOE Office of River Protection (DOE-ORP) formed an Integrated Project Team (IPT) to: (1) develop the strategy for addressing chemical vapors and (2) define the future chemical vapor protection actions at the Tank Farms. The actions are designed to address the recommendations from the external assessments as part of the overall effort to mitigate vapors-related exposure incidences, and to ensure workers are safe and feel safe while working in and around the Hanford Tank Farms. A comprehensive vapor management communication plan, engagement processes, and effectiveness measurements were established as essential components of the IPT effort. The Chemical Protection Program Office (CPPO) was formed, in part, to deliver on these IPT initiatives, monitor performance, and drive improvements to WRPS's vapors-related communications and engagement efforts at the Hanford Tank Farms. The CPPO was created as a temporary program office tailored to address these unique challenges by augmenting traditional company performance monitoring and communications (i.e. all employee e-mails, posters, and formal briefings). Modeled in broad concept after the successful program office WRPS created to support the American Recovery and Reinvestment Act, CPPO has also proven successful in its mission. Because concerns about chemical vapors in the workplace were expressed by the workforce, they are a key stakeholder. As such, the CPPO has concentrated its information sharing efforts toward the WRPS workforce. With a focus on empathetic engagement, continuous improvement, and transparent information sharing, the CPPO has developed and implemented a strategy for improving worker trust in vapors-related communications and increasing the workforce knowledge of responses taken to address chemical vapors. Effective implementation of this strategy is demonstrated by the results of workforce surveys, which indicate measured and important improvement in the effectiveness of vapors-communications and the knowledge level workers report about vapor issues compared to the previous year. This paper discusses the utilization of a temporary program office and the unique approach that the CPPO implemented to achieve success, including: strategic application of the technical and communications staff skill mix of the organization (including talent development opportunities such as stretch assignments for WRPS's Strategic Talent Development program members and support from WRPS college interns), teaming with other WRPS' organizations such as IH, Engineering and Communications and Public Relations (C and PR), the development of new types of information sharing to support the effort, and the methods by which the effectiveness of the communications efforts are measured to drive continuous improvement. (authors)

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Conducting Industrial Hygiene Exposure Assessments at Scale Using Non-Parametric Upper Tolerance Limits at the Hanford Site - 20439

Chemical vapors are generated in the radioactive waste storage tanks at the Hanford Site due to ongoing chemical and radiological activity. Hanford's Tank Operations Contractor conducts exposure assessments for individual tank farms to identify, evaluate, and recommend controls or other worker protection measures for chemical, physical, and biological hazards present within each tank farm. These exposure assessments conform to the American Industrial Hygiene Association assessment strategy and recommended statistical procedures. The exposure assessment process involved manually processing tens of thousands of records that were collected over several years and entered into a central database. Working with Pacific Northwest National Laboratory, this process has been largely automated, providing a scalable analysis process that reduced processing time by over 90%, while providing defensible results and improved data quality. (authors)

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LABORATORY TESTING TO SIMULATE VAPOR SPACE CORROSION IN RADIOACTIVE WASTE STORAGE TANKS

Radioactive liquid waste has been stored in underground carbon steel tanks for nearly 70 years at the Hanford nuclear facility. Vapor space corrosion of the tank walls has emerged as an ongoing challenge to overcome in maintaining the structural integrity of these tanks. The interaction between corrosive and inhibitor species in condensates/supernates on the tank wall above the liquid level, and their interaction with vapor phase constituents as the liquid evaporates from the tank wall influences the formation of corrosion products and the corrosion of the carbon steel. An effort is underway to gain an understanding of the mechanism of vapor space corrosion. Localized corrosion, in the form of pitting, is of particular interest in the vapor space. CPP testing was utilized to determine the susceptibility of the steel in a simulated vapor space environment. The tests also investigated the impact of ammonia gas in the vapor space area on the corrosion of the steel. Vapor space coupon tests were also performed to investigate the evolution of the corrosion products during longer term exposures. These tests were also conducted at vapor space ammonia levels of 50 and 550 ppm NH{sub 3} (0.005, and 0.055 vol.%) in air. Ammonia was shown to mitigate vapor space corrosion.

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