Progress 05/15/23 to 05/14/24
Outputs
Target Audience:We have received a Provisional Patent for the technology we developed. We are in touch with two major fertilizer manufacturing companies and they are Nano-Yield and The Mosaic Company Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? Two graduate students, three undergraduate students, and one postdoctoral researcher worked on different aspects of this project. They designed experiments and conducted them under the supervision of the PI and Co-PIs. The data obtained were analyzed by the students. The students were trained in research methods and data analysis/interpretation. Graduate students, PI, and Co-PIs attended several conferences where they shared the findings, gained feedback, and networked with experts in the field, fostering collaboration and advancing knowledge. How have the results been disseminated to communities of interest?Some of the findings from the project were presented at the following conferences by the PD, Co-PDs, Graduate Students, Post-doctoral Fellow, and Undergraduate Researchers: SNO Conference 2023: Presentation/Talk by Davidson E., Pestereva A., and Santra S. on 'Effects of sulfur nanoparticles incorporation in a biopolymeric coating of phosphorus fertilizers' at Marina del Rey, CA during November 10 - 12, 2023. ACS Fall Meeting 2023: Presentation/Talk by Davidson E., Pestereva A., and Santra S. on 'Chitosan gel embedded with Nano S as a coating film for Phosphorus fertilizers to enhance use efficiency' at Moscone Center, San Francisco, CA during August 13 - 17, 2023 SNO Conference 2023: Presentation/Talk and Poster by Mazumdar S., Quadir M., and Bezbaruah A. on 'Nano-based modification of Phosphorous platforms for sustainable delivery of Phosphate' at Marina del Rey, CA during November 10 - 12, 2023. 11th annual Midwest Geobiology Symposium: Poster by Mazumdar S., Quadir M., and Bezbaruah A. on 'Nano-based modification of Phosphorous platforms for improving Phosphorous use efficiency' at University of Minnesota, MN during September 22 - 23, 2023. Student Research Day 2024: Presentation/Talk by Mazumdar S., Quadir M., and Bezbaruah A. on 'The Promise of Nano-Modified Phosphate Fertilizers for Sustainable Agriculture' at North Dakota State University, ND during April 9-10, 2024 What do you plan to do during the next reporting period to accomplish the goals?Our future work will include focusing on the evaluation of the P release pattern in soils treated with coated and uncoated RP fertilizers followed by run-off studies to evaluate the impact of coating and particle size on P transport in soil. Evaluation of the coatings on P bioavailability and plant performance in soil-plant systems is another important area for our immediate future studies. We also plan to investigate the phytotoxicity of the developed products under hydroponic conditions. Subsequently, we plan to apply the same coatings to hydroxyapatite and other commercial P fertilizers to gain a better understanding of the P release patterns. The results will be disseminated through conferences/meetings/seminars and peer-reviewed journal paper publications.
Impacts
What was accomplished under these goals?
Goal: Development of coating for P-fertilizers (Rock Phosphate, RP) Objective: Develop and characterize coated granular and nano P fertilizer Task 1. Prepare and characterize coated granular P fertilizer:CS-TAN (chitosan-citric acid gel combined with tannic acid) and CS-NanoS (chitosan-citric acid-tannic acid in combination with sulfur nanoparticles) were synthesized in a one-step process and characterized in Year 1. Following this, topological analysis of the coated fertilizer was performed and that confirmed that no significant difference exists between the surface roughness (Sa) of the RP uncoated and coated with (CS, CS-NanoS, CS-TAN, and CS-TAN-NanoS) with values ranging from 110 to 150 Sa. The coating hardness was determined using AFM. Due to the submicron thickness of the coatings, there was no significant difference in coatings hardness. The Nano IR studies provided evidence of the bands from 1660 to 1760 cm-1 corresponding to C=O, N-H, and O=C-O functional groups which corroborated the effective coverage of chitosan and tannic acid on the RP surface. Task 2. Prepare and characterize coated nano P fertilizer: Commercially available RP was milled to get 118.88 ± 33.72 nm size nano RP particles. Chitosan and Poly(citric) acid (PCA) (synthesized in Year 1) was coated Layer-by-layer (LbL) on the nano RP particles, and the layers were repeated alternately. The FTIR spectra displayed characteristic peaks, confirming the successful deposition of the coatings. In RP-CH, the protonation of CH amine functionalities was suggested by the presence of the band, attributed to NH3+ groups (1386 cm−1). This was conditioned by the formation of electrostatic bonds with RP. Moreover, a low-frequency shift of the amide in CH (1661 cm−1) in RP-CHindicates the participation of the carbonyl groups of the CH amide groups in hydrogen bonding. The peak of 1582 cm− 1 moved to a low-frequency region (1560 cm− 1) for RP-CH-PCA. This result indicates the NH2 in RP-CH has been protonated to NH3+. Consequently, it is confirmed that ionic interactions exist in RP-CH-PCA. Overall, we demonstrated that L-b-L coating technique (using immersive assembly) to coat nano rock phosphate (RP) fertilizers works effectively. Task 3. Phosphate leaching rate: We performed a solution study to determine the P leaching rate. In solution, the available phosphorus release was evaluated for up to 6 days with a maximum phosphorusrelease of 10 µM for RP, and the CS-coated RP released 33 µM and CS-TAN-coated ones released 53 µM. These results showcased that enhancement in phosphate release after coating RP with CS and CS-TAN provides available phosphorus from an insoluble source of phosphorus. Similarly, nano RP saw a maximum phosphate release of about 11 µM while chitosan-coated nano RP (RP-CH) saw a much lower maximum phosphate release of about 6 µM as it acts as a barrier. The highest phosphate release could be seen after the PCA coating on the nano RP which was about 173 µM where RP-CH-PCA exhibited an initial burst release of phosphorus, followed by a slow release. A lowering of the pH and faster mineral dissolution by the organic acids through the actions of the H+ and carboxylic groups might be responsible for the higher phosphate release. Subsequent coatings were successful in lowering the P release from the nano RP core. Task 4. Evaluate the safety and Rainfastness of the coated fertilizers: There was no detrimental effect on lettuce seed germination showing that our coated RP are not phytotoxic to lettuce seeds (100% germination). Following this, soil leaching studies were performed to assess the leaching effect of the coated RP. RP and the coated RP had minimal leaching of phosphate under simulated conditions. The soil had 32 µM phosphate leachate, RP 45 µM, and the coated RP leachate varied from 25 to 39 µM. These results supported that there is no significant of the coating on the leaching behavior of RP. Task 5. Preliminary product analysis at CAES: Coated rock phosphate products received from the University of Central Florida (UCF) and North Dakota State University (NDSU) were characterized to understand their dissolution characteristics. The result shows that coating of the pristine rock phosphate rock materials significantly reduced the pH and increased the acidity of the samples. However, coating the materials with nanosulfur in combination with organic acid had lesser influence on the pH of the original material, compared to samples coated with organic acids only. Coating RP with organic acids and an organic acid-nanosulfur combination (UCF) reduced RP pH by 46-50% and 27-34%, respectively. Organic acid coating (NDSU) reduced sample pH by 43%. The coating of pristine RP materials with organic acids significantly increased water solubility of available phosphorus in the fertilizer materials from both UCF and NDSU. Coating pristine RP with organic acids and organic acids-nanosulfur increased the water solubility of phosphorus in the materials from UCF by 917-1241% and 308-576%, respectively. Coating of materials with tannic acid influenced phosphorus bioavailability in water than acetic acid. On the other hand, coating of pristine nanosized RP material from NDSU with organic acid increased the water solubility of phosphorus by 894%. Plant available P was higher in the uncoated RP than in the organic acid-coated samples from UCF. A significantly higher concentration of phosphate was extracted from organic acid-coated nanosized RP material from NDSU, compared with the uncoated nanosized RP. It was also found that coating pristine RP materials with organic acids increased the bioavailability of sulfur in water extract. Coating samples with organic acids increased sulfur solubility in water by 291-343%, while coating the samples with nanosulfur in combination with organic acids increased sulfur solubility in water by 697-868%. Tannic acid enhanced the solubility of sulfur than acetic acid. Conversely, the coating of pristine nanosized RP material with organic acid lowered sulfur solubility in water by 89%.
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Progress 05/15/22 to 05/14/23
Outputs
Target Audience:PD Bezbaruah used some of the initial findings from this project in his ENVE 370 (Sustainability Engineering) class in the fall semester (2022) while discussing life-cycle assessment and technology for sustainable agriculture. This class had 5 undergraduate students including 3 females. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?1. Eight graduate students worked on different aspects of this project. They designed experiments and conducted them under the supervision of the PI and Co-PIs. The data obtained were analyzed by the students. The students were trained in rsearch method and data analysis/interpretation. 2. Graduate students, PI, and Co-PI attended a conference (NanoFlorida 2023) at theUniversity of Central Florida (March 2023) How have the results been disseminated to communities of interest?Some of thefindings from the project were presented in the following conferences: Conference Presentation or talk Presenter Location Date NanoFlorida 2023 Development of a coating technology based on nano S embedded in chitosan gel to increase phosphorus bioavailability and use efficiency. Edwin Davidson University of central Florida, USA March 4, 2023 NanoFlorida 2023 Messing Up with Nature for Crop Production and Protection using Nanotechnology? Achintya Bezbaruah University of central Florida, USA March 5, 2023 Student Scholar Symposium 2023 Development of a Coating Technology Based on NanoS Embedded in Chitosan Gel to Increase Phosphorous Bioavailability and Use Efficiency Felicity Rizzi and Anastasiia Pestereva University of central Florida, USA March 27, 2023 What do you plan to do during the next reporting period to accomplish the goals?We will continue to work on the development of the of the coatings for the P-fertilizers and test their efficacy. Greenhouse and field trials will be done as laid out in the proposal. The results will be disseminated through conferences/meetings/seminars and peer-reviewed journal paper publications.
Impacts
What was accomplished under these goals?
Goal:Development of coating for P-fertilizers: Objective:Develop and characterize coated granular P fertilizers. Task 1. Synthesize and characterize CSTAN and CSnanoS film materials:The proposed coating materials CS-TAN and CS-NanoS were synthesized in a one-step process and characterized with SEM, EDS, FTIR, XRD, and zeta potential. The zeta potential of CS-TAN and CS-NanoS was +47 mV and +55 mV, respectively. We assessed the elemental mapping distribution of S and N with EDS. The EDS spectra corroborated the presence of N and S on the surface of the film materials. To corroborate that the CS-TAN film material didn't form any undesired chemical bond between chitosan and tannic acid we recorded the FTIR spectra in comparison with the control chitosan-citric acid (CS-CA). Both FTIR spectra showed similar characteristic peaks with no distinctive difference between the CS-TAN and the control. Additionally, to determine the formation of NanoS we characterized it individually. The SEM showed nanoparticles had an average size diameter of ~180 nm. The zeta potential was +29 mV and the XRD diffraction patterns corresponded to previously reported S nanoparticles. Overall, we demonstrated the effective synthesize and characterization of the CS-TAN and CS-NanoS. In a parallel effort, Layer-by-Layer (L-b-L) coating technique (immersive assembly) was used to develop coated granular rock phosphate (RP) fertilizers where RP granules were dipped in chitosan solution, followed by sonication and centrifugation to facilitate binding. Task 2:Prepare and characterize coated granular:We evaluated the morphology of the coated P fertilizer with SEM and EDS. The SEM images showed uniform coating of both commercially available phosphorus fertilizers (RP and MAP). We evaluated the coating thickness under SEM and determined that 3 rounds of spraying or dipping provided the proper thickness and surface coverage of the fertilizers (MAP and RP). For the L-b-L coated product, The CH coated RP granules were observed under a stereo microscope which revealed a shiny layer formed over the surface of the RP. FTIR spectra also confirmed the presence of coating with additional peaks arising in the case of CH coated RP spectrum due to the presence of amine groups in chitosan. Using a ZetaSizer, we assessed the zeta potential of naked RP and CH coated RP which also revealed that the layering process was successful since the zeta potential of bare RP was -22.1 mV due to the negative phosphate groups while the zeta potential for CH coated RP was 45.3 mV which was due to the positive amine groups present on chitosan. Task 3.Evaluate the safety and rainfastness of the film material:Seed Germination: We evaluated the percentage of tomato seeds germinated under greenhouse conditions for 9 days with our coated fertilizers and controls. The CS-NanoS exhibited the highest germination percentage and root length in comparison to all the controls. CS-TAN showed the highest shoot length. However, further trials are needed to provide a statistically significant difference between the treatment and controls. Task 4.Synthesis of polycitric acid::Polycitric acid, a hyperbranched polyester consisting of citric acid and glycerol monomers, was synthesized using a thermal polycondensation method at a progressively raised temperature up to 150 ºC, which is to be used as the second layer on the RP after CH. The synthesized polycitric acid was characterized using FTIR spectroscopy, carbon-13 and proton nuclear magnetic resonance spectroscopy which confirmed that our synthesis was successful. End group analysis using titration was also done to determine the functional -COOH groups (acid number) and ester number of the synthesized polyester which would be used in binding with chitosan to form the second layer. Task 5.Phosphate leaching studies:Phosphate leaching investigations were conducted on three different types of samples: pure hydroxyapatite, pure rock phosphate, and chitosan-coated RP. Colorimetric methods were employed during the tests, and both short-term (1-day) and long-term (1-week) results were obtained. In highly acidic or basic conditions, hydroxyapatite demonstrated significant phosphate leaching. Conversely, the leaching rate of phosphate decreased as the pH value increased for RP. Chitosan coated rock phosphate exhibited a considerably higher rate of phosphate release compared to unaltered rock phosphate, and this release rate increased proportionally with the quantity of chitosan applied.
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