1.8 SOW Notice .pdf

SOW

89304021CEM000014

STATEMENT OF WORK: Volatile radioiodine capture using engineered membranes:

Bridging laboratory studies to pre-pilot-scale testing

C.1 BACKGROUND

Economically viable solutions to controlling radionuclide air emissions during U.S.

Department of Energy (DOE), Office of River Protection (ORP) waste processing are upon the development of innovative sorbent technologies. A main concern is the capture and immobilization of iodine-129 present in these emissions. Silver-functionalized high specific surface area (SSA) silicates (e.g., aerogels, xerogels) have been shown to provide high waste loading capacities and be easily transformed into waste forms suitable for a repository environment. However, additional studies are needed to enable the implementation of high SSA silicates into a reprocessing facility.

Applications are sought that propose innovative methods to engineer high SSA sorbents into configurations that can be realistically implemented into a reprocessing facility. Information should also be provided on how NOx in the gas stream affects the iodine sorption capacity. The proposed effort should conclude with specifications to allow for the development of these functional materials by an external vendor and information on expected performance in a realistic off-gas environment.

Silver-containing sorbents have become the standard for removing volatile iodine because of the high trapping capability and low solubility of AgI in water [1]. Silver-nitrate-impregnated alumina (AgA) and silver-functionalized silica aerogel (AgAero) have been identified as two of the most promising iodine sorbents with clear pathways for waste forms.

Adsorption capacities of ~0.1 g iodine per gram sorbent were reported for AgA and ~0.3 g iodine per gram of AgAero1.

Feasibility studies on Ag- functionalized silica aerogels were conducted by the PI’s group in 2019. The aim of this project was to expand upon previously funded PNNL work, engineering these viable Ag-functionalized aerogels into a morphology that has the potential to be implemented in a plant capture system. Membrane formation was successfully demonstrated by introducing a scaffold into a sol during gelling, which was then dissolved during the aerogel formation process. Once membrane formation feasibility was established, the membranes were loaded with silver nanoparticles and iodine sorption testing was conducted. Traditional silica aerogels containing silver (T-0-Ag) had an iodine loading capacity of 93 mg I g-1 compared to 192 mg I g-1 for aerogels with the interconnected porosity (T-40-Ag). Aerogels aged in NOx showed a lower loading capacity of 108 mg I g-1 for T-40-Ag and 67 for T-0-Ag. Recently, studies have focused on xerogels due to the increased mechanical durability compared to the

1 J. Jordan, R. Jubin, Stability of tritium and iodine sorbents under tritium-pretreatment off-gas conditions, in:

U.S.D.o. Energy (Ed.) U.S. Department of Energy, Oak Ridge National Laboratory, 2017 aerogels.

In studies requiring commercially realistic fluxes, packed bed systems were used for sorbent testing. This configuration allowed for the high surface area media to be utilized in a manner most effective for the intrinsic morphology of the aerogel (i.e., extremely high surface area with low permeability). However, the material could be more effective if macroscale interconnected porosity were present to increase the gas permeability through the sample. The proposed gas treatment system would consist of a stack a crack-free high specific surface area silica membranes loaded with metals (e.g., Ag, Bi) demonstrated to be effective at chemically binding iodine. Calculations based on material created in the laboratory indicate that interconnected macropores in the membrane would provide the permeability needed to maintain a minimal pressure drop.

The aim of this effort is to expand on work previously conducted by PNNL and the PI;

engineering viable Ag-functionalized xerogels into a form that has the potential to be implemented in a plant capture system. Prior work by the PI has led to the development of mechanically robust metal-loaded xerogels with permeability values suitable for implementation into an off-gas system (~10 Pa with flow rate ~100 m3/hr). The goal of this research will be to develop a pre-pilot-scale system to test the iodine sorption capacity of membrane stacks before and after prolonged exposure to NOx (10,000 ppm). Information will also be collected on how the iodine sorption capacity of the unaged membranes is affected when the NOx is in the gas stream containing iodine. Understanding of the residence time needed to meet a specific DF while maintaining a minimal pressure drop will be developed. The efficacy of these xerogel membrane stacks will be compared to conventional packed bed systems of silver-loaded zeolite (IONEX Ag-400), as this material is used as a benchmark evaluation. The deliverable of this endeavor will result in a material specification that will allow a commercial vendor to deliver materials that can be qualified for use in a LAW off-gas facility guard bed.

C.2 SCOPE OF WORK

(a) The contractor shall provide:

Task 1: Synthesis and characterization of metal-loaded xerogel membranes

- Synthesis and characterization of silver- and bismuth-loaded xerogel membranes with dimensions of 1.0” diameter and 0.5” thick

- Deliverable: Data in the Y1 report showing the characterization results from SEM, surface area (BET), porosity (BJH), XRD, XPS, TEM, FTIR, hydrophobicity, mechanical testing

Task 2: Fabrication of static iodine sorption testing system

- Deliverable: System description in Y1 report

Task 3: Static iodine sorption testing on aged and unaged membranes

- The loading capacity using silver- and bismuth-loaded xerogel membranes will be determined. Standard physiochemical characterization will be performed.

- Deliverable: Data in the Y1 and Y2 reports showing the iodine sorption capacity and characterization results.

Task 4: Submission of Y1 annual report

- Deliverable: Technical report summarizing the results from Y1

Task 5: Design, development, and fabrication of a pre-pilot-scale system to evaluate membranes in a flowing gas stream

- A system and protocol will be developed to evaluate the performance of the membranes in a flowing gas stream. Standards of known material will be used to help develop a robust protocol.

- Deliverable: Description of the protocol in the Y2 report

Task 6: Evaluation of the iodine sorption efficacy of metal-loaded xerogel membranes

- The system and protocol developed in Task 5 will be used to evaluate the performance of metal-loaded membranes before and after aging. Information will also be collected on pressure drop and residence time need to meet specified decontamination factors.

Additionally, testing will be conducted to determine if fines are produced during operation. The results will be compared to a packed bed of IONEX Ag-400, as this material is used as a benchmark evaluation.

- Deliverable: Description of results in the final report

Task 7: Submission of Y2 annual report

- Deliverable: Technical report summarizing the results from Y2

Submission of final report

- The final report will be submitted 3 months after the end of the project.

- Deliverable: A technical report summarizing the findings from the work, including suggested next steps in order to inform design basis input for a capture system that could be implemented within the WTP. The proposed effort should conclude with specifications to allow for the development of these functional materials by an external vendor and information on expected performance in a realistic off-gas environment.

Period of Performance: 36 months

Collaboration: The contractor shall work closely with the Glass Team at PNNL and ORP to share results, techniques, and interpretations and to avoid duplication of efforts. Interactions with PNNL will include teleconferences and, possibly, periodic site visits. ORP believes that having an integral university component to the glass research currently underway at PNNL, Vitreous

State Laboratory of The Catholic University of America, and other institutions, will provide the opportunity for training some of the next generation of scientists that will be needed to support the DOE/ORP clean-up mission, particularly in the area of glass waste forms. For this effort to be effective, PNNL and DOE need to have the right of access to work performed by the contractor. Efforts by all parties to cooperate in the present modeling product must be a major effort in this undertaking as many aspects of this work are yet to be defined because of its exploratory and scoping nature.

Release of Information: Any release of the technical and scientific information developed as a result of conducting the contract scope of work shall only be provided, shared or communicated after receiving acknowledgement of receipt of said information from the DOE Contracting Officer and the Contracting Officers Representative.

Quality Assurance: Test and procedure requirements must be documented as defined in the Deliverable [C.3(a)]for the QA program. Test activities and procedures will be defined in the submitted Test Plan and will be used to govern the scope of work as it is implemented throughout the project cycle. As is recognized in the ORP Implementing Procedure (IP) (TRS-

QSH-IP-10 R2, “U.S. DEPARTMENT OF ENERGY, OFFICE OF RIVER PROTECTION

GRADED APPROACH”) the extent of management and QA controls applied to an activity will vary as a function of the degree of confidence needed to achieve the desired quality of the activity. The grading process provides the flexibility to design and implement controls that best suit the activity. The QA program shall contain the appropriate rigor of controls necessary to manage these activities necessary to achieve ORP’s mission. The nature of the effort described in the SOW is a basic research activity whose objective is data collection. Therefore it conforms to the definition of an “Excluded Work Activity” as defined in Section 4.2 of the cited ORP IP.

It is in the best interest of ORP to Assign a level of rigor this work activities so that it shall be managed in a manner that ensures that the grading methods or rigor do not grade the QA criterion to zero.

It is recognized that this work is basic research of an exploratory and scoping nature; therefore, some of the work may require Subject Matter Experts (SME) to define safety and quality issues as planning and project implementation are progressing. The issue at hand is that safety and quality issues must in no way minimized. In addition, it is to be understood that the product of this effort is not to be used as design-basis input.

DELIVERABLES AND REQUIREMENTS

(a) Quality assurance. Test and procedure requirements will be documented consistent with the requirements defined in ORP implementing procedure DOE-ORP-PRO-QA-50121, Rev 2-0.2 Though the DOE procedure referenced is the guiding document, compliance by

2 DOE-ORP-PRO-QA-50121, Rev 2-0, 2021 Graded Application of Quality Assurance Requirements for Nuclear Related Research and Development, Rev. 2-0, U.S. Department of Energy, Office of River Protection, Richland, Washington, February 24.

the contractor with it is ensured by complying with the work practices described below in Requirements 1-18. For example, self-certified calibration of balances and thermocouples will be performed, with periodic verification by external personnel. Test activities and procedures will be defined in the submitted test plan and will be used to govern the scope of work as it is implemented throughout the project cycle. It is recognized that this work is basic research of an exploratory and scoping nature as defined in ASME NQA-13 and DOE/RW-0333P4; therefore, some of the work may require subject matter experts to define safety and quality issues as planning and project implementation are progressing.

The work conducted under this contract is applicable uniquely to low-activity waste treatment. Therefore the work practices for quality assurance described in DOE/RW-0333P are not applied. Basic research is recognized as a process, the objective of which is to gain fuller knowledge or understanding of the fundamental aspects of phenomena and of observable facts without specific applications toward processes or products in mind. The issue at hand is that safety and quality issues must in no way be minimized. Two cornerstones of the work under this contract shall be that

(1) Results can be reproduced by qualified personnel in the field being investigated

(2) Results get validated through a peer review process.

In addition, it is understood that the product of this effort is not to be used as design-basis input.

(b) The contractor shall submit a test plan for ORP review and concurrence prior to project commencement or testing. The test plan shall include:

(1) Strategy to accomplish the technical task description

(2) Defined test and procedure requirements

(3) Directive for QA conditions

(4) Evidence of the required education/certification or qualification required of the researcher(s)

(5) Documentation of appropriate training required of the researcher(s)

The directive for QA conditions required in the test plan shall be in compliance with the graded approach defined herein and as follows. The graded approach is the application process for administrative controls. It is a process by which the level of analysis, extent of documentation, and degree of rigor of process control are applied commensurate with their significance, importance to safety, life-cycle state of a facility or work, or programmatic mission.

(c) Final work shall be documented in a formal report due to DOE-ORP for review no later than 45 days after the completion of testing.

(d) The primary deliverables during the work shall be manuscripts accepted and published in scholarly professional journals and graduate dissertations. Additionally, keynote lectures, 3 ANSI/ASME NQA-1, 2008, Quality Assurance Requirements for Nuclear Facility Applications, American National Standards Institute/American Society of Mechanical Engineers, New York, New York.

4 DOE/RW-0333P, 2008, Quality Assurance Requirements and Description, Rev. 20, Office of Civilian Radioactive Waste Management, U.S. Department of Energy, effective date October 1.

university seminars, and invited presentations to nationally and internationally accredited conferences are encourage.

(e) All quality affect activities must be completed under some type of procedures that implement the contract QA requirements.

Requirement 1: Organization The organization responsible for research and development (R&D) work shall be defined and its roles, responsibilities, and authorities that support achievement of R&D work objectives shall be described. Interface responsibilities shall be defined between R&D and support functional elements. An authoritative relationship shall be defined for basic research. It shall identify those involved in collaboration and peer review activities to document the credibility of the research process.

Requirement 2: Quality Assurance Program The R&D QA program shall be based on the proven processes that govern the performance of successful scientific research. Only qualified individuals shall engage in selective investigation activities. Investigative activities shall be carefully reviewed by independent competent peers and the documented results will be verifiable and able to withstand scrutiny by reviewers, potential users, and the entire research community.

The purpose of software review activities is to provide adequate confidence that the software performs all intended functions, provides correct solutions, and does not perform or cause any adverse unintended functions. The extent of the software review activities should be commensurate with the risk associated with the failure of the software. Factors affecting this risk include the potential impact on safety and/or operation, complexity of computer program design, degree of standardization, state of the art, and similarity with previously proven computer programs.

Performance requirements or acceptance criteria should be developed. Determining that the software complies with the performance requirements should provide reasonable assurance that the software can operate within the defined functional capabilities. Defining the required functional capabilities should be performed in conjunction with the identification of capabilities and limitations for intended use.

Requirement 3: Design Control Design control does not apply.

Requirement 4: Procurement Document Control The application approach shall be to anticipate the needs of the next phase of the R&D life cycle.

For example, if final results of the work are expected in the next stage of the work, and if the pedigree of materials being used could influence the usefulness of the results of the work during applied research, procurement document specifications should be controlled appropriately.

Requirement 5: Instructions, Procedures, and Drawings Basic research shall be documented in proposals, conceptual drawings, sketches, and notebooks.

The level of documentation shall be sufficient to withstand a successful peer review. The protocol required to comply with this requirement will safeguard the data, and process development of this effort will address the partial compliance with that set forth in Requirement 2, namely subsequent independent review by competent peers and without recourse to the originator. The contractor shall utilize laboratory notebooks that both generate carbonless copies and allow for the copy to be separated from the bound notebook without compromising the integrity of the notebook. Each researcher shall be assigned a uniquely identified laboratory notebook. Each page shall be consecutively numbered. Entries shall be made in indelible ink.

Errors or corrections will be made by a single line through the offending item, with the date and initials of the party making the change. If the correction is being made by a person other than the person to whom the laboratory notebook is assigned, then the initials shall be followed by legibly writing the full name of the individual making the correction. On a regular basis (e.g., weekly) the principal investigator (PI) shall review each completed page, inscribe the statement “Read and understood,” and sign and date the page. On a quarterly or more frequent basis (as established in the test plan), the contractor shall submit to the Contracting Officer’s Representative the collection of indexed laboratory notebook pages from that period being covered.

The criterion that scientific notebooks shall be reviewed by an independent qualified individual is imposed so as to verify there is sufficient detail to:

• Retrace investigations and confirm results

• Repeat the investigation and achieve comparable results, independent of the original investigator

• Ensure data shall be identified in a manner that facilitates traceability to associated documentation

• Ensure data shall be identified in a manner that facilitates traceability to its qualification status

• Ensure identification and traceability shall be maintained throughout the lifetime of the data

• Ensure data reduction shall be described to permit independent reproducibility by another qualified individual.

Requirement 6: Document Control Meeting this requirement, at a minimum, is satisfied by subjecting laboratory notebooks to the defined document control procedure. The process for development of intellectual property documentation is subject to document control, and this shall be met by utilizing the laboratory notebooks to report and control such intellectual property.

Requirement 7: Control of Purchased Materials, Items, and Services If the quality of work results depends on the quality verification of materials, items, or services, the work shall be planned to include this Requirement. Procurement planning shall:

• Identify what is to be accomplished, who is to accomplish it, how it is to be accomplished, and when it is to be accomplished.

• Ensure supplier-generated documents shall be controlled, processed, and accepted in accordance with established methods.

• Identify how suppliers shall verify furnished items or services comply with the contractor’s procurement documented requirements before offering the items or services for acceptance. This is met by:

− Evaluation of the supplier certificate of conformance (items and related services).

− Technical verification of data produced (services only).

− Surveillance and/or audit of the activity (services only).

− Review of objective evidence (e.g., certifications and test reports) for conformance to procurement document requirements (services only).

Requirement 8: Identification of Control Items As the quality of work results depends on the pedigree of materials or items (e.g., analytical chemistry), this requirement applies. External calibration services for balances, etc. shall be documented. Organizational responsibilities, including those for individuals or groups that are trained and qualified are to be documented in the project records. Records are to be maintained for each special process method. Qualification requirements for personnel, implementing documents, and equipment, which comply with specified requirements. Evidence that the manufacturer’s recommendations for servicing, calibration, and compliant usage by research staff shall be documented.

Requirement 9: Control of Processes In basic research, control of processes is left to the researcher to define. Process control shall be recorded in a laboratory notebook.

Requirement 10: Inspection This requirement does not apply to basic research because it requires work to be inspected to predetermined acceptance criteria.

Requirement 11: Test Control Test control does not apply to basic research activities in which hypotheses are being evaluated.

It does apply to support activities associated with the conduct of research. Requirement 5 sets forth the requirements for data identification and data reduction. In basic research, test methods are not well-defined and are usually determined by the researcher as work progresses.

Requirement 12: Control of Measuring and Test Equipment The PI shall specify the requirements of accuracy, precision, and repeatability of measuring and test equipment (M&TE). Depending upon the need for accuracy, precision, and repeatability of M&TE used in research, standard M&TE procedures shall be followed. Where standard M&TE procedures are not used, effects of the instrument’s performance on the uncertainty of the measurements and tests shall be considered in the research. It is recognized that in basic research, calibration might not be necessary during the initial (or scope-setting) stages of an activity.

Requirement 13: Handling, Storage, and Shipping Good laboratory practices shall be defined as instructions used for conducting the activity. These instructions shall be included in the test plan, or by revisions or additions to the applicable section of the test plan. The primary item envisioned to be included in this element are samples between collaborating laboratories (e.g., PNNL or WSU) and submission of records to ORP.

Requirement 14: Inspection, Test, and Operating Status This criterion has severely limited applicability for basic research activities. Inspection, test, and operational status of equipment or systems that support research are controlled at the discretion of the PI. Attention is called to the requirements placed upon the contractor for the data collected and reported.

Requirement 15: Control of Nonconforming Items/Control of Nonconformance of Contract Conditions Several conditions exist for reporting nonconformance of established contract conditions. These requirements are for the contractor to report nonconformances to ORP, and the contractor must obtain Contracting Officer approval of contractor-recommended dispositions.

The Contracting Officer will establish and contractually document with the contractor the process for disposition of services that do not meet procurement document requirements in accordance with the following;

(a) The contractor shall submit a report of nonconformance to ORP that includes contractor-recommended disposition (e.g., “use as is” or “repair”) and provide technical justification for such disposition.

(b) The contractor shall submit to ORP for approval, reports of nonconformances to procurement document requirements or documents approved by ORP. Examples of conditions requiring a report of nonconformance include:

(1) Failure to meet technical or material requirements.

(2) Failure to meet a requirement in contractor documents that have been approved by

ORP.

(3) Nonconformances that cannot be corrected by continuation of the original research process or by rework.

(c) Data or products that do not conform to the original requirement even though the service or product can be restored to a condition such that its value to ORP is unimpaired.

Requirement 16: Corrective Action The documentation, reporting, and tracking of conditions adverse to quality are done at the discretion of the researcher. As this is a basic research effort, the use or formality of corrective action identification and tracking systems shall be defined by the PI and researcher(s), depending on the need to transmit information to peers. In all cases, the contractor will report to ORP when a need to transmit information to peers on conditions adverse to quality are done.

Requirement 17: Quality Assurance Records The notebook or journal of the researcher is the QA record. Controls are needed for these documents; for example, maintain copies of critical pages or access-controlled filing when not in use to preserve process repeatability and the QA record. Electronic media may be used to record data and shall be subject to appropriate administrative controls for handling and storage of data.

The method of record storage shall be defined in the test plan submitted to ORP. The Contracting Officer’s Representative shall approve the record keeping methods.

Requirement 18: Audits As this effort has been defined as basic research, the objectives of the audit process shall be achieved as a part of peer review activities if the peer review process is sufficiently comprehensive. Part of this peer review process shall be an audit by ORP prior to the start of the work. The audit will establish the effectiveness of record keeping and the quality of written records generated by the contractor.

(a) Final work shall be documented in a formal report due to ORP for review no later than 45 days after the completion of testing.

(b) The primary deliverables during the work shall be manuscripts accepted and published in scholarly professional journals and graduate dissertations; contractor personnel and students working under this contract may also deliver keynote lectures, university seminars, and invited presentations to nationally and internationally accredited conferences.