EFFICIENT NANOTECHNOLOGY METHODS TO REMOVE CONTAMINANTS FOR IMPROVING WATER QUALITY

• Sponsoring Institution: National Institute of Food and Agriculture
• Project Status: COMPLETE
• Funding Source: OTHER GRANTS
• Reporting Frequency: Annual
• Accession No.: 1018115
• Grant No.: 2019-38821-29050
• Cumulative Award Amt.: $499,675.00
• Proposal No.: 2018-04958
• Project Start Date: Mar 1, 2019
• Project End Date: Feb 29, 2024
• Grant Year: 2019
• Program Code: [EQ]- Research Project

Recipient Organization
LINCOLN UNIVERSITY
820 CHESTNUT ST
JEFFERSON CITY,MO 651023537

Performing Department
(N/A)

Non Technical Summary
Groundwater and surface water quality are critical areas of research for many reasons, but primarily because these water sources are the basis for all drinking water supplies and irrigation in the US.Drinking contaminated water can have serious health effects on humans.Diseases such as cholera, hepatitis, and dysentery may be caused by contamination from human and animal waste. The quality of groundwater and surface water is directly impacted by natural and human-made contaminants. Controlling the exposure of surface and groundwater to these contaminants, should improve water quality. According to water quality reports, the major sources of ground and surface water contamination in the US, and especially in Missouri, are from modern agricultural activities and concentrated animal feeding operations (CAFOs). The Clean Water Act defines CAFOs as point sources of pollution that are required to obtain permits to discharge into rivers or other drinking sources. All other agricultural sources are considered nonpoint and are not regulated under federal law.Numerous studies over the past decades have documented the fact that runoff from intensively managed CAFOs include extremely high levels of natural organic matter (NOM), nutrients (primarily nitrogen and phosphorus), pathogens, hormones, antibiotics, synthetic organic chemicals (used as cleaning agents, algaecides, etc.), disinfectants (used on the animals and in their pens), and other miscellaneous chemicals, such as copper sulfate (used in footbaths for cows). Despite current Best Management Practices (BMPs), the contaminants from agriculture activities and CAFOs continue to find their way into impoundments and streams as runoff pollution and contaminate drinking water sources. Conventional processes include direct filtration, coagulation-based treatment, membrane-based systems, and absorption based systems.However, these methods resulted in only limited success. Regulators, environmentalists, and the agriculture and animal farm industries should all look to science and engineering to explore possible solutions to this critical problem affecting human life and water quality. Further advances in the removal of organic contaminants from water runoff sources will require the development of novel approaches and modalities for effective removal and purification. As a possible solution our hypothesis is that magnetic iron oxide nanoparticles coated with coagulants (herein referred to as magnetic nanosponges, MNSs) due to their inherent high-surface area with active absorption capabilities will effectively remove organic contaminants (NOM and SOCs) efficiently and cost-effectively from the water before entry into critical waterways.

Animal Health Component

60%

Research Effort Categories

Basic

20%

Applied

60%

Developmental

20%

Classification

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
111	0210	2000	80%
601	0210	2000	20%

Knowledge Area
601 - Economics of Agricultural Production and Farm Management; 111 - Conservation and Efficient Use of Water;

Subject Of Investigation
0210 - Water resources;

Field Of Science
2000 - Chemistry;

Keywords

cafo

nanotechnology

water quality

Goals / Objectives
The mainobjective of the proposed research is to develop an innovative nanotechnology-based technique to remove organic contaminants, such as natural organic matterNOM and synthetic organic chemicalsSOCs, at point sources, develop a protocol for best management practices (BMPs), and thereby improve surface and groundwater quality.Specific Aim 1: Design and synthesize a library of magnetic nanosponges (MNSs).1a: Choice of coagulants1b: Synthesis and characterization of MNSs1c: Stability testing1d: Sorption kinetics1e: Specificity and selectivity of sponges1f: Interference of other ions/compoundsSpecific Aim 2: Investigate the efficacy of magnetic sponges in the removal of organiccontaminants from water samples.2a: Optimal amount of MNSs in removing natural organic matter (NOM)2b: Optimal amount of MNSs in removing synthetic organic chemicals (SOCs)2c: Determination of the optimal amount of MNSs required to remove the NOM and SOCmixture2d: Evaluation of water qualitySpecific Aim 3: Pilot test and develop protocols for BMPs using MNSs.3a: Pilot testing3b: Development of standard operating protocols for field setting

Project Methods
Traditionally, polymer and aluminum-based coagulants have been used to remove contaminants in drinking water and wastewater treatment plants by a coagulation sedimentation process. The effectiveness of the process can be improved by introducing magnetic nanoparticles coated with coagulants that will enhance the absorption capacity,allowing quicker floc formation and settling using a magnet. We have already demonstrated the feasibility of Magnetic Nano-Sponge (MNS) synthesis with a representative National Sanitation Foundation (NSF)-approved coagulant. The efficiency of MNSs in contaminant removal has been demonstrated by analyzing TOC and performing turbidity measurements on treated water. To improve the efficacy and use this method for real-time applications for integration with current BMPs requires further study. Towards this objective, we will fabricate MNSs using iron oxide magnetic nanoparticles coated with coagulants, evaluate their efficacy in removing a spectrum of NOM and SOCs, and establish standard protocols for integrating this new process with current BMPs.

Progress 03/01/23 to 02/29/24

Outputs
Target Audience:Scientific community in the fields of Agriculture, Animal Sciences, Environmental Sciences, and Chemistry including both students and educators at the national and international level Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?As Acheived in the previous years of this project: -Undergraduate and Graduate students' engagement in the project, and their professional training with supervision of scientists involved in this project were continued. -The involved scientists' expertise in the field further improved during the process of experimental design and analysis of the results at every step of the project. -During the publication and peer-review process, every experimental step and presented data were evaluated by scientists in the field and exchange of comments and learning different view points were great addition to the professional developent of the research team How have the results been disseminated to communities of interest?American Chemical Society is an international conference and our presentation was very well received by the scientific community who are currently working in the field of wastewater purification. In addition our recent published papers in the internationally well recognized journals of Processes and Applied Sciencesdisseminated our research results very effectively among the scientific community. What do you plan to do during the next reporting period to accomplish the goals?This is the final year of this project. However we are continuing our research in this field and building up on the valuable results we collected during this project period. We submitted new USDA grants in 2023 based on our findings.

Impacts
What was accomplished under these goals? Data collection and analysis of results were completed on evaluating the efficiency of magnetic nanosponges in removing pollutants in wastewater collected from local BeefCAFO lagoons. Result will be published. New methods were designed and preliminary testing was completed for detection of other wastewater contaminants such as microplastics and heavy metals. These data will serve as basic information for future USDA grants.

Publications

• Type: Journal Articles Status: Published Year Published: 2023 Citation: Gangula, A.; Chhetri, T.; Atty, M.; Shanks, B.; Kannan, R.; Upendran, A.; Afrasiabi, Z. Unaccounted Microplastics in the Outlet of Wastewater Treatment PlantsChallenges and Opportunities. Processes 2023, 11, 810. https://doi.org/10.3390/pr11030810
• Type: Journal Articles Status: Published Year Published: 2023 Citation: Lindenmayer, R.; Lu, L.; Eivazi, F.; Afrasiabi, Z. Atomic Spectroscopy-Based Analysis of Heavy Metals in Sea Algae Species. Appl. Sci. 2023, 13, 4764. https://doi.org/10.3390/app13084764
• Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: Fall 2023 National Meeting & Expo, American Chemical Society in San Francisco, ENVR 3929045 : Detecting unaccounted microplastics in the environment | Poster Board #835

Progress 03/01/19 to 02/13/24

Outputs
Target Audience:Scientific community in the fields of Agriculture, Animal Sciences, Environmental Sciences, and Chemistry including both students and educators at the national and international level Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?During the project period: -Undergraduate and Graduate students were engaged in the various steps of the project including literature survay, experimental design, labworks, fieldworks, data analysis, instrumentation, publication, presentation of the results' engagement, and future plans brainstorming! -Every step of the project was a professional growth for the involved scientists' expertise in the field. New ideas were immerged by the end of project period, which will serve as a foundation for the future USDA projects. -During the publication and peer-review process, every experimental step and presented data were evaluated by scientists in the field and exchange of comments and learning different view points were great addition to the professional developent of the research team How have the results been disseminated to communities of interest?Through peer reviewed publications in the prestigous internation journals, Presentation at local andnational conferences for both national and international researchers, andlocal farmers and CAFO facility staff. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? All the proposed specific aims for the project were accomplished. The details are provided in each progress reports.

Publications

Progress 03/01/22 to 02/28/23

Outputs
Target Audience:Scientific community in the fields of Agriculture, Animal Sciences, Environmental Sciences, and Chemistry including both students and educators at the national and international level Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? During the ongoingpublication and peer-review process, every presented data has beenevaluated by scientists in the field and exchange of comments and learning different view points have been greatly impacted theprofessional growth of the research team. Graduate student's engagement in the project, and their professional training with supervision of scientists involved in this project were continued. The involved scientists' expertise in the field further improved during the process of experimental design and analysis of the results at every step of the project. How have the results been disseminated to communities of interest? In addition to our regular research meetings we are in the process of preparing other manuscripts to shar with scientific community. What do you plan to do during the next reporting period to accomplish the goals? Analyze collected data from the beef CAFO Complete and publish our data Presend our collected data at national meetings Evaluate methodologies for detection and removal ofpollutants such as microplastics and heavy metals from wastewater.

Impacts
What was accomplished under these goals? We evaluated the water quality improvement with the use of magnetic nanosponges (MNSs) in removing impurities from the wastewater lagoons collected from beef farm CAFO facility located at the University of Missouri. We measured the turbidity, total organic content (TOC), biological oxygen demand (BOD), and total suspended solids (TSS) of the collected samples. Flocculation experiments were performed. We added varying concentrations of coagulants to water samples collected from the beef CAFO lagoon and determined the optimal concentration of coagulant that can form and hold the flocs. Purification efficiencies were determined. The optimal concentration of coagulants and MNPs were mixed at different ratios in Pilot water purification system. Purified water samples were collected at several time points and analyzed for turbidity, TOC, BOD, TSS post treatment. We have been evaluating specific methodologies to purify wastewater targeting pollutants such as microplastics and heavy metals.

Publications

Progress 03/01/21 to 02/28/22

Outputs
Target Audience:-Scientific community in the fields of Agriculture, Animal Sciences, Environmental Sciences, and Chemistry including both students and educators at the national and international level Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?-Graduate students' engagement in the project, and their professional training with supervision of scientists involved in this project were continued. -The involved scientists' expertise in the field further improved during the process of experimental design and analysis of the results at every step of the project. -During the publication and peer-review process, every experimental step and presented data were evaluated by scientists in the field and exchange of comments and learning different view points were great addition to the professional developent of the research team How have the results been disseminated to communities of interest?Our recent published paper in the internationally well recognized journal of "Water" disseminated our research results very effectively among the scientific community. What do you plan to do during the next reporting period to accomplish the goals?Our limited access to the Beef CAFO (Due to COVID) delayed our data collection. We will coninue our data collection and analysis on wastewater collected from BEEF CAFO.

Impacts
What was accomplished under these goals? Data collection and analysis of results were completed on evaluating the efficiency of magnetic nanosponges inremoving pollutants in wastewater collected from local diary and swine CAFO lagoons. Result was published in a peer reviewed journal.

Publications

• Type: Journal Articles Status: Published Year Published: 2022 Citation: Citation: Chhetri, T.; Cunningham, G.; Suresh, D.; Shanks, B.; Kannan, R.; Upendran, A.; Afrasiabi, Z. Wastewater Treatment Using Novel Magnetic Nanosponges. Water 2022, 14, 505. https://doi.org/10.3390/w14030505

Progress 03/01/20 to 02/28/21

Outputs
Target Audience:-Scientific community in the fields of Agriculture, Animal Sciences, Environmental Sciences, and Chemistry including both students and educators at the national and international level Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?-Graduate students' engagement in the project, and their professional training with supervision of scientists involved in this project were continued. -The involved scientists' expertise in the field further improved during the process of experimental design and analysis of the results at every step of the project. How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals? --Synthesis and evaluation of other types of MNS to improve the water quality levels for consumer consumption by EPA. --Integrate the purification process into Best management procedure and utilize in waste water treatment plants.

Impacts
What was accomplished under these goals? --Several experiments were conducted with varying concentrations of coagulants. The optimal concentrations of coagulants that can form and held the flocs for different lagoon wastewaters were determined. --Optimal ratio of magnetic nanoparticles to coagulants in the nanosponges were determined for the best purification result. --Weutilizedtwodifferentmagnetic nanoparticles, (commercial and in-house prepared) along with conventional coagulants (polymer and aluminum) totreat CAFO wastewater collected in lagoons andmonitored the water quality parameters.Weevaluatedthe waterquality improvement withtheuseof magnetic nanosponges inremoving impurities from the waste water lagoons collected from our dairy and swine farm CAFO facilities locatedinUniversityof Missouri. The well-established four different parameters of water quality viz., turbidity, total organic carboncontent(TOC),biologicaloxygendemand(BOD) andtotal suspendedsolids(TSS)weredeterminedpre-andpost-treatmentofthewastewaters from both lagoons.

Publications

Progress 03/01/19 to 02/29/20

Outputs
Target Audience:-Scientific community in the fields of Agriculture, Animal Sciences, Environmental Sciences, and Chemistry including both students and educators at the national and international level -Farming community Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?-Two graduate students were effectively engagedin all steps of the project andrecieved professional training with supervision of scientists involved in this project including lab work and field work. -The involved scientists' expertise in the field further improvedduring the process of experimental design and analysis of the results at every step of the project. How have the results been disseminated to communities of interest?Results were presented in Environmental Chemistry section of 2019 American Chemical Socity meeting and very well recieved by the stuednts and scientists in the field. Productive discussions took place during the meeting and visitors of related fields found the projectvery helpful,interesting, and applicable. What do you plan to do during the next reporting period to accomplish the goals?Future studies include: Evaluation ofother parameters such as biological oxygen demand and total suspended solids on the purified water. Synthesis and evaluation of other types of MNS to improve the water quality levels for consumer consumption by EPA. Integrate the purification process into Best management procedure and utilize in waste water treatment plants.

Impacts
What was accomplished under these goals? Hypothesis: We hypothesized that magnetic iron oxide nanoparticles along with coagulants (herein referred to as magnetic nanosponges, MNSs), due to their inherent high-surface area with active absorption capabilities, will effectively remove NOM and SOCs efficiently with economically from the water. Method: As a first step, we synthesized MNS and mixed with commercial coagulants for our investigation. The sponges were characterized using conventional analytical techniques. Second, to evaluate the efficiency of MNSs for purification of water, we used turbidity, total organic content, biological oxygen demand, and total suspended solids as parameters. These parameters have been continuously used as indicators for establishing the final water quality for consumer consumption by EPA. We evaluated the efficacy of MNSs in two types of CAFO facilities (i) DIARY FARM (II) SWINE Farm. The results from the present study are presented. Our results show that the coagulation process has been enhanced by using magnetic materials that can improve formation of flocs quickly and efficiently with the ability to completely settle in the sedimentation tanks. Choice of Coagulants Different lagoon water has different levels of turbidity and contaminants present in them. The optimal amount of pure coagulant required to form a floc and removal of contaminants with no residual amounts have to be determined. Two polymer based (Zetag 8814 and Zetag 8816, both from BASF) and three aluminum based coagulants were tested. A "TOSS TEST" was performed to compare the ease of "floc formation". The polymer based coagulants formed floc ata faster rate compared to aluminum based and therefore chosen to use form MNS. Purification Of Water By Jar Testing Procedure An in-house water jar tester that simulates water purification in a waste water treatment plant has been designed for water treatment using MNS. The coagulants were mixed with magnetic nanoparticles in different ratios to form MNS, added to water collected from different lagoons, stirred and contaminants were allowed to settle down using a magnet. The sedimentation time was varied and water was collected. The turbidity and TOC values of water were compared pre and post treatment with MNS.

Publications

• Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Presented at Fall 2019 National Meeting & Expo, American Chemical Society in San Diego, ENVR 415: Improvement of water quality based on nanotechnology methods