N233-117 TITLE: Defluorination of PFAS-impacted Matrices and Detection Methodologies
OUSD (R&E) CRITICAL TECHNOLOGY AREA(S): Advanced Materials;Sustainment
OBJECTIVE: This topic seeks to: (1) demonstrate the integration of new treatment technologies for Per- and Polyfluoroalkyl substances (PFAS) impacted matrices to enable complete on-site disposal/management of PFAS-containing wastewater and solid wastes; (2) demonstrate and validate a rapid field portable solution for PFAS detection in wastewater and solid waste; and (3) develop a standardized analytical approach to properly quantify microplastics in drinking water, wastewater, and solid matrices.
DESCRIPTION: The Department of the Navy (DON) installations vary significantly in their missions, industrial operations, and functions but common to all of them is the generation of wastewater streams. Ensuring proper treatment of these wastewater streams is critical to comply with the installations� permits and secure the availability of potable and non-potable water supplies to sustain missions. Currently, treatment of wastewater streams impacted by contaminants of emerging concern (CEC), such as Per- and Polyfluoroalkyl Substances (PFAS) and potential microplastics, present DON installations with an ongoing challenge.
With present interest in replacing aqueous film forming foam (AFFF) with fluorine-free foam (F3) alternatives, there is a need to dispose of AFFF stockpiles and to treat wastewater streams derived from cleaning fixed (hangars) and mobile (firetrucks) fire suppression systems to less than 70 parts per trillion (ppt.) before discharging into sewers [Refs 1-4]. Often these wastewater streams are treated via conventional methods that involve granular activated carbon (GAC) and ion-exchange (IX) resin�thus producing PFAS-impacted waste that requires off-site disposal. In addition, wastewater treatment plants (WWTP) owned by DON installations may produce PFAS-impacted sewage-sludge and biosolids as a result of processing PFAS-impacted wastewaters from households using products containing PFAS (e.g., cleaning/degreasing agents; water-resistant, stain resistant, and fire-resistant fabrics; non-sticky cookware; personal-care products, etc.). Treated sewage-sludge or biosolids are often applied to crops and fields to supply plant organic nutrients without the use of synthetic fertilizer. If biosolids are PFAS-impacted, they have the potential to become a direct source of PFAS release into the soil and groundwater. In a similar manner, microplastics may end up in soil and groundwater due to the application of treated sewage-sludge or biosolids derived from the processing of domestic wastewater streams containing personal care products (e.g., toiletries and cosmetics) and washing of synthetic textiles [Refs 5-6].
As such, there is a need for PFAS destruction technologies for wastewater and solid waste (e.g., PFAS-impacted wastewater, PFAS-laden GAC, PFAS-laden IX-resin, and PFAS-impacted biosolids) [Refs 6-11]. Prototype technologies must demonstrate the ability to mineralize total PFAS to benign products without producing toxic waste and/or by-products. Particular emphasis must be placed in the mineralization of the six PFAS compounds�perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorononanoic acid (PFNA), hexafluoropropylene oxide dimer acid (HFPO-DA, commonly known as GenX Chemicals), perfluorohexane sulfonic acid (PFHxS), and perfluorobutane sulfonic acid (PFBS)�for which the U.S. Environmental Protection Agency (USEPA) is set to establish maximum contaminant levels (MCLs) under the National Primary Drinking Water Regulation (NPDWR). Conversely, it is also critical to have a rapid field portable solution for PFAS detection in wastewater, solid waste and treated PFAS-impacted sources (i.e., wastewater and solid waste). The rapid field portable solution for PFAS detection must be capable of reading PFAS concentration levels for PFOA and PFOS as low as 4 ppt. whereas PFNA, GenX chemicals, PFHxS, and PFBS must attained a combined Hazard Index of 1 (unit less) as proposed by the USEPA [Ref 12]. The latter implies that individual concentrations for these 4 PFAS compounds may be as low as single digit ppt. to double-digit ppt. In the case of microplastics, for which there is no USEPA health advisory and/or proposed federal regulations but are set to become the next major environmental concern in drinking water, wastewater, and solid waste, there is a need to first develop a standardized analytical approach to properly quantify microplastics in drinking water, wastewater, and solid matrices. Once the standardized analytical approach is reliable and consistent across testing, a strategy must be developed to quantify sources of microplastics entering WWTPs and their effectiveness in removing microplastics. If WWTPs are not capable of addressing the removal of microplastics, an explanation must be provided and potential prototype treatment solutions must be identified.
PHASE I: Determine the feasibility of utilizing an emerging PFAS destruction technology to process PFAS-impacted matrices (i.e., wastewater and solid waste) of relevance to DON stakeholders. Some PFAS-impacted matrices of interest include (i) spent granulated activated carbon (GAC), (ii) spent powdered activated carbon (PAC), (iii) spent ion exchange resins (IXR), and/or (iv) complex PFAS-impacted wastewaters (e.g., fire truck rinse out byproducts). Ensure that matrices must be treated using lab-scale systems. Evaluate treatment success through measuring PFAS destruction levels, assessing the fate of fluorine after treatment, and assessing the fate of co-contaminants and matrix constituents (e.g., the filter material) during treatment.
For the rapid field portable solution for PFAS detection, the solution must be practical and not cumbersome as it will be conducted by personnel with and without engineering or scientific backgrounds. In addition, the rapid field portable solution must provide reliable PFAS concentration readings in the presence of other contaminants that may be present in real-life samples provided by DON stakeholders. PFAS detection and concentration levels by the field portable solution must be double-checked by PFAS analytical methods such as USAEPA Methods 533, 537.1, and/or 1633. Information on the capabilities of the solution as well as its shortcomings must be explained. This will provide information as to what areas still need development and how realistic it is to bring a solution into Phase II.
In the case of the standardized analytical approach to properly quantify microplastics in drinking water, wastewater and solid matrices, define, develop, and identify analytical tools that are both microplastic selective (i.e., specific only for some types of microplastics) and inclusive (i.e., able to detect all types of microplastics with adequate recoveries). Ensure that the microplastics comprise a variety of sizes, colors, and chemical compositions to include fibers, fragments, pellets, flakes, sheets, or foams. Discuss the advantages and disadvantages based on analytical tools in a summary of results and provide the best approach for a path forward to improve analysis of microplastics in the aforementioned matrices.
At the end of Phase I, include in the final deliverables information substantiated by results and a Phase II plan that includes a concept for the Phase II field test and demonstration.
PHASE II: Demonstrate the PFAS destruction technology at a DON installation by treating one of the PFAS-impacted matrices identified in Phase I. Based on the results of Phase I, use the demonstration to validate the PFAS destruction performance at a realistic field site, processing a real waste stream. Use demonstration results to assess the feasibility of integrating the proposed technology into longer-term waste management projects.
Demonstrate and validate the rapid field portable solution for PFAS detection at a DON installation that has different sources of PFAS-impacted matrices. Use the equipment in real-time in the field test and demonstration and have it validated with support from DON personnel. Field testing readings must be supported by PFAS analytical testing as indicated in Phase I. Assess ease of use and portability of solution by personnel in the field.
Develop and test a step-by-step protocol of the microplastics standardized analytical approach to standardize collection, extraction, quantification, and identification of microplastics in drinking water, wastewater, and solid matrices to improve reliability, consistency and comparability across testing.
PHASE III DUAL USE APPLICATIONS: Integrate the Phase II-demonstrated technology with full-scale waste disposal and compliance-related PFAS management efforts and coordinate with the Air Force Civil Engineer Center (AFCEC) and the U.S. Army Corps of Engineers (USACE) to transition the technology to tackle broader (not just DON) Department of Defense (DoD)-wide challenges around PFAS-impacted sites. Address non-DoD Governmental and commercial needs including remediation of PFAS-impacted airport and fire training facilities, industrial wastewater treatment, and waste disposal.
Work with USEPA regulators to qualify Phase II rapid field portable PFAS detection and microplastics standardized analytical approach in order to mainstream them. Use rapid field portable PFAS detection and microplastics standardized analysis to quantify sources entering WWTPs and their effectiveness in removing them. If WWTPs are not capable of addressing the removal of PFAS and/or microplastics, provide an explanation and identify potential prototype treatment solutions.
REFERENCES:
KEYWORDS: Per- and polyfluoroalkyl substance; PFAS; PFAS destruction; Perfluorooctane sulfonic acid; PFOS; Perfluorooctanoic acid; PFOA; Aqueous film-forming foam; AFFF; Environmental Compliance; Environmental Restoration; AFFF-impacted media; Granular Activated Carbon; GAC; Ion Exchange Resin; Solid-derived Wastes; Rapid Field PFAS Detection; Portable PFAS Detection; PFAS Detection in Real-Time; Microplastics; Microfibers
** TOPIC NOTICE ** |
The Navy Topic above is an "unofficial" copy from the Navy Topics in the DoD 23.3 SBIR BAA. Please see the official DoD Topic website at www.defensesbirsttr.mil/SBIR-STTR/Opportunities/#announcements for any updates. The DoD issued its Navy 23.3 SBIR Topics pre-release on August 23, 2023 which opens to receive proposals on September 20, 2023, and closes October 18, 2023 (12:00pm ET). Direct Contact with Topic Authors: During the pre-release period (August 23, 2023 through September 19, 2023) proposing firms have an opportunity to directly contact the Technical Point of Contact (TPOC) to ask technical questions about the specific BAA topic. Once DoD begins accepting proposals on September 20, 2023 no further direct contact between proposers and topic authors is allowed unless the Topic Author is responding to a question submitted during the Pre-release period. SITIS Q&A System: After the pre-release period, until October 4, 2023, at 12:00 PM ET, proposers may submit written questions through SITIS (SBIR/STTR Interactive Topic Information System) at www.dodsbirsttr.mil/topics-app/ by logging in and following instructions. In SITIS, the questioner and respondent remain anonymous but all questions and answers are posted for general viewing. Topics Search Engine: Visit the DoD Topic Search Tool at www.dodsbirsttr.mil/topics-app/ to find topics by keyword across all DoD Components participating in this BAA.
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| 10/3/23 | Q. | During the phase I program would we be given access to any of the specified PFAS contaminated matrices directly from end users or would we need to source them ourselves? |
| A. | We can work the logistics to provide PFAS-impacted samples based on need/requirement. | |
| 10/3/23 | Q. | What is the desired entry TRL of the PFAS destruction technology? |
| A. | For Phase I a lower level TRL is expected. | |
| 10/3/23 | Q. | The references on PFAS destruction utilize processes at high temperatures and pressures. Does the Navy desire the implementation of these processes (and associated hardware), or does the Navy seek improvement upon these processes to near STP conditions thereby easing implementation? |
| A. | Proposing small businesses must decide on the best approach based on the capabilities of their technologies. | |
| 10/3/23 | Q. | Are there any limitations on reactants used for the desired system? What about energy input? |
| A. | SBIR Topic Idea N233-117 calls for "PFAS destruction technologies for wastewater and solid waste (e.g., PFAS-impacted wastewater, PFAS-laden GAC, PFAS-laden IX-resin, and PFAS-impacted biosolids) [Refs 6-11]. Prototype technologies must demonstrate the ability to mineralize total PFAS to benign products without producing toxic waste and/or by-products." Proposing small businesses must access their de-fluorinating process to account for complete PFAS mineralization and zero production of any additional contaminants of concern and/or byproducts. | |
| 10/3/23 | Q. | Is the Navy interested in destruction of AFFF, or treatment of the waste water/solids streams associated with it? |
| A. | As mentioned in a previous response, and within the topic details, "Some PFAS-impacted matrices of interest include (i) spent granulated activated carbon (GAC), (ii) spent
powdered activated carbon (PAC), (iii) spent ion exchange resins (IXR), and/or (iv) complex PFAS-impacted wastewaters (e.g., fire truck rinse out byproducts)."
Destruction of AFFF concentrate (e.g., 3 or 6 percent) also qualifies as a PFAS-impacted matrix. |
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| 10/3/23 | Q. | At what scale will this process need to be performed at in Phase I in order to demonstrate feasibility? |
| A. | There are no scale requirements for Phase I. However, it is important to note that the size of the final technology prototype must be scalable and functional for mobility as it may be transported to different locations within a region if a Phase II is requested. | |
| 10/3/23 | Q. | What is the ratio of solid to liquid waste? Is there a waste stream that is more dominant? |
| A. | The ratio of solid to liquid waste is subject to the type of PFAS-impacted source. Specific ratios will not be provided at this time as they vary from source to source. | |
| 10/3/23 | Q. | What are the typical starting concentrations of PFAS the waste streams? |
| A. | PFAS concentrations vary depending on the PFAS-impacted waste streams. For example, the total PFAS concentration for PFAS-laden GAC and PFAS-laden IX-resin may range from ppb to ppm. The latter is subject to PFAS concentration of the feed wastewater used for processing/treatment with the media. For PFAS-impacted wastewaters, PFAS concentrations range from ppt. to ppb. | |
| 10/3/23 | Q. | Is the Navy interested in a single process for both solid and liquid waste streams, or can they be separate processes? |
| A. | SBIR Topic Idea N233-117 calls for "PFAS destruction technology to process PFAS-impacted matrices (i.e., wastewater and solid waste) of relevance to DON stakeholders. Some PFAS-impacted matrices of interest include (i) spent granulated activated carbon (GAC), (ii) spent powdered activated carbon (PAC), (iii) spent ion exchange resins (IXR), and/or (iv) complex PFAS-impacted wastewaters (e.g., fire truck rinse out byproducts)." The technology and/or process approach is left to the consideration of the proposing small businesses. | |
| 9/18/23 | Q. | 1. In the topic there is a sentence "the rapid field portable solution must provide reliable PFAS concentration readings in the presence of other contaminants that may be present in real-life samples provided by DON stakeholders". What are these contaminants? Knowing more about the contaminants help developing the sensor with high specificity.
2. Is it possible to get some field samples for sensor evaluation in Phase I? |
| A. | 1. PFAS-impacted matrices/samples may have other co-contaminants present in addition to PFAS such as natural organic matter, non-fluorinated surfactants, suspended solids, total dissolved solids, different ions (iron, manganese, sodium, potassium, nitrate, nitrite, phosphate, etc.), metals, oils, hydrocarbons. Of course, specific co-contaminants vary depending on the origin of the PFAS-impacted matrix/sample. ???????
2. Yes, we can work the logistics to provide PFAS-impacted samples based on need/requirement. |
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| 9/15/23 | Q. | Does Navy expect solutions to be able to treat a diverse array of PFAS-impacted matrices, or are solutions that are focused on one specific matrix (eg wastewater) acceptable? |
| A. | DoD SBIR 2023.3 Topic Idea N233-117 states that "some PFAS-impacted matrices of interest include (i) spent granulated activated carbon (GAC), (ii) spent powdered activated carbon (PAC), (iii) spent ion exchange resins (IXR), and/or (iv) complex PFAS-impacted wastewaters (e.g., fire truck rinse out byproducts). Hence, submission can propose to one or multiple matrices depending on the technical capabilities/features of the of the technology put forward. | |
| 8/31/23 | Q. | Are there any cost or size requirements at this stage for the proposed technologies? |
| A. | Assuming the cost is associated with the final technology prototype, at this time there is no particular value in mind. However, for the PFAS destruction technology and field portable detection solution, they must be competitive with conventional technologies for which there is a cost already established and associated per gallon of PFAS-impacted wastewater treated, drum of PFAS-impacted waste disposal, and/or analysis per sample (e.g., PFAS-impacted wastewater and/or solid waste).
The size of the final technology prototype for PFAS destruction must be functional for mobility as it may be transported to different locations within a region. The field portable detection solution must be compact enough for field use. |
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| 8/31/23 | Q. | The PFAS detection describes being able to measure three different model PFAS in ppt range. Is there also interest in a total PFAS method to measure the total amount of PFAS regardless of the specific type? |
| A. | The rapid field detection portable solution for PFAS must be capable of reading total PFAS concentration in wastewater, solid waste and/or treated PFAS-impacted sources (i.e., wastewater and/or solid waste). In addition, particular emphasis must be placed in the detection of the six PFAS compounds � perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorononanoic acid (PFNA), hexafluoropropylene oxide dimer acid (HFPO-DA, commonly known as GenX Chemicals), perfluorohexane sulfonic acid (PFHxS), and perfluorobutane sulfonic acid (PFBS)�for which the U.S. Environmental Protection Agency (USEPA) is set to establish maximum contaminant levels (MCLs) under the National Primary Drinking Water Regulation (NPDWR). | |
| 8/31/23 | Q. | N233-117 makes mention of three different solicitated proposed works (PFAS destruction, PFAS detection, and microplastics analytical method). Would submissions be expected to propose a solution to one of these or could they also potentially propose multiple in the same submission (e.g., PFAS destruction + detection)? |
| A. | SBIR N233-117 has three main objectives. Submissions can propose solutions to one or potentially multiple objectives as long as they address the specific questions of the respective phases. |