Progress 04/15/23 to 04/14/24
Outputs
Target Audience:The target audiences reached by our efforts during this reporting period were mostly undergraduate and graduate students interested in nutrient recovery from agricultural waste, academics from other institutions interested in our efforts on Donnan dialysis processes for nutrient recovery, industry collaborators that currently produce flat-sheet, ion-exchange membranes or hollow-fiber membranes (without ion-exchange capabilities), and other agricultural stakeholders interested in our Donnan dialysis technology. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?Currently, the training and professional development has mostly focused on two postdoctoral research associates, Dr. Hui Chen (woman) and Dr. Michael Rose, one PhD student, Ms. Sahar Souizi (woman, Environmental Engineering), and four undergraduate researchers, Ms. Kaylyn Stewart (African American woman, Chemistry major), Mr. Fabian Amurrio (Hispanic American man, Chemical Engineering major), Ms. Zaira Castillo Diaz (Hispanic American woman, Chemical Engineering major), and Ms. An Dang (woman, Chemical Engineering major). Hui Chen joined in April 2021 and concluded her work on this project in Summer 2023; she will begin as Assistant Professor at James Madison University in Fall 2024. Michael Rose joined the project in November 2020, finished his work in May 2022, and began a job at the US Environmental Protection Agency. Sahar Souizi joined the project in Fall 2022 and will lead the project through its conclusion in 2025. Kaylyn Stewart and Fabian Amurrio began working with Hui Chen in September 2021, whereas Zaira Castillo Diaz started in June 2022. Fabian Amurrio graduated in December 2022, and Zaira Castillo Diaz wrapped up her work on this project at the same time. An Dang began working with Sahar Souizi in August 2023 through her graduation in May 2024. Kaylyn Stewart (University of Washington) and An Dang (University of Michigan) began PhD programs following the completion of their BS degrees. All postdoctoral research associates, graduate students, and undergraduate researchers have been trained in agricultural waste production and chemistry, reactor design, polymer chemistry, membrane production and modification techniques, environmental chemistry, Donnan dialysis, ion exchange, mass transport, and chemical equilibrium modeling. They have also learned about and gained experience using the following analytical and characterization techniques: scanning electron microscopy with energy dispersive x-ray spectroscopy; ion chromatography; inductively coupled plasma mass spectrometry; and, UV-visible absorbance spectrophotometry, which is employed with colorimetric assays for orthophosphate (P(V)) and ammonium (NH4+) analysis. Postdoctoral research associates meet with the PI each week to discuss progress, obstacles, and related literature, and these meetings often involve professional development discussions about mentoring, leadership, and scientific writing. The PhD and undergraduate researchers meet with the PI on a biweekly schedule, and all student team members meet (without the PI) in the intervening weeks. All team members also join the full 2-h group meeting each week, where they provide updates and presentations on their recent work. This multi-level strategy ensures that all trainees receive feedback from the PI, their teammates, and the rest of the lab group on a regular basis. The impacts of training and professional development are highlighted by the following recent accomplishment. Ms. Souizi shared the results of her research to the Chesapeake Water Environment Association and Chesapeake Section of the American Water Works Association in May 2024. She won first place in the student poster competition. This outcome highlighted the technical merits of her work, but also provided opportunities to interface with industry professionals interested in translating our Donnan dialysis technologies to the real world to address issues with nutrient pollution from animal waste and other sources. Her abstract is provided below. Souizi, S.; Dang, A.H.; Chen, H.; Blaney, L. Sustainable and rapid nutrient recovery by advanced Donnan dialysis reactors. 2024 Chesapeake Water Environment Association and Chesapeake Section of the American Water Works Association Joint Spring Meeting (Perryville, MD), May 23, 2024. Donnan dialysis leverages electrochemical potential gradients across ion-exchange membranes to selectively separate nutrients from wastewater. This project aimed to improve the rate of nutrient recovery and scale-up potential through development of novel Donnan dialysis reactors. A batch-recycle system was used to evaluate the impacts of mixing, flow rate, and waste-to-draw solution volume ratio. With the optimal conditions, 90% orthophosphate recovery was achieved, and nutrient flux was increased by 30%. These results informed development of modular, tube-in-tube Donnan dialysis reactors, which enabled rapid nutrient recovery as struvite. These results support the role of Donnan dialysis systems to achieve circular nutrient economies. How have the results been disseminated to communities of interest?(continued from above in major accomplishments section) We have received a no-cost extension to continue this project for an additional year. During that time, we will work to complete Objective 3, which involves incorporation of brackish water, seawater, and reverse osmosis concentrates as alternative draw solutions for recovery of nutrients from real animal wastes. We are currently finalizing one manuscript with a working title, "Alternative Donnan dialysis draw solutions for phosphorus recovery from wastewater: sustainable use of reverse osmosis concentrate", based on the use of reverse osmosis concentrate from brackish groundwater as an alternative (free) draw solution. The results of that study were encouraging, especially because the reverse osmosis concentrates could be directly integrated into our Rd/w framework for designing Donnan dialysis systems. The working abstract for this paper is provided below. Shashvatt, U.; Raphael, M.; Boby, A.; Walker, S.; Blaney, L. Alternative Donnan dialysis draw solutions for phosphorus recovery from wastewater: sustainable use of reverse osmosis concentrates. In preparation High salinity wastes can serve as alternate draw solutions in Donnan dialysis processes for orthophosphate (P(V)) recovery to reduce operational costs and improve process sustainability. Brackish groundwater, seawater, and reverse osmosis (RO) concentrates generated from brackish groundwater and seawater desalination are promising alternate draw solutions due to the high chloride (Cl-) content. Typical concentrations of Cl- in seawater, brackish water RO concentrate, and seawater RO concentrate range from 0.53-0.64 M, 0.08-0.40 M, and 0.57-1.23 M, respectively. In this study, a novel framework was developed and employed to predict P(V) recovery efficiency in Donnan dialysis using these alternate draw solutions. Draw solutions comprised of brackish groundwater, brackish water RO concentrate, seawater, and seawater RO concentrate achieved 59.7%, 93.8%, 98.2%, and 98.8% P(V) recovery, respectively, from 10 mM P(V) wastewater; Cl- contributed 24.9%, 86.9%, 97.8%, and 98.4%, respectively, to the overall P(V) recovery efficiency. The remaining contributions to the overall P(V) recovery efficiency were mostly from bicarbonate and sulfate, which were present at low-to-moderate concentrations in the alternative draw solutions. Brackish water RO concentrate, which is a widely available inland resource, was further evaluated as an alternative draw solution in Donnan dialysis experiments. Using brackish water RO concentrate, 99.8% and 74.5% P(V) were removed from wastewater with 1 and 10 mM P(V) via Donnan dialysis. The presence of calcium and magnesium in the brackish water RO concentrate favorably interacted with the recovered P(V) to form struvite and hydroxyapatite solids. Addition of chelating agents, such as ethylenediaminetetraacetic acid, and magnesium led to formation of high-purity struvite, which is a valuable slow-release fertilizer. Overall, this work highlights new opportunities for sustainable resource recovery via Donnan dialysis with alternative draw solutions. As noted in our previous report, we have constructed ten tube-in-tube membrane modules (i.e., five anion-exchange and five cation-exchange systems). Those systems required some iteration over the past year to prevent leaks and ensure ease of construction and maintenance. The tube-in-tube reactors have now been finalized and are being applied to address nutrient recovery from real animal waste in Objective 3. As noted in the above ACS abstract, Ms. Souizi has also begun investigating nutrient recovery from real animal wastes, namely poultry litter slurries for the time being although other animal wastes will be considered moving forward. The high organic matter content in the slurry resulted in some limitations on the recovery of orthophosphate; however, that outcome was attributed to the design of the draw solution, which did not account for dissolved organic matter. We are currently working to account for competition from organic matter to ensure that the actual reactor performance matches the designed recovery efficiencies. Overall, we are confident that high nutrient recovery efficiencies and fast rates of nutrient recovery can be achieved with the tube-in-tube reactors during the final year of this project. We presented work from this project at several key conferences, including the 2023 AEESP Research and Education Conference (Boston, MA), Fall 2023 ACS National Meeting (San Francisco, CA), AIChE 2024 Mid-Atlantic Student Conference (Baltimore, MD), 2024 UMBC Undergraduate Research and Creative Achievement Day (Baltimore, MD), and the 2024 Chesapeake Water Environment Association and Chesapeake Section of the American Water Works Association Joint Spring Meeting (Perryville, MD). The PI was invited to serve as Discussion Leader for a session on "Reimagining wastewater" at the 2024 Environmental Sciences: Water Gordon Research Conference (Holderness, NH). We also shared our findings in invited seminars to the following groups: New York University (May 2023); University of California, Irvine (January 2024); Stony Brook University (June 2024); and the Meyerhoff Scholars Program (July 2024). In addition, we published one paper in Current Opinions in Chemical Engineering (impact factor = 8.0). Chen, H.; Souizi, S.; Stewart, K.; Blaney, L. (2023). Application of the Rd/w framework to assess Donnan dialysis performance. Current Opinion in Chemical Engineering 42, 100967. https://doi.org/10.1016/j.coche.2023.100967 What do you plan to do during the next reporting period to accomplish the goals?In the next reporting period, we plan to complete the project and wrap up the remaining manuscripts, which will focus on application of the tube-in-tube Donnan dialysis reactors for nutrient recovery from real wastes.
Impacts
What was accomplished under these goals?
Our work to date has focused on Objectives 1-3. One important outcome from this work is our recent publication in Current Opinions in Chemical Engineering (impact factor = 8.0), which demonstrated our framework for the design and interpretation of Donnan dialysis systems using our Rd/w framework. We were particularly excited about this research product, because we applied our fundamental framework for Donnan dialysis to previously published data from other groups. While most of the literature data supported our framework, the remainder allowed us to elaborate deficiencies in previous studies and highlight best practices for designing and interpreting Donnan dialysis systems for nutrient recovery applications; however, the impacts of this work can also be extended to recovery of other resources. The abstract for this article is provided below for more information. Chen, H.; Souizi, S.; Stewart, K.; Blaney, L. (2023). Application of the Rd/w framework to assess Donnan dialysis performance. Current Opinion in Chemical Engineering 42, 100967. https://doi.org/10.1016/j.coche.2023.100967 Donnan dialysis exploits electrochemical potential gradients across ion-exchange membranes to separate ions between feed and draw solutions. This technique has been applied for treatment and recovery of chemicals in water and wastewater. Previous studies have arbitrarily selected the draw solution chemistry, making it difficult to fairly compare experimental outcomes. A universal framework is needed to standardize design and interpretation of Donnan dialysis systems. We calculated the Rd/w parameter, which is related to the draw ion concentrations in the feed and draw solutions at Donnan equilibrium, for previous studies. Rd/w values were used to determine theoretical recoveries and compare them to experimental outcomes. Of the literature data, 57% matched the theoretical recovery, 37% underperformed due to operating time constraints or transport limitations, and 6% outperformed Donnan equilibrium due to use of integrated processes. Ultimately, this work highlights the benefits of the Rd/w framework for standardizing interpretation of Donnan dialysis systems. As indicated in our previous report, we decided to focus on development of novel tube-in-tube reactors for the remainder of this project. The transport phenomena involved with these novel reactors required fundamental study due to the complexities introduced by the continuous flow of process influent and effluent, unlike the conventional, flat-sheet, batch reactors used in most Donnan dialysis studies. Over the past year, Ms. Sahar Souizi (PhD student) and Ms. An Dang (BS student) have been conducting experiments with the tube-in-tube reactors. These reactors involve an inner tube, through which we circulate the salt-laden draw solution (e.g., brackish groundwater), and an outer tube, through which we pump the waste solution (e.g., animal agriculture wastewater enriched with nutrients). These reactors provide advantages with respect to scale up and throughput due to their modular design and high ratio of membrane surface area to reactor volume, respectively. The main accomplishments involve both experimental and modeling outcomes. Ms. Souizi will present these findings at the upcoming Fall 2024 American Chemical Society National Meeting (Denver, CO); her abstract is provided below. Importantly, she has derived a complex (and long) first principles-based model to explain the transport phenomena in the tube-in-tube Donnan dialysis reactors. This model has been validated and successfully applied to describe the change in nutrient concentrations for both the waste and draw solutions; with these data, we plan to submit a manuscript with the working title, "Enhanced Donnan dialysis for sustainable nutrient recovery from waste streams using a first principles-based model", by the end of the year. With her model, the reactor design and operation can be further optimized to improve the overall rate of nutrient recovery from waste streams. These results reinforce our excellent progress on Objectives 1-2, which have now been completed. Souizi, S.; Dang, A.H.; Blaney, L. Enhanced Donnan dialysis for nutrient recovery via tube-in-tube reactors: impact of operating conditions and application to real waste. Fall 2024 American Chemical Society National Meeting (Denver, CO), August 18-22, 2024. Donnan dialysis has been promoted for selective separation and recovery of vital resources from waste. We developed an innovative Donnan dialysis reactor that leverages a tube-in-tube configuration to concurrently recover anionic (e.g., orthophosphate) and cationic (e.g., ammonium, potassium) nutrients from wastewater. The specific objective of this work was to accelerate scale up and application of the tube-in-tube Donnan dialysis reactor for nutrient recovery from real waste by (1) deriving a first principles-based model to design and optimize nutrient recovery for batch-recycle and continuous flow operations, (2) applying Donnan dialysis to recover nutrients from real agricultural waste, and (3) benchmarking the performance against synthetic solutions to identify potential impacts of fouling and competing ions present in real waste. Modified brominated-poly(phenylene oxide) cation- and anion-exchange membranes were used to separate the nutrient-laden wastewater and saline draw solution, which induces an electrochemical potential gradient across the ion-exchange membranes and instigates nutrient recovery. A flat-sheet Donnan dialysis system was employed in batch-recycle mode to determine the impact of mixing (e.g., with, without), volumetric flow rate (e.g., 150, 300, 630 mL min-1), and waste-to-draw solution volume ratio (e.g., 1:1, 3:1, 6:1) on nutrient recovery and to calculate diffusion coefficients for nutrients and draw ions. With the optimal operating conditions, nearly 90% orthophosphate recovery was achieved within 48 hours. Increasing the waste-to-draw solution volume ratio from 1:1 to 6:1 boosted orthophosphate flux by 30.2%, highlighting scale-up benefits. These results informed operation of the modular, tube-in-tube Donnan dialysis reactors for nutrient recovery from real animal waste slurries. The recovered nutrients were precipitated as struvite by adjusting the pH to 9 and adding exogenous magnesium. This presentation will highlight the aforementioned advances, which are essential for scale up of Donnan dialysis technologies to recover nutrients from real waste. (continued below in results dissemination section)
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Chen, H.; Souizi, S.; Stewart, K.; Blaney, L. (2023). Application of the Rd/w framework to assess Donnan dialysis performance. Current Opinion in Chemical Engineering 42, 100967. https://doi.org/10.1016/j.coche.2023.100967
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Progress 04/15/22 to 04/14/23
Outputs
Target Audience:The target audiences reached by our efforts during this reporting were mostly undergraduate and graduate students interested in nutrient recovery from agricultural waste, academics from other institutions interested in our efforts on Donnan dialysis processes for nutrient recovery, industry collaborators that currently produce flat-sheet, ion-exchange membranes or hollow-fiber membranes (without ion-exchange capabilities), and other agricultural stakeholders interested in our Donnan dialysis technology. We presented work from this project at several key conferences, including the Fall 2022 LSAMP Research Symposium (College Park, MD), Summer 2022 AEESP Research and Education Conference (St. Louis, MO), and Spring 2022 Undergraduate Research and Creative Achievement Day (Baltimore, MD). Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?Currently, the training and professional development has mostly focused on two postdoctoral research associates, Dr. Hui Chen and Dr. Michael Rose, one PhD student, Ms. Sahar Souizi (women, Environmental Engineering), and three undergraduate researchers, Ms. Kaylyn Stewart (African American woman, Chemistry major), Mr. Fabian Amurrio (Hispanic American man, Chemical Engineering major), and Ms. Zaira Castillo Diaz (Hispanic American woman, Chemical Engineering major). Hui Chen joined in April 2021, and she leads the student team in the laboratory. Michael Rose joined the project in November 2020 and finished his work in May 2022. Sahar Souizi joined the project in Fall 2022 and has quickly gotten up to speed on our protocols and reactors. Kaylyn Stewart and Fabian Amurrio began working with Hui Chen in September 2021, whereas Zaira Castillo Diaz started in June 2022. Fabian Amurrio graduated in December 2022, and Zaira Castillo Diaz wrapped up her work on this project at the same time. The current team consists of Hui Chen, Sahar Souizi, and Kaylyn Stewart. All postdoctoral research associates, graduate students, and undergraduate researchers will be trained in agricultural waste production and chemistry, reactor design, polymer chemistry, membrane production and modification techniques, environmental chemistry, Donnan dialysis, ion exchange, mass transport, and chemical equilibrium modeling. They have also learned about and gained experience using the following analytical and characterization techniques: scanning electron microscopy with energy dispersive x-ray spectroscopy; ion chromatography; inductively coupled plasma mass spectrometry; and, UV-visible absorbance spectrophotometry, which is employed with colorimetric assays for orthophosphate (P(V)) analysis. Postdoctoral research associates meet with the PI each week to discuss progress, obstacles, and related literature, and these meetings often involve professional development discussions about mentoring, leadership, and scientific writing. The PhD and undergraduate researchers meet with the PI on a biweekly schedule, and all student team members meet (without the PI) in the intervening weeks. All team members also join the full 2-h group meeting each week, where they provide updates and presentations on their recent work. This multi-level strategy ensures that all trainees receive feedback from the PI, their teammates, and the rest of the lab group on a regular basis. Dr. Chen led the manuscripts reported above, but the other trainees contributed to specific sections. While the research articles serve as key outcomes of the research, the writing process was also a beneficial exercise for all trainees, leading to important professional development and team-building activities that motivated the team and helped to strengthen their scientific writing skills. How have the results been disseminated to communities of interest?The target audiences reached by our efforts during this reporting were mostly undergraduate and graduate students interested in nutrient recovery from agricultural waste, academics from other institutions interested in our efforts on Donnan dialysis processes for nutrient recovery, industry collaborators that currently produce flat-sheet, ion-exchange membranes or hollow-fiber membranes (without ion-exchange capabilities), and other agricultural stakeholders interested in our Donnan dialysis technology. We presented work from this project at several key conferences, including the Fall 2022 LSAMP Research Symposium (College Park, MD), Summer 2022 AEESP Research and Education Conference (St. Louis, MO), and Spring 2022 Undergraduate Research and Creative Achievement Day (Baltimore, MD). Three of these presentations were given by Ms. Kaylyn Stewart (BS student), and the other was made by Dr. Hui Chen. In addition, we have published two papers from this project in Chemical Engineering Journal (impact factor = 16.7): Chen, H.; Amurrio, F.; Stewart, K.; Shashvatt,U.; Blaney, L. (2023). Sustainable nutrient recovery from synthetic urine by Donnan dialysis with tubular ion-exchange membranes. Chemical Engineering Journal 460, 141625. https://doi.org/10.1016/j.cej.2023.141625 Chen, H.; Rose, M.; Fleming, M.; Souizi, S.; Shashvatt, U.; Blaney, L. (2023). Recent advances in Donnan dialysis technologies for contaminant treatment and resource recovery: a critical review. Chemical Engineering Journal 455, 140522. https://doi.org/10.1016/j.cej.2022.140522 What do you plan to do during the next reporting period to accomplish the goals?In the next reporting period, we plan to complete Objectives 1-2, initiate pilot-scale testing with real agricultural wastes (Objective 3), and submit at least two manuscripts for publication in high-impact journals.
Impacts
What was accomplished under these goals?
Our work to date has focused on Objectives 1-3. Two important outcomes of this work are our recent publications in Chemical Engineering Journal (impact factor = 16.7). One of those papers was a review on Donnan dialysis and its potential application for resource recovery from agricultural wastes. The other paper reported experimental results collected with the tubular Donnan dialysis reactor. The abstracts are provided below for more information: https://doi.org/10.1016/j.cej.2022.140522: Due to its low chemical and energy consumption, Donnan dialysis offers major opportunities to improve contaminant removal and resource recovery from water and wastewater. Conventional Donnan dialysis reactors involve (i) a feed solution that contains a target ion to be removed, (ii) a draw solution with a high concentration of acid, base, or salt, and (iii) an ion-exchange membrane that separates the two solutions. The electrochemical potential gradients of the target and draw ions across the membrane facilitate transport phenomena that can be exploited for contaminant removal or resource recovery. In this critical review, we highlight the need for a consistent framework for the design and interpretation of Donnan dialysis systems using the Rd/w concept, evaluate the impacts of solution properties (e.g., pH, draw ion, competing ions), membrane characteristics (e.g., thickness, ion-exchange capacity, hydration, surface modifications), and system configuration (e.g., membrane surface area, reactor volume, mixing speed, crossflow velocity, integrated processes), and discuss Donnan dialysis applications for treatment and recovery of metals, nutrients, and other inorganic and organic chemicals. In each section, we make recommendations for future studies to both fill knowledge gaps and promote new opportunities. This critical review will serve as an important resource for future Donnan dialysis efforts to address grand challenges related to clean water and circular economies of essential elements. https://doi.org/10.1016/j.cej.2023.141625: To address interconnected issues related to deteriorated water quality and unsustainable fertilizer production, Donnan dialysis was employed for nutrient recovery from model waste solutions and synthetic urine. Conventional Donnan dialysis reactors with flat-sheet, ion-exchange membranes and 500-mL solutions were deployed to determine the impact of the synthetic urine matrix on nutrient recovery relative to model wastes that only contained sodium phosphate (NaH2PO4) or ammonium chloride (NH4Cl). Compared to the model wastes, the competing ions in the synthetic urine caused orthophosphate (P(V)) and ammonium (NH4+) removal to decrease from 90.4% to 55.2% and from 87.8% to 84.8%, respectively. To improve reactor design for future scale up, an innovative Donnan dialysis system was established by placing tubular anion- and cation-exchange membranes into a 30-L waste solution and continuously recirculating 5 L of an NaCl-based draw solution through the inside of the membranes. P(V), NH4+, and other nutrients were simultaneously recovered, and the concentrations in the draw solution exceeded those in the initial synthetic urine in accordance with Donnan equilibrium for unequal solution volumes. Over 75% P(V) and 74% NH4+ were removed from the synthetic urine. MgCl2 and NaOH were added to the nutrient-enriched draw solution to precipitate solids and reset the electrochemical potential gradient, enabling enhanced nutrient recovery. Chemical equilibrium modeling and solids characterization confirmed that the recovered precipitates were ∼73-90% struvite. The proof-of-concept tubular reactor represents a promising strategy for scaling up Donnan dialysis systems for selective nutrient recovery from urine and other wastes. As indicated in last year's report, we decided to focus on development of novel tube-in-tube reactors for the remainder of this project. These reactors provide advantages with respect to scale up and throughput due to their modular design and high ratio of membrane surface area to reactor volume, respectively. So far, we have conducted experiments to determine (i) the impact of the number of membrane modules on the extent and rate of nutrient recovery from the waste solution to confirm benefits associated with the modular design, (ii) the impact of flow rate on the extent and rate of nutrient recovery to determine potential rate limitations from advection and liquid film diffusion, and (iii) the impact of draw solution volume to ensure optimal performance and downstream struvite precipitation. The results have been promising. Dr. Chen will present our recent work at the June 2023 Association of Environmental Engineering and Science Professors meeting (Boston, MA). In addition, Ms. Souizi will present her work with the tube-in-tube reactors at the Fall 2023 American Chemical Society conference (San Francisco, CA). Her abstract is provided below: New strategies are needed to address nutrient pollution through the lens of circular nutrient economies. We propose Donnan dialysis, which is driven by electrochemical potential gradients across ion-exchange membranes, as a sustainable approach to selectively recover nitrogen and phosphorus from waste(water). While conventional, flat-sheet Donnan dialysis reactors are appropriate for evaluating fundamental ion-exchange and transport parameters, these systems cannot be effectively scaled up for real applications or simultaneous recovery of both anionic and cationic nutrients. The objectives of this work were to (1) construct an innovative tube-in-tube Donnan dialysis reactor with high membrane surface area and (2) apply the novel system to enhance the rate and concurrent recovery of anionic and cationic nutrients from model and real wastewaters. In the tube-in-tube reactors, the waste and draw solutions were separated by modified brominated-poly(phenylene oxide) cation- or anion-exchange membranes; the waste solution flowed through the outer tube, and the draw solution was pumped countercurrent in the inner tube. The modular tube-in-tube reactors can be easily scaled up for pilot- and full-scale operations. First, a model waste was used to demonstrate the relative performance of the flat-sheet and tube-in-tube Donnan dialysis systems with respect to the rate and extent of nutrient recovery. Then, nutrient recovery from real animal waste slurries was investigated to record the performance in more challenging matrices. The following parameters were evaluated: flow rate (e.g., 325, 650, 1300 mL/min); draw ion type (e.g., NaCl, HCl); and the number of tube-in-tube modules (e.g., two, four). The flow rate was varied to minimize mass transfer limitations at the solution-membrane interfaces; the draw ion type was changed to investigate diffusion limitations stemming from the draw ion; the number of membrane modules was varied to demonstrate scale-up potential. Baseline removal efficiencies for orthophosphate, ammonium, and potassium in the model waste were 76.5%, 74.8%, and 73.2%, respectively. The recovered nutrients were precipitated as struvite (slow-release fertilizers) by adjusting the solution pH to 9 and adding exogenous magnesium. Overall, the novel tube-in-tube Donnan dialysis reactors were identified as a promising technology for rapid recovery of nutrients from wastewater. Overall, we are in a good position to complete Objectives 1 and 2 in the coming year. For Objective 3, we have constructed a pilot-scale reactor with ten tube-in-tube membrane modules (i.e., five anion-exchange and five cation-exchange systems). As we wrap up the system testing with synthetic waste solutions in the coming months, we will begin testing real agricultural waste and brackish groundwaters.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Chen, H.; Amurrio, F.; Stewart, K.; Shashvatt,U.; Blaney, L. (2023). Sustainable nutrient recovery from synthetic urine by Donnan dialysis with tubular ion-exchange membranes. Chemical Engineering Journal 460, 141625. https://doi.org/10.1016/j.cej.2023.141625
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Chen, H.; Rose, M.; Fleming, M.; Souizi, S.; Shashvatt, U.; Blaney, L. (2023). Recent advances in Donnan dialysis technologies for contaminant treatment and resource recovery: a critical review. Chemical Engineering Journal 455, 140522. https://doi.org/10.1016/j.cej.2022.140522
- Type:
Journal Articles
Status:
Other
Year Published:
2023
Citation:
We have drafted a manuscript tentatively titled, Application of the Rd/w framework to the performance of Donnan dialysis systems for water and wastewater treatment , for submission to Current Opinions in Chemical Engineering (impact factor = 6.1). The authors are Hui Chen, Sahar Souizi, Kaylyn Stewart, and Lee Blaney. This manuscript will be submitted by June 2023.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Stewart, K.; Chen, H.; Amurrio, F.; Blaney, L. Development of novel tube-in-tube Donnan dialysis reactors for simultaneous recovery of anionic and cationic nutrients from synthetic urine. UMBC Undergraduate Research and Creative Achievement Day (Baltimore, MD), April 18-24, 2022.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Chen, H.; Stewart, K.; Amurrio, F.; Shashvatt, U.; Blaney, L. Advances in Donnan dialysis reactor configuration for efficient nutrient recovery. AEESP Research and Education Conference (St. Louis, MO), June 30, 2022.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Stewart, K.; Chen, H.; Amurrio, F.; Blaney, L. Advances in Donnan dialysis reactor configuration for efficient nutrient recovery. Fall 2022 LSAMP Research Symposium (College Park, MD), December 3, 2022.
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2023
Citation:
Chen, H.; Souizi, S.; Stewart, K.; Amurrio, F.; Blaney, L. Development of novel tube-in-tube Donnan dialysis reactors for sustainable and efficient nutrient recovery. AEESP Research and Education Conference (Boston, MA), June 20-23, 2023.
- Type:
Conference Papers and Presentations
Status:
Accepted
Year Published:
2023
Citation:
Souizi, S.; Chen, H.; Stewart, K.; Blaney, L. Sustainable nutrient recovery with novel tube-in-tube Donnan dialysis reactors. Fall 2023 ACS National Meeting (San Francisco, CA), August 13-17, 2023.
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Progress 04/15/21 to 04/14/22
Outputs
Target Audience:The target audiences reached by our efforts during this reporting were mostly undergraduate and graduate students interested in nutrient recovery from agricultural waste, academics from other institutions interested in our efforts on Donnan dialysis processes for nutrient recovery, industry collaborators that currently produce flat-sheet, ion-exchange membranes or hollow-fiber membranes (without ion-exchange capabilities), and other agricultural stakeholders interested in our Donnan dialysis technology. We presented work from this project at several key conferences, including the 2022 INFEWS PI Workshop (Princeton, NJ), the Spring 2022 ACS National Meeting (San Diego, CA), and the AEESP Research and Education Conference (St. Louis, MO). Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?Currently, the training and professional development has mostly focused on two postdoctoral research associates, Dr. Hui Chen and Dr. Michael Rose, and three undergraduate researchers, Ms. Kaylyn Stewart (African American woman, Chemistry major), Mr. Fabian Amurrio (Hispanic American man, Chemical Engineering major), and Ms. Zaira Castillo Diaz (Hispanic American woman, Chemical Engineering major). Hui Chen joined in April 2021, and she leads the student team in the laboratory. Michael Rose joined the project in November 2020 and finished his work in May 2022. Kaylyn Stewart and Fabian Amurrio began working with Hui Chen in September 2021, whereas Zaira Castillo Diaz started in June 2022. We have also recruited a female PhD student, Sahar Souizi, who planned to join this project in Fall 2021, but she ran into visa delays and will now start in Fall 2022 (she has already arrived to UMBC). All postdoctoral research associates, graduate students, and undergraduate researchers will be trained in agricultural waste production and chemistry, polymer chemistry, membrane production and modification techniques, environmental chemistry, and chemical equilibrium modeling. They have also learned about and gained experience using the following analytical and characterization techniques: scanning electron microscopy with energy dispersive x-ray spectroscopy; ion chromatography; inductively coupled plasma mass spectrometry; and, UV-visible absorbance spectrophotometry, which is employed with colorimetric assays for orthophosphate (P(V)) analysis. Postdoctoral research associates meet with the PI each week to discuss progress, obstacles, and related literature, and these meetings often involve professional development discussions about mentoring, leadership, and scientific writing. The incoming PhD and current undergraduate researchers meet with the PI on a biweekly schedule, and all student team members meet (without the PI) in the intervening weeks. All team members also join the full 2-h group meeting each week, where they provide updates and presentations on their recent work. This multi-level strategy ensures that all trainees receive feedback from the PI, their teammates, and the rest of the lab group on a regular basis. Dr. Chen also led the drafting of a review manuscript on "Recent advances in Donnan dialysis technologies for contaminant treatment and resource recovery". Several of the other trainees contributed to this critical review, which provides an excellent discourse on Donnan dialysis systems and bolsters the need for resource recovery from agricultural waste. This manuscript will serve as a key training and reference document for the duration of this project, and we expect that it will be highly cited. Importantly, it served as a strong team-building activity for trainees on this project. How have the results been disseminated to communities of interest?The target audiences reached by our efforts during this reporting were mostly undergraduate and graduate students interested in nutrient recovery from agricultural waste, academics from other institutions interested in our efforts on Donnan dialysis processes for nutrient recovery, industry collaborators that currently produce flat-sheet, ion-exchange membranes or hollow-fiber membranes (without ion-exchange capabilities), and other agricultural stakeholders interested in our Donnan dialysis technology. We presented work from this project at several key conferences, including the 2022 INFEWS PI Workshop (Princeton, NJ), the Spring 2022 ACS National Meeting (San Diego, CA), and the AEESP Research and Education Conference (St. Louis, MO). Specific references for presentations and planned article submissions are available in the Products section. What do you plan to do during the next reporting period to accomplish the goals?In the next reporting period, we plan to complete Objectives 1 and 2 and submit three manuscripts for publication in high-impact journals.
Impacts
What was accomplished under these goals?
Our work to date has mostly focused on Objectives 1 and 2, which involve the fabrication and deployment of ion-exchange membranes in novel Donnan dialysis reactors for recovery of cationic (e.g., ammonium (NH4+), potassium (K+)) and anionic (e.g., orthophosphate (P(V))) nutrients. We decided to pivot away from the hollow-fiber, ion exchange membranes listed in Objective 1 due to their poor physical properties. In particular, the hollow-fiber, ion-exchange membranes produced in collaboration with our colleague, Dr. Chengpeng Chen, from the Chemistry Department at UMBC were brittle and not uniform. The membranes were not suitable for deployment in nutrient recovery systems, and so we decided to take an alternative approach that would improve the overall performance and opportunity for translation to agricultural operations. We ran a number of experiments to identify the performance and advantages of conventional flat-sheet, commercial tubular, and novel tube-in-tube configurations, which employ the same fundamental advantages as hollow fibers, in Donnan dialysis processes for nutrient recovery. The flat-sheet configuration involves a waste solution separated from a draw solution by a flat-sheet, ion-exchange membrane, whereas the tubular reactor consisted of commercial, tubular ion-exchange membranes placed into a rectangular tank filled with the waste solution. Using data from the flat-sheet and tubular reactor configurations, postdoctoral research associate, Dr. Hui Chen, has prepared one manuscript (for submission in 4-6 weeks) that shows how Donnan dialysis systems can achieve approximately 90% removal of nutrients from challenging wastes and 75% recovery of nutrients into simple draw solutions; note, the difference in the removal and recovery efficiencies stemmed from nutrient retention in the membranes during batch-mode operation. This work provided important information about nutrient diffusion coefficients in the membranes, mass transport limitations in the tubular reactor, and the effects of competing ions on nutrient recovery. Compared to the flat-sheet reactor configuration, the rate of recovery decreased by a factor of 9.1, 5.7, and 7.3 for NH4+, K+, and P(V), respectively, in the tubular reactor. This outcome stemmed from the lower membrane surface area-to-reactor volume in the tubular Donnan dialysis system. Nevertheless, we were able to show the potential for continuous nutrient recovery in the tubular reactor, along with periodic precipitation of struvite minerals in the draw solution (during operation). The nutrient concentration profiles, chemical equilibrium modeling, and solids characterization results were all in agreement with each other, reinforcing our general approach. Based on these findings, we designed and fabricated the aforementioned tube-in-tube reactors, which exhibit much higher surface area-to-volume ratios. Over this past year, Hui Chen has been working with three undergraduate research assistants to design, fabricate, and test the performance of tube-in-tube reactors that contain the optimal anion- and cation-exchange membranes identified in Year 1. These reactors involve an inner tube, through which we circulate the salt-laden draw solution (e.g., brackish groundwater), and an outer tube, through which we pump the waste solution (e.g., animal agriculture wastewater enriched with nutrients). The reactors are modular and can be connected in series or parallel, depending on the treatment needs. We fabricated the tube-in-tube modules by wrapping a flat-sheet, ion-exchange membrane around a polymeric mesh support (with minimal contact area). The inner tube is set within the outer tube, but each tube has separate inlet and outlet ports; therefore, the waste solution is never in direct contact with the draw solution, and nutrients can only be exchanged across the membranes. Our new approach with the tube-in-tube reactors has been enabled by the promising performance of the modified brominated poly(2,6-dimethyl-1,4-phenylene oxide) membranes mentioned in our Year 1 report. These membranes exhibited fast nutrient diffusion and provided high nutrient recovery in reasonable times. Within 10 h of batch-mode operation, we were able to achieve Donnan equilibrium, which allowed approximately 90% recovery of cationic and anionic nutrients for our operating conditions. We believe that these performance outcomes will be suitable for nutrient recovery from swine manure using brackish groundwater draw solutions. To date, we have mainly tested the tube-in-tube reactors with synthetic waste solutions for proof-of-concept and optimization studies. Three important advantages of the tube-in-tube reactors are as follows: (1) the ratio of membrane surface area to reactor volume was increased, resulting in faster mass transport; (2) the high crossflow velocity at the membrane interface with the inner and outer solutions reduced mass transfer resistance from the liquid film layers and facilitated faster nutrient recovery; and, (3) a lower volume of draw solution can be used to facilitate higher nutrient concentrations than the initial waste solution and, thereby, enhancing precipitation of struvite-based fertilizers. Dr. Chen has started to prepare a manuscript with the corresponding data, and we expect to submit this manuscript in 2023. Overall, we are in a good position to complete Objectives 1 and 2 in the coming year.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Shashvatt, U.; Chen, H.; Amurrio, F.; Stewart, K.; Raphael, M.; Boby, A.; Portner, C.; Blaney, L. Development of sustainable Nutrient Extraction and Recovery Devices (NERDs) for municipal and agricultural wastewater. 2022 INFEWS PI Workshop (Princeton, NJ), February 9-11, 2022.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Chen, H.; Stewart, K.; Amurrio, F.; Shashvatt, U.; Blaney, L. Advances in Donnan dialysis reactor configuration for efficient nutrient recovery. Spring 2022 ACS National Meeting (San Diego, CA), March 20-24, 2022.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Shashvatt, U.; Chen, H.; Amurrio, F.; Stewart, K.; Portner, C.; Blaney, L. Phosphorus recovery by Donnan dialysis: Membrane selectivity, diffusion coefficients, and speciation effects. Spring 2022 ACS National Meeting (San Diego, CA), March 20-24, 2022.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Stewart, K.; Chen, H.; Amurrio, F.; Blaney, L. Development of novel tube-in-tube Donnan dialysis reactors for simultaneous recovery of anionic and cationic nutrients from synthetic urine. UMBC Undergraduate Research and Creative Achievement Day (Baltimore, MD), April 18-24, 2022.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2022
Citation:
Chen, H.; Stewart, K.; Amurrio, F.; Shashvatt, U.; Blaney, L. Advances in Donnan dialysis reactor configuration for efficient nutrient recovery. AEESP Research and Education Conference (St. Louis, MO), June 30, 2022.
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Progress 04/15/20 to 04/14/21
Outputs
Target Audience:The target audiences reached by our efforts during this reporting were mostly undergraduate students interested in nutrient recovery from agricultural waste, potential industry collaborators that currently produce flat-sheet, ion-exchange membranes or hollow-fiber membranes (without ion-exchange capabilities), and other agricultural stakeholders interested in our Donnan dialysis technology. The COVID-19 pandemic inhibited much of our progress due to lab closures and personnel restrictions, but we have been able to make good connections to (1) recruit undergraduate students to this project, (2) get free products from potential industry collaborators to be tested during the project, and (3) establish additional connections for testing in later stages of the project. Changes/Problems:The COVID-19 pandemic affected our start to the project due to laboratory closures and restrictions; however, we are now making good progress on the Objective 1 and 2 tasks. I feel confident that we will be able to make up some time in the next reporting period. What opportunities for training and professional development has the project provided?Currently, the training and professional development has mostly focused on two postdoctoral research associates, Hui Chen and Michael Rose. Michael Rose joined the project in November 2020, and Hui Chen joined in April 2021. Since then, they have dived into the project and made good progress on the tasks described in the previous section. We have also recruited a female PhD student, Sahar Souizi, who plans to join this project in Fall 2021 (pending visa approval). Through several outreach activities, we have received numerous applications from undergraduate researchers interested in this project. After interviews with me and Hui Chen, we have decided to hire Kaylyn Stewart, who is a female African American student in the UMBC Chemistry program. She will begin working with Hui Chen in Fall 2021. All postdoctoral research associates and students will be trained in agricultural waste production and chemistry, polymer chemistry, membrane production and modification techniques, environmental chemistry, chemical equilibrium modeling, and a variety of analytical and characterization techniques. Postdoctoral research associates meet with the PI each week to discuss progress, obstacles, and related literature, and these meetings often involve professional development discussions about mentoring, leadership, and scientific writing. The incoming PhD and undergraduate students will begin biweekly meetings with the PI this fall, and all student team members will meet (without the PI) in the intervening weeks. All team members will also join the full group meeting each week. This multi-level strategy ensures that all trainees receive feedback from the PI, their teammates, and the rest of the lab group on a regular basis. How have the results been disseminated to communities of interest?Given the slow start due to the COVID-19 pandemic, we have not yet disseminated our findings to communities of interest through formal publications or presentations. Building upon the literature review involved with the original proposal and project startup, we are currently working on a review article about Donnan dialysis applications for resource recovery, and I plan to submit that manuscript by early 2022. We are also outlining a publication based on the enhanced performance of the modified BPPO membranes compared to previously reported commercial membranes, but we have not yet set a timeline for submission. I expect that we will give at least two presentations at the Spring 2022 meeting of the American Chemical Society. In addition, I spoke about this project to a number of student groups in Spring 2021 and have planned seminars/lectures for Fall 2021. What do you plan to do during the next reporting period to accomplish the goals?In the next reporting period, we plan to continue working on the Objective 1 and 2 tasks associated with membrane production and evaluation. The team is making good progress right now, and the addition of Sahar Souizi (PhD student) and Kaylyn Stewart (undergraduate student) this fall will enable us to further speed up progress and make up for some of the delays incurred from the COVId-19 pandemic.
Impacts
What was accomplished under these goals?
Our work to date has mostly focused on Objective 1, which involves the generation of novel, hollow-fiber, ion-exchange membranes; however, we have performed some Objective 2 tasks to evaluate the performance of the membranes and inform the membrane chemistries explored under Objective 1. As indicated in the 'Other Products' section, the start of the project was delayed by the COVID-19 pandemic and its effects on laboratory access and capacity restrictions. Regardless of the delay, we have made good progress on developing our capacity to produce hollow-fiber membranes and vet the optimal membrane chemistry. In the first area, we conducted an extensive literature review of techniques for (1) direct production of hollow-fiber membranes with ion-exchange capabilities and (2) modification of conventional hollow-fiber membranes to include ion-exchange sites. These techniques differ in both chemistry and production potential. We are exploring both options to ensure that we have the best strategy in place for future production. In particular, we are using an electrospinning apparatus in the UMBC Chemistry Department with a specialized nozzle to produce hollow-fiber membranes from monomer mixtures that contain positively-charged (e.g., R4N+) and negatively-charged (e.g., RSO3-) species that will serve as the anion- and cation-exchange sites, respectively. To date, we have focused on production of solid fibers to gain experience with the electrospinning apparatus, but we are moving forward with modifications to ensure generation of robust hollow-fiber, ion-exchange membranes. Alternatively, we have secured a partnership with a commercial producer of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) hollow-fiber membranes. Those membranes are not enabled for ion exchange. The partner has committed to sending us membrane bundles for research purposes. We have developed a scheme to modify these membranes with ion-exchange groups for use in Donnan dialysis operations. In the second area, we have performed experiments to measure the ion-exchange capacity and diffusion coefficients of key nutrients through anion-exchange modified BPPO flat-sheet membranes. This work was meant to confirm the performance of the novel ion-exchange membrane chemistries proposed in the project for phosphate recovery from agricultural waste. As indicated in the 'Other Products' section, the results from these experiments have been very encouraging. In particular, we have achieved almost 30x faster recovery of phosphate from synthetic waste solutions compared to the commercial membranes used in our previous work. These results have major implications for real-world applications that require high throughput to be effective on the farm scale. Based on these findings, we are excited about the synergy between the faster diffusivity and higher surface area-to-volume ratio of the planned hollow-fiber membranes.
Publications
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