Progress 01/01/21 to 12/17/24
Outputs
Target Audience:This project is investigating biopolymer based carrier systems for phosphorus as a novel andsustainably approach for fertilizer delivery to enhance crop yield and minimize run-off andenvironmental damage. The target audience includes growers, regulators, agrochemical companies, aswell as scientists investigating food safety and insecurity, climate changeimpacts on agriculture and sustainable approaches to increasing food production. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?The CAES post-doc left for a new position relatively early in 2024 but continued to work at the Yale University Core facility, using their high-resolution scanning and transmission electron microscopes for material characterization. The JHU graduate student also gave a poster presentation at the USDA-NIFA 2024 AFRI Nanotechnology for Agriculture and Food Systems (A1511) program review, which was held at the Gordon Research Conference on Nanoscale Science and Engineering for Agriculture and Food Systems in mid-2024; several team members were present at this meeting. Project findings were also presented at annual CAES Plant Science Day (public open house with over 1000 attendees) by the CAES post-doc, as well as at several weekly meetings of the NSF Center of Sustainable Nanotechnology by the JHU graduate students. The two JHU graduate students supported on this grant have used the materials characterization core facility housed in the Department of Materials Science and Engineering to explore the properties of the phosphorous-containing biodegradable composites synthesized as part of this project. The graduate students have continued to operate a rainfall simulator to assess groundwater run-off and constructed columns to measure phosphorous leachate for different treatments, measured as a function of time. These researchers have also interacted with other graduate students and undergraduate students at JHU and helped in assembling their research findings into publications, all of which provides them with an opportunity to disseminate their scientific findings to the broader community and enhance their professional development. How have the results been disseminated to communities of interest?During the 4 years of this project, our team completed all proposed work. Two papers were published in 2024 (Biomacromolecules, NanoImpact; see Products); one additional paper is under review, and another will be submitted prior to the end of the calendar year. In addition, experiments currently underway that will lead to an additional publication in early 2025. Project findings were presented at a large number of scientific meetings by team members, including by the graduate student, post-doc, and PI/CoPIs. In addition, study findings were presented at the CAES Annual Plant Science Day (Aug. 2024), which is a public event that was attended in nearly 1000 citizens and stakeholders. In terms of scientific meetings and seminars, project findings were presented atthe 6th International Conference on Agriculture for Sustainable Development in Cuttack India; the National Nanotechnology Initiative Nanometrology Webinar Series: Nanometrology for Food, Agriculture, and the Environment; at the New Jersey Institute of Technology (invited seminar); the University of New Haven (invited seminar); NanoFlorida 2024 International Conference; the University of Connecticut (invited seminar); the 2024 Gordon Research Conference on Nanoscale Science and Engineering for Agriculture and Food Systems (multiple presentations by the team); Guangdong University of Technology (invited seminar); 5th International Conference on Agriculture, Food Security, and Safety in Colombo, Sri Lanka (invited seminar); the Joint Conference of ISEH ICEPH & ISEG on Environment and Health , Galway, Ireland; the American Chemical Society meeting in Denver CO (multiple presentations by the team); at the National Academies of Sciences, Engineering, and Medicine's Committee on the Quadrennial Review of the National Nanotechnology Initiative; at the Connecticut Agricultural Experiment Station seminar series; a ZOOM presentation on nanotechnology as part of the 2024 National Nano Day to students at the Dr. Martin Luther King Jr. Middle School in San Francisco CA; the 18th International Phytotechnologies Conference at the University of Calicut in Kerala India; the Pocker Sahib Memorial Orphanage College and Korambayil Ahamed Haji Memorial Unity Women's College in Kerala India; the Materials Innovation for Sustainable Agriculture Symposium, University of Central Florida, Orlando Florida; the 13th Sustainable Nanotechnology Conference (SNO) in Providence Rhode Island; and the 50th Anniversary meeting of Connecticut Association of The Conservation and Inland Wetlands Commissions (CACIWC) in Bristol CT. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
In the final year, work progressed along several different tracks. The first line of investigation was looking at the impact different types of phosphorus in a single type of polymer and this has been completed; a paper was published in mid-2023 and reported in the year 3 progress update. Experiments investigating the ability to deliver phosphorus using different polymer types to create P-containing polymer composites continued in year 4. The goal is to investigate how these different nanocomposites tune the release of phosphate to plants. These studies were designed to answer two questions: how does functionalization influence polymer swelling and phosphate availability? How do polymer structure and functional groups influence biodegradation and P release? Based on previous work (see #1) identifying amorphous calcium phosphate (CaP) and dibasic calcium (DCP) as two phosphorous sources that maximized P uptake while minimizing P loss due to runoff and leachate, a study was conducted with a suite of biodegradable polymers to directly compare their effects. The polymers included pectin, starch, chitosan, PCL, PLA, and PHB. Plant growth experiments have now concluded, and data analysis is underway. Chitosan treated plants showed enhanced biomass and plant P uptake but did not reduce P leachate from soil. Pectin and starch treated plants showed significantly reduced biomass and P uptake, and increased leaching. PLA did not influence biomass or plant P, but reduced leaching when used with CaP. PHB and PCL treated plants had lower biomass and plant P than the controls but did not perform as poorly as pectin and starch. Longer term experiments were also conducted to elucidate the effect of higher plant P on fruiting timeline and volume. Plants treated with chitosan alone had equal biomass to those treated with chitosan-CaP and chitosan-DCP but did not produce any fruit. Soil based biodegradation studies were also conducted, with the polyesters showing slower rates. Specifically, biodegradation amounts (%) after 42 days were as follows.; Pectin ~75%, Starch ~75%, Chitosan ~45%, PHB ~ 11% PCL ~3%, PLA ~2%. This work demonstrates the significant tunability and control that can be achieved by choosing different polymer types for precision P delivery. A manuscript describing this work is under preparation. In a separate line of investigation, the ability to control phosphorus (as well as nitrogen and potassium) delivery efficiency in nanocellulose was explored. Specifically, nanocellulose-based hydrogels were regenerated from mixed softwood in acidic media and immersed in varied concentrations of an NPK-rich fertilizer solution. Building upon previous results which showed the potential of surface-esterified nanocellulose hydrogels to significantly slow the release of embedded NPK fertilizers, a structure-function relational study was conducted to determine how both the esterifying reagent and the degree of surface esterification impacted nutrient release kinetics. The gas-phase, deposition-based modification method results in formation of hydrophobic shells on the hydrogel particles. This study showed that surface esterification can extend the release of soluble NPK from the nanocellulose matrix from less than an hour up to 2 weeks with a high degree of control, which represents a significant step towards an agriculturally relevant timescale for a controlled release fertilizer. Further, a kinetic analysis revealed that the surface layer of esterified cellulose acts as a hydrophobic diffusion barrier to soluble NPK release, causing non-Fickian stress-driven diffusion that was not affected by aqueous solution conditions. Moreover, this study identified optima in terms of both the hydrophobicity (i.e., alkyl chain length) of the reagent and the degree of substitution; long-chain reagents and significant modification induced stress fractures and delaminations that ultimately sped NPK release, while short-chain reagents were ineffective diffusion barriers at any level of substitution. Additionally, in-soil aerobic biodegradation studies revealed that at the levels of substitution which provide the slowest NPK release, the nanocellulose remains completely mineralizable on a reasonable timescale (< 1 year). Overall, the results of this study (i) provided fundamental structure-function relationships on the factors governing nutrient release in coated polymer systems, widely applicable to other systems and (ii) demonstrated the significant potential of surface-esterified nanocellulose prills to create a suite of highly tunable precision agricultural tools. In a separate line of investigation towards a more diverse agrochemical delivery platform, nascent studies also explored the efficacy of similar surface-esterified nanocellulose hydrogels to extend the release of pesticides. For these studies, nanocellulose hydrogels were generated from mechanically defibrillated soybean hulls subjected to a cold alkaline-urea homogenization. As an additional variable, some of the hydrogels were then subjected to an elemental chlorine free bleaching process to remove residual lignin, while some hydrogels remained in this less-refined state. Ultimately, the presence of residual (3%) lignin and hemicelluloses did not impact release behavior, which demonstrates the promise of utilizing unrefined feedstocks in this and similar systems to reduce costs. Imidacloprid, a neonicotinoid insecticide, and propiconazole, a triazole fungicide, were separately embedded in these bleached and unbleached nanocellulose hydrogels. Surface esterification with hexanoyl chloride did not induce undesired reactions with these active ingredients, as evidenced by ATR-FTIR spectroscopy and 13C-CPMAS NMR spectroscopy. Surface modification did extend pesticide release for both treatments - from 1 to 12 weeks in the case of propiconazole, with a less pronounced effect for imidacloprid. However, in contrast to previous work with NPK, the release rate of propiconazole was found to be entirely invariable to the level of modification over a wide range of values. More studies are underway to probe the mechanisms underlying this significant variability in release behavior. Overall, this study highlights the potential of nanocellulose hydrogels to deliver a variety of agrochemicals in agricultural settings and suggests the need for future studies at larger scales. Greenhouse investigations evaluating how P-loaded biopolymers impacted on drought/heat tolerance of tomato were completed at CAES. The post-doctoral associate conducting these experiments left CAES for another position; data analysis has slowed but is ongoing. Parts of this concept have been spun off into a grant proposal currently under review at NIFA. The above work was done in year 4 of this project. As a general conclusion for the work done across the entire project duration, all proposed objectives have been met and significant discoveries have been made. Specifically, we were able to identify and control different polymer degradation rates and leaching profiles for P-containing biodegradable nanocomposites in soil (Objective 1). In addition, we were able to demonstrate the unique ability of the materials to positively impact plant growth and phosphorus delivery/use efficiency across a range of growth conditions (Objectives 2 and 3). A number of systems were investigated in each of the three objectives. A total of 6 papers were published, with 2 more currently in process. The data produced in this grant also generated an additional grant proposal currently under review at USDA NIFA, as well as significant interactions with OCP (a multinational phosphorus mining company).
Publications
- Type:
Peer Reviewed Journal Articles
Status:
Published
Year Published:
2024
Citation:
Phillips, S.G.; Lankone, A.R.; Sommerkamp OHagan, S.; Ganji, N.; Fairbrother, D.H. 2024. Gas-phase functionalization of phytoglycogen nanoparticles and the role of reagent structure in the formation of self-limiting hydrophobic shells. Biomacromolecules, 25 (5), 29022913.
- Type:
Other Journal Articles
Status:
Published
Year Published:
2024
Citation:
Vaidya, S.; Deng, C.; Wang, Y.; Zuverza-Mena, N.; Dimkpa, D.; White, J.C. 2024. Nanotechnology in agriculture: A solution to global food insecurity in a changing climate? NanoImpact 34: 100502.
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Progress 01/01/23 to 12/31/23
Outputs
Target Audience:This project is investigating biopolymer based carrier systems for phosphorus as a novel and sustainably approach for fertilizer delivery to enhance crop yield and minimize run-off and environmental damage. The target audience includes growers, regulators, agrochemical companies, as well as scientists investigating food safety and insecurity, climate change impacts on agriculture and sustainable approaches to increasing food production. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?The CAES post-doc continued to work at the Yale University Core facility, using their high-resolution scanning and transmission electron microscopes for material characterization. The CAES post-doc (Dr. Shital Vaidya) also gave a poster presentation at the USDA-NIFA 2023 AFRI Nanotechnology for Agriculture and Food Systems (A1511) at the University of Tennessee, Knoxville; and at annual CAES Plant Science Day (public open house with over 1000 attendees). The CAES post-doc gave a zoom presentation at the NSF Center of Sustainable Nanotechnology NanoChem-Plant group, as well as platform presentations at the American Chemical Society (ACS) Spring 2023 and the CAES Spring Seminar series. The two JHU graduate students supported on this grant have used the materials characterization core facility housed in the Department of Materials Science and Engineering to explore the properties of the phosphorous-containing biodegradable composites synthesized as part of this project. The graduate students have also constructed and operated a rainfall simulator to assess groundwater run-off and constructed columns to measure phosphorous leachate for different treatments, measured as a function of time. One of the JHU graduate students has recently spent a week at CAES working with the post-doc to set up the growth experiments described in section 4 (above). These researchers have also interacted with other graduate students and undergraduate students at JHU and helped in assembling their research findings into publications, all of which provides them with an opportunity to disseminate their scientific findings to the broader community and enhance their professional development. How have the results been disseminated to communities of interest?After three years of work, our team is on track to complete and likely exceed all proposed work. Three papers were published in 2023 (ACS Agricultural Science and Technology, Environmental Science: Nano; Journal of Agricultural and Food Chemistry; see Products); experiments currently underway will lead to two additional publications in early 2024. Project findings were presented at a large number of scientific meetings by team members, including by the graduate student, post-doc, and PI/CoPIs. In addition, study findings were presented at the CAES Annual Plant Science Day (Aug.2022), which is a public event that was attended in nearly 1000 citizens and stakeholders. In terms of scientific meetings and seminars, project findings were presented at the University of Texas El Paso (Department seminar); Atlantic Basin Conference on Chemistry (ABCChem) in Marrakech Morocco; International Conference on Food and Nutritional Security in Mohali India; National Institute of Food Technology Entrepreneurship and Management (NIFTEM) in Sonepat India); Rutgers University (Department seminar); North Carolina State University at the NSF Center for Science and Technologies for Phosphorus Sustainability (STEPS); Auburn University (Department seminar); Princeton University (Department seminar); the American Chemical Society Spring 2023 Conference; Brookhaven National Laboratory (visiting seminar); with staff scientists of the fertilizer companies Mosaic and Nutrien; University of Wisconsin (NSF site visit); Society for Environmental Toxicology and Chemistry (SETAC) Europe 33rd Annual Meeting in Dublin Ireland; staff scientists from Land o Lakes and Vulpes Corporation; University of Massachusetts Amherst; International Network For Researching, Advancing, and Assessing Materials for Environmental Sustainability (INFRAMES) in Venice Italy; 2023 International Phytotechnologies Conference at Argonne National Laboratory; Workshop on Novel Fertilizers and Plant Nutrition at the University of Delaware; The International Conference on Sustainable and Applied Nanotechnology for Agriculture and Health (SANTAH)(remote); 2023 International Symposium on the Advances of Plant Nanobiotechnology; Huazhong Agricultural University, Wuhan, Hubei Province (remote); American Chemical Society (ACS) Fall 2023 Conference, San Francisco CA; University of Parma in Parma Italy; the University of Minnesota, 9-9-9 Workshop on Science and Engineering in Agriculture and Biology; University of Delaware (Department seminar); the 2023 ASA, CSSA, SSSA International Annual Meeting; University of Athens, Greece; and the Sustainable Nanotechnology Organization (SNO) in Los Angeles CA. What do you plan to do during the next reporting period to accomplish the goals?Work will continue on all 5 tracks described above. This will include evaluating the impact of both different polymer types and different phosphorus sources on P dissolution, leaching, and run-off, as well as on the growth of a number of crops under greenhouse and field conditions. Experiments will also be expanded explore and identify the underlying molecular mechanisms for drought and temperature tolerance conveyed to plants by the phosphorus nanocomposites.
Impacts
What was accomplished under these goals?
In the current year, work is progressing along several different tracks. The first line of investigation is looking at the impact different types of phosphorus in a single type of polymer. Here, tomato was grown in soil amended with five P-sources, used as-is or embedded within a biodegradable polymer, polyhydroxyalkanoate (PHA). Correlation analyses identified treatments that maintain plant growth, improve bioavailable soil P, and reduce P loss. Three performance classes were identified: (i) micro- and nano-hydroxyapatite, which did not increase bioavailable P, plant P-uptake, or change P in runoff/leaching compared to controls; (ii) monocalcium phosphate (MCP), dicalcium phosphate (DCP), calcium pyrophosphate nanoparticles (CAP), and PHA-MCP that increased P-uptake and/or bioavailable P but also increased P loss in runoff/leaching; and (iii) PHA-DCP and PHA-CAP, where increased bioavailable P and plant P-uptake were achieved with minimal P loss in runoff/leaching. In addition to identifying treatments that maintain plant growth, increase bioavailable P, and minimize nutrient loss, correlation plots also revealed that (i) bioavailable P was a good indicator of plant P-uptake; (ii) leached P could be predicted from water solubility; and (iii) P loss through runoff versus leaching showed similar trends. This study highlights that biopolymers can very effectively promote plant P-uptake and improve bioavailable soil P, with implications for mitigating the negative environmental impacts of P loss from agricultural systems. The paper describing much of this work was published in the Journal of Agricultural and Food Chemistry in mid-2023. In a separate line of investigation, the ability to control phosphorus (as well as nitrogen and potassium) delivery efficiency in nanocellulose was explored. Specifically, nanocellulose-based hydrogels were regenerated from mixed softwood in acidic media and immersed in varied concentrations of an NPK-rich fertilizer solution. High loading of NPK was achieved within the hydrogel, but immersion in the matrix provided only slight slowing of nutrient release compared to rapid solubility of conventional formulations. Densification, crosslinking, and coating of the hydrogels with beeswax were ineffective strategies to further slow NPK release. Following these results, both gas and solution-phase esterification of the cellulose matrix with hexanoyl chloride were performed after NPK loading to introduce a hydrophobic surface layer. While solution-phase modification led to phosphorus leaching and was overall ineffective in altering nutrient release, the gas-phase modification slowed the release of P and K by more than an order of magnitude. Moreover, evidence suggests that varying the properties of the hydrophobic surface layer provides a means to tune release rates. Overall, this work demonstrates the potential of agriculturally derived nanocellulose-based hydrogels to be used as an environmentally safe and sustainable vehicle for the controlled release of nutrients in agricultural applications. A paper describing this work will be published in late 2023 in Environmental Science: Nano. During greenhouse investigations at CAES, we made the observation that tomato plants grown in soil containing phosphorus embedded within PHA exhibited significantly greater tolerance to drought and high temperature. This qualitative observation is now being investigated in a large greenhouse experiment. An initially screening study evaluating six different sources of PHA/PHB was completed to find the form and P-solution blending conditions that were most biocompatible with tomato. This has been completed and an experiment looking specifically at P-loaded biopolymer impacts on drought/heat tolerance of tomato is currently underway. At CAES, we are also investigating the ability to deliver phosphorus using different polymers types to create P-containing polymer composites. The goal is to investigate how these different nanocomposites tune the release of phosphate to plants. These studies will be designed to answer two questions: how does functionalization influence polymer swelling and phosphate availability? How do polymer structure and functional groups influence biodegradation and P release? The polymers being investigated include PCL, chitosan, starch, and pectin, among others. Synthesis and nanocomposite characterization has been completed at JHU and plant growth experiments at CAES are currently underway. Collaborative experiments with Professor Deb Jaisi of the University of Delaware were continued. Here, a series of citrate-stabilized amorphous calcium phosphate (ACP) nanoparticles doped with micronutrients (B, Cu, Mg, and Zn) were synthesized, characterized and used in plant studies. The results show that non-doped ACPc stimulated higher lettuce crop yield (by 20%) than MCP and that multi-micronutrient doping in ACPcs enhanced the yield than that in single micronutrient doping. More importantly, P resource use efficiency (RUE), calculated by accounting for crop yield and P lost in leachate, was significantly higher in all ACPc than MCP and was about a log order higher in undoped and multi-micronutrient doped ACPcs. These results demonstrate that the multi-micronutrient doping in ACPc is a more efficient and sustainable way of fertilizing crops than conventional fertilizers. This was published in mid-2023 in ACS Agricultural Science and Technology.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Sigmon, L.R.; Vaidya, S.; Thrasher, C.; Mahad, S.; Dimkpa, C.O.; Elmer, W.; White, J.C.; Fairbrother, D.H. 2023. Role of phosphorus and biodegradable polymer type on phosphorus fate and efficacy in a plant-soil system. J. Agric. Food Chem. 71, 44, 1649316503.
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Sakhno, Y.; Esposti, L.D.; Adamiano, A.; Borgatta, J.; Cahill, M.; Vaidya, S.; White, J.C.; Iafisco, M.; Jaisi, D. 2023. Citrate-stabilized amorphous calcium phosphate nanoparticles doped with micronutrients as a highly efficient nanofertilizer for environmental sustainability. ACS Agric. Sci. Technol. 3, 10, 845854.
- Type:
Journal Articles
Status:
Published
Year Published:
2023
Citation:
Gomez-Maldonado, D.; Phillips, S.G.; Vaidya, S.; Bartley, P.C.; White, J.C.; Fairbrother, D.H.; Peresin, M.S. 2023. Modifying soluble NPK release with hydrophobized nanocellulose-based hydrogels for sustainable enhanced efficiency fertilizers. Environ. Sci.: Nano https://doi.org/10.1039/D3EN00306J.
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Progress 01/01/22 to 12/31/22
Outputs
Target Audience:This project is investigating biopolymer based carrier systems for phosphorus as a novel andsustainably approach for fertilizer delivery to enhance crop yield and minimize run-off andenvironmental damage. The target audience includes growers, regulators, agrochemical companies, aswell as scientists investigating food safety and insecurity, climate changeimpacts on agriculture and sustainable approaches to increasing food production. Changes/Problems:The CAES post-doc (Dr. Jaya Borgatta) got a full time position at Corteva in March of 2022. Dr. Shital Vaidya was hired to fill this position in April of 2022. What opportunities for training and professional development has the project provided?The CAES post-doc continued to work at the Yale University Core facility, using their high-resolution scanning and transmission electron microscopes for material characterization. The CAES post-doc also gave a poster presentation at the Gordon Conference on Nanoscale Science and Engineering for Agriculture and Food Systems, as well as the associated GRS. In addition, the CAES post-doc gave a platform presentation at the Yale University Sussex Plant Biology Symposium. The two JHU graduate students supported on this grant have used the materials characterization core facility housed in the Department of Materials Science and Engineering to explore the properties of the phosphorous-containing biodegradable composites synthesized as part of this project. The graduate students have also constructed and operated a rainfall simulator to assess groundwater run-off and constructed columns to measure phosphorous leachate for different treatments, measured as a function of time. The two graduate students have also given posters at an in-person meeting of the NSF-funded Center for Sustainable Nanotechnology, held in Atlanta and oral presentations at group meetings. These researchers have also interacted with other graduate students and undergraduate students at JHU and helped in assembling their research findings into publications, all of which provides them with an opportunity to disseminate their scientific findings to the broader community and enhance their professional development. How have the results been disseminated to communities of interest?After two years of work, our team is on track to complete and likely exceed all proposed work. One paper was published in 2022 (ACS Sustainable Chemistry and Engineering; see Products); another is under review at the same journal and a third is in the final stages of preparation. Project findings were presented at a large number of scientific meetings by team members, including by the graduate students, post-doc, and PI/CoPIs. In addition, study findings were also presented at the CAES Annual Plant Science Day (Aug.2022), which is a public event that was attended in nearly 1000 citizens and stakeholders. The work was also featured in a 2022 CAES Podcast that was widely distributed to stakeholders and the general public. In terms of scientific meetings and seminars, project findings were presented at The International Chemical Congress of Pacific Basin Societies (Pacifichem)(remote), US-NA Nanotechnology Convergence for Energy, Environment, and Health (remote); the University of Massachusetts (Department Seminar)(remote), the University of Rhode Island (Department seminar)(in person); the University of Texas El Paso (Department seminar)(in person); the Johns Hopkins University (Department seminar)(in person); Rutgers University (Department seminar)(in person); Nanoscale Science and Engineering for Agriculture and Food Systems Gordon Research Conference (in person); Materials Innovation for Sustainable Agriculture (MISA) 2022 Symposium (in person); 2022 Global Summit: Nanotechnology for a Healthier and Sustainable Future, University of Waterloo, Ontario, Canada (remote); all hands meetings of the NSF Center for Sustainable Nanotechnology; and the 21st World Congress of Food, Science and Technology; Future of Food: Innovation, Sustainability and Health in Singapore (in person). What do you plan to do during the next reporting period to accomplish the goals?Work will continue on all 3 experiments described above. This will include evaluating the impact of both different polymer types and different phosphorus sources on P dissolution, leaching, and run-off, as well as on the growth of a number of crops under greenhouse and field conditions. Experiments will also be conducted to explore the potential drought and temperature tolerance conveyed to plants by the phosphorus nanocomposites.
Impacts
What was accomplished under these goals?
In the current year, work progressedalong several different tracks. Work was completed that investigated synthesized biodegradable polymer nanocomposite (PNCs; 10% polyhydroxyalkanoate [PHA]-Ca- P] as phosphorous (P) delivery vehicle with four different crop species (tomato, lettuce, soybean and zucchini) in a 40-day exposure assay. The plants were grown in 2 soil types. The "old" soil (soil retained from Sigmon et al. 2021) and newly treated soil with the equivalent amount of 10% PHA-Ca-P nanocomposite and the conventional salt (CaHPO4). Soil leachates were collected at week 2 and 4 to determine the amount of P loss from soil as a function of amendment type; similar to the previous study, the PNCs retained approximately 40-500% more P than conventional phosphorus, depending both on plant species and soil age. The plants were harvested at the flowering stage and analytical endpoints include plant biomass, tissue element content, chlorophyll content (leaf) and enzymatic activity (root, leaf), and soil element concentrations were determined. After significant data analysis, the effects clearly vary with plant species and P type. However, conclusions were difficult to draw due to large replicate variability. A follow up experiment is currently under consideration. A second line of investigation was conducted looking at the impact of different phosphorus types, including amorphous nanoscale calcium pyrophosphate (Ca-P); nanoscale hydroxyapatite (HAN); microscale hydroxyapatite (HAM); monocalcium phosphate (MONO); and dicalcium phosphate CaHPO4 (DI). These phosphorus types were used as neat soil amendments or as amendments embedded in PHA. Studies involving these materials included abiotic column leaching studies, aqueous dissolution studies, and a run-off simulation study done at JHU, as well as a 50-day greenhouse experiment with tomato. The materials are also being characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), energy dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). In the greenhouse study, a range of plant parameters were measured, including biomass and tissue nutrient content. P loss to leaching was also determined, as was the total and bioavailable amounts of P in the soil after plant growth. The data for the column and run-off simulator experiments is still pending. The plant study was completed, and manuscript preparation is under way. In brief, plant biomass varied little with P type, although the amount of P lost to leaching varied with P type and was significantly reduced across all P types by incorporation into PHA. In addition, several PHA-P composites had increased bioavailable P in the soil after growth, suggesting potential transgenerational benefit. In addition, it was anecdotally noted that certain PHA-P amended plants exhibited increased tolerance to drought and high temperature. Additional greenhouse experiments are being planned to explore this phenomenon. Last, a field study was conducted in 2022 to investigate the effect of phosphorus nanocomposites at full scale (100 % P) and half scale (50 % P) application rates. Tomato seedlings grown for three weeks were transplanted to the CAES Griswold farm with following treatments: control (nothing added), Pure PHA, Mono 100%, Mono 50%, HAN 100%, HAN 50%, PHA mono 100%, PHA Mono 50%, PHA HAN 100%, and PHA HAN 50%. Data analysis is currently underway. At CAES, our investigation of different polymer types continued, although at a reduced pace given our focus on other topics (above). We hope to expand this again in year 3 though. Here, polysaccharide-based nanocomposites will be investigated to tune the release of phosphate to plants. These studies will be designed to answer two questions: how do moieties influence polymer swelling and phosphate availability? How do polymer structure and functional groups influence biodegradation and P release? Specifically, a series of cellulose-based hydroxyapatite nanocomposites will be prepared using amorphous films of carboxymethyl-cellulose, cellulose, and ethyl-cellulose to look at how water retention and polymer complexation influence phosphate ion release, polymer biodegradation and plant growth. The composites will be evaluated for phosphate release in abiotic dissolution experiments and will be assessed for efficacy of phosphate delivery plants in greenhouse experiments. A collaboration with Professor Deb Jaisi of the University of Delaware was initiated. Prof. Jaisi's group synthesized HAN and dicalcium phosphate anhydride (DCPA) under varying crystallization conditions and we determined the efficacy of these materials to improve lettuce yield in a greenhouse studies. Comparative analyses of shoot and root biomass, tissue nutrient content, and P loss in the leachate show that all HANPs and DCPA stimulated lettuce growth, but the extent of enhancement was a function of synthesis condition. Lettuce fertilized with DCPA, a more soluble Ca-P product, showed two times higher crop yield than controls but P loss in leachate was the highest. On the other hand, lettuce fertilized with HANPs synthesized at pH 7.0 resulted in a 73% greater crop yield than the control and the least P leachate among all Ca-P products tested. Considering the 'green' efficiency that accounts for both promoting plant growth and limiting P loss, HANP synthesized at pH 7.0 is more optimal. These results demonstrate that tuning the properties of HANPs is an ideal approach to optimize the effectiveness of nanofertilizer to enhance crop growth and yield and minimize P loss. A manuscript based on this work was published this year. A second set of experiments with Prof. Jaisi is investigating amorphous calcium phosphate (ACP) is a viable alternative to tune P release. A series of citrate-stabilized ACP nanoparticles (ACPcs) doped with micronutrients (B, Cu, Mg, and Zn) and analyzed their dissolution and release rates of P and micronutrients. Comparative analysis of residual ACPcs, dissolved ions, and pH of eluted buffer showed a strong positive correlation among proton absorption capacity of ACPcs, change in pH of the eluted buffer, and P release rate. The competitive advantage of ACPs against conventional fertilizer (monocalcium phosphate, MCP) providing P nutrition to plants was tested in lettuce (Lactuca sativa) in a greenhouse study. The results show that non-doped ACPc stimulates higher lettuce crop yield (by 20%) than MCP and that multi-micronutrient doping in ACPcs enhanced the yield than that in single micronutrient doping. More importantly, P resource use efficiency (RUE), calculated by accounting for crop yield and P lost in leachate, was significantly higher in all ACPc than MCP and was about a log order higher in undoped and multi-micronutrient doped ACPcs. These results demonstrate that the multi-micronutrient doping in ACPc is a more efficient and sustainable way of fertilizing crops than conventional fertilizers. A manuscript based on this work is currently under review.
Publications
- Type:
Journal Articles
Status:
Accepted
Year Published:
2022
Citation:
Sakhno, Y.; Ma, C.; White, J.C.; Jaisi, D. 2022. Role of cation substitution and synthesis condition in calcium phosphate based novel nanofertilizer on lettuce (Lactuca sativa) yield. ACS Sust. Chem. Eng. 10, 47, 1541415422.
- Type:
Journal Articles
Status:
Under Review
Year Published:
2023
Citation:
Sakhno, Y.; Esposti, L.D.; Adamiano, A.; Borgatta, J.; Cahill, M.; Vaidya, S.; White, J.C.; Iafisco, M.; Jaisi, D. 2023. Development of citrate-stabilized amorphous calcium phosphate nanoparticles doped with micronutrients as an efficient and sustainable fertilizer. ACS Sus. Chem. Eng. Submitted
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Progress 01/01/21 to 12/31/21
Outputs
Target Audience:This project is investigating biopolymer based carrier systems for phosphorus as a novel and sustainably approach for fertilizer delivery to enhancecrop yield and minimize run-off and environmental damage. The target audience includes growers,regulators, agrochemical companies, as well as scientists investigating food safety and insecurity, climate change impactson agriculture and sustainable approaches to increasing food production. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?The CAES post-doc has been spending time at the Yale Core facility learning how to use their high resolution scanning electron microscope. How have the results been disseminated to communities of interest?Although the pandemic has somewhat slowed progress, our team is on track after one year to complete and likely exceed all proposed work. Work on one manuscript is on going. In addition, project findings were alsopresented at the CAES Annual Plant Science Day (Aug.2021), which is a public event that was attended in person (withCOVID protocols) by over 1000 citizens and stakeholders. The work was also presented at the Sustainable Innovation ofMicrobiome Applications in the Food System (SIMBA) training course entitled "Regulation, legislation, and safety ofbiostimulants and biofertilizers, including nanoformulates" (Venice, Italy [virtual]; Sept.2021) What do you plan to do during the next reporting period to accomplish the goals?Referencing the three tracks above under Accomplishments: 1. For project 1, sample analysis, data analysis and manuscript preparation will be completed. 2. For projects 2 and 3, the plant-based studies will be completed, including harvest, sample analysis, and data analysis
Impacts
What was accomplished under these goals?
In the current year, work is progressing along 3 different tracks. Prior to the start of our funded project, a series of experiments were initiated by a non-USDA funded CAES post-doc as a follow up experiment to Sigmon et al. 2021 ACS Agric. Sci. Technol. DOI: 10.1021/acsagscitech.1c00149. This work continues investigation of synthesized biodegradable polymer nanocomposite (PNCs; 10% polyhydroxyalkanoate [PHA]-Ca-P] as phosphorous (P) delivery vehicle with four different crop species (tomato, lettuce, soybean and zucchini) in a 40-day exposure assay. The plants were grown in 2 soil types. The "old" soil (soil retained from Sigmon et al. 2021) and newly treated soil with the equivalent amount of 10% PHA-Ca-P nanocomposite and the conventional salt (CaHPO4). Soil leachates were collected at week 2 and week 4 to determine the amount of P loss from soil as a function of amendment type; similar to the previous study, the PNCs retained approximately 40-500% more P than conventional phosphorus, depending both on plant species and soil age. The plants were harvested at the flowering stage and analytical endpoints include plant biomass, tissue element content, chlorophyll content (leaf) and enzymatic activity (root, leaf), and soil element concentrations were determined. At JHU, experiments under the grant have begun and continue to expand our previous work which showed that calcium pyrophosphate nanoparticles within a biodegradable polymer nanocomposite provided controlled release of P to plants and reduced P leachate by 10-fold (Sigmon et al. 2021). Our first step will be to examine how different P sources contained within biodegradable polymer composites affect plant performance and runoff/leachate composition. Biodegradable polymer composites will be made with the polymer PHA as noted in item 1 above and will contain a variety of nanoscale and bulk P sources, including calcium pyrophosphate nanoparticles, hydroxyapatite particles at both the nano- and microscale, and the bulk materials monocalcium phosphate and dicalcium phosphate. Plants will be grown in soil amended with each of these five materials in composite form and neat (without polymer). This variety of P materials and delivery methods will allow us greater insight into how physicochemical factors of the sources such as solubility, and of the soil such as pH, affect P release from composites. Additional experiments without plants will be performed to further probe the P release kinetics as a function of composite type in soil, employing soil columns and ICP analysis along with various chemical characterization techniques, including attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), energy dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). At CAES, a different line of investigation will focus on different polymer types. Here, polysaccharide-based nanocomposites will be investigated to tune the release of phosphate to plants. These studies will be designed to answer two questions: how do moieties influence polymer swelling and phosphate availability? How do polymer structure and functional groups influence biodegradation and P release? Specifically, a series of cellulose-based hydroxyapatite nanocomposites will be prepared using amorphous films of carboxymethyl-cellulose, cellulose, and ethyl-cellulose to look at how water retention and polymer complexation influence phosphate ion release, polymer biodegradation and plant growth. In addition, cellulose is linked by 1-4 glycosidic bonds that are more resistant to degradation when compared to 1-6 glycosidic linkages that can be found in starch or dextran. As such, polymer degradation of starch nanocomposites will be evaluated to further understand and tune phosphate release. Cellulose is structurally similar to chitosan; however, chitosan's structure results in deprotonation and swelling under acidic conditions, making it useful as a pH-responsive polymer for phosphate release. In parallel, we will also work to understand how the chemistry of the phosphate-containing nanomaterial influences phosphate delivery and plant health; here, hydroxyapatite will be compared to copper-phosphate and zinc-phosphate nanocomposites. Tuning the coordinating cation may alter the dissolution rate and will enable possible co-dosing of macro- and micronutrients. The composites will be evaluated for phosphate release in abiotic dissolution experiments and will be assessed for efficacy of phosphate delivery to lettuce, tomato, soybean, corn, and wheat in greenhouse experiments. The most effective materials will be evaluated in field experiments in June 2022.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2021
Citation:
44. Sigmon, L.R.; Adisa, I.; Liu, B.; Elmer, W.H.; White, J.C.; Dimkpa, C.O.; Fairbrother, D.H. 2021. Biodegradable polymer nanocomposites provide effective delivery and reduced runoff of phosphorus during plant growth. ACS Agric. Sci. Technol. DOI: 10.1021/acsagscitech.1c00149
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2021
Citation:
Project findings were also presented at the CAES Annual Plant Science Day (Aug.2021), which is a public event that was attended in person (with COVID protocols) by over 1000 citizens and stakeholders
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2021
Citation:
The work was also presented at the Sustainable Innovation of Microbiome Applications in the Food System (SIMBA) training course entitled Regulation, legislation, and safety of biostimulants and biofertilizers, including nanoformulates (Venice, Italy [virtual]; Sept.2021)
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