Source: UNIVERSITY OF DELAWARE submitted to
TOWARDS GLOBAL PHOSPHORUS SECURITY: DEVELOPMENT OF A NOVEL NANOFERTILIZER USING PHOSPHORUS RECOVERED FROM AGRICULTURAL WASTES
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
TERMINATED
Funding Source
Reporting Frequency
Annual
Accession No.
1015268
Grant No.
2018-67021-27965
Project No.
DEL00781
Proposal No.
2017-07840
Multistate No.
(N/A)
Program Code
A1511
Project Start Date
May 1, 2018
Project End Date
Apr 30, 2023
Grant Year
2018
Project Director
Jaisi, D. P.
Recipient Organization
UNIVERSITY OF DELAWARE
(N/A)
NEWARK,DE 19717
Performing Department
Plant & Soil Sciences
Non Technical Summary
Phosphorus (P) recovery from agricultural wastes could provide a solution towards sustainable agriculture; fabrication of recovered P into a potent nanofertilizer could alleviate untimely P release from commercial fertilizers. In this proposal, we aim to 1) fabricate hydroxyapatite nanoparticles (HANPs) using P recovered from agricultural wastes and 2) develop a quantitative structure and function relationship as a scientific basis for the development and optimization of a novel controlled release nanofertilizer. We will partially replace Ca by Zn and P by B (borate) in the HANP structure as micronutrients for plants. Furthermore, we will modify crystal structure by varying cation and anion composition to achieve desired rate and timing of P and micronutrient release to synchronize with plant needs. These goals will be achieved by 1) HANPs synthesis tuned for optimal P release rate; 2) selecting best-suited HANPs as the target product to be synthesized from agricultural wastes; and 3) testing and comparing the effectiveness of HANPs with commercial and other slow/controlled release fertilizers in greenhouse studies. To achieve these goals, we will merge nano- and interface- and isotope-geochemistry with colloidal science and apply advanced spectroscopic, mineralogical, microscopic, and elemental methods. Synthesis of 18O-isotope labeled HANPs will allow tracking of P during dissolution, plant uptake, and potential transformation in soil and thus provide direct and unequivocal evidence and sufficiency of plant P uptake from HANPs. Overall, closely integrated results from molecular to controlled greenhouse studies will provide fundamental understanding that will eventually benefit both agroecosystem and environment.
Animal Health Component
0%
Research Effort Categories
Basic
30%
Applied
40%
Developmental
30%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
4030120100050%
1025210200050%
Goals / Objectives
The major goal is to synthesize hydroxyapatite nanoparticles (HANPs) from agricultural wastes and develop a quantitative crystal chemical structure and function relationship as a scientific basis for the development and optimization of a novel controlled release fertilizer. Specific objectives to realize this goal are to:1) Synthesize HANPs as a novel nanofertilizer and develop a quantitative structure-function relationship based on a) structural (crystal lattice structure, cation and anion compositionsand ratios, and hydroxyl ion and mineral-bound water), b) morphological (shape andsurface area), and c) hydrodynamic (size and surface charge/potential) properties with Prelease efficiency;2) Develop a method to maximize P recovery from animal wastes (manure and poultry litter)and fabricate into a high purity nanofertilizer;3) Discriminate P uptake from HANPs, evaluate its potential as a source of supplemental Pfor plants and compare the nutrient use efficiency and loss with commercial controlled andslow release fertilizers.
Project Methods
We will merge methods on nano- and interface- and isotope geochemistry with colloidal science and apply advanced spectroscopic, mineralogical, microscopic to meet the listed objectives. In general, it will include: i) synthesis of 18O-isotope labeled HANPs using agricultural wastes, run series of controlled experiment to identify and track P during dissolution, run greenhouse crop growth experiment to test plant uptake of HANP released P, and general assessment of potential transformation of HANP derived P in soil.

Progress 05/01/18 to 04/30/23

Outputs
Target Audience:Academics; federal, state, and local governments, fertilizer producing companies, nutrient recycling companies, stakeholders on the nutrient management; farmers and commodity groups Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Following undergraduate and graduate students and postdoctoral associate were mentored and provided following major opportunities as follows: o Gulcin Tosun (2018-2021, Ph.D. in 2021). She completed the project on extraction of agricultural sources of P from manure and poultry litter and fabrication into hydroxyapatite nanofertilizer. She successfully completed the dissertation defense and is now a researcher at Shell Technologies, Houston, TX. Her work is published in ACS Sustainable Chemistry and Engineering (Tosun et al., 2021). She is wrapping up the two additional manuscripts in cation incorporation and dissolution from her dissertation project. o Yuriy Sakhno (Postdoctoral Associate, 2018-2023). He made a significant breakthrough in the incorporation of ions and altering the solubility of apatite. He utilizes FTIR, nano-FTIR coupled with AFM, FE-SEM, XRD, and DS-TGA techniques to characterize and differentiate HANPs from different synthesis and modification routes. The outcomes of his efforts are presented in three keynote talks and published in four papers. He is moving forward in his next career as senior scientist at AsymChem, Boston, MA. o Sarah Tuoni (undergraduate student, 2019-2022). She made significant outcome on characterization of soils used in which HANPs were used to for crop growth. She made five presentations at Undergraduate research celebratory symposium, DENIN symposium, Soil Science Society meetings and ACS Fall meeting. She completed undergraduate degree in Plant and Soil Sciences and now under a new degree program in Chemistry and Biochemistry. oYouness Sedki and Chaymma Banini (visiting students from Mohammed VI Polytechnic University (UM6P)) will continue research on advanced characterization of activating rock phosphate to enhance solubility as a continuation of their PhD and MS projects. The project training included following: i) training nanochemistry and material characterization using most advanced analytical instruments; ii) honing skills by work closely and train to develop their supervisory and interpersonal skills; iii) develop management skills by working closely on lab/project management; iv) training on logic building on manuscript writing, highlighting key scientific findings; v) training on reviewing manuscripts, vi) honing critical thinking skills; v) improving speaking and poster/presentation skills, vi) attending meetings, workshops, and discussion forums to broaden the knowledge and to establish the connection to peers and professionals. Professional development for them included collaboration in 21st century, work-life balance, successful career placement, and job search and negotiations. PIs and collaborators are dedicated scientists and are generating a highly skilled workforce. How have the results been disseminated to communities of interest?Project results are disseminated through publication in peer-reviewed journals, presentations at national/international meeting and conferences. Key interactions include: Interacted with local stakeholders through DENIN and EPSCoR projects in the state and through giving takes in a major non-profit organization (Center for the Inland Bays, CIB) Significant effort on outreach made through presentations in the stakeholders in the region (commodity groups, poultry and animal husbandry industries, regional fertilizer suppliers), connecting to collaborations, student and postdoc mentoring, publications, and keynote/invited/volunteered presentations in conferences and meetings New collaboration established with OCP Group (which has 31% market share of the world phosphate product market) and the university it established in phosphorus and plant nutrition research (Mohammed VI Polytechnic University) What do you plan to do during the next reporting period to accomplish the goals?Outcomes of the project exceeded the expected outcomes originally proposed. It fully met all objectives listed. Now the project is complete and we will start newly funded project next month.

Impacts
What was accomplished under these goals? Major science outcomes and breakthroughs of the project (all years): This project on hydroxyapatite nanoparticles (HANPs) as a potential nanofertilizer generated significant scientific and technological breakthroughs. For the first time, it made a scientific breakthrough in the successful structural incorporation of two soluble ions (sodium and potassium) into the HANPs lattice (Sakhno and Jaisi, 2021) (highlighted on the AS&T cover page (AS&T, 2021)) and protonated phosphate (HPO4) in the crystal structure (Sakhno et al., 2022b). These two developments along with carbonate substitution (Sakhno et al., 2021) allowed enhancing as well as tuning of the solubility of HANPs, which were tested and confirmed using macro-dialysis dissolution technique (Sakhno et al., 2022c). For the first time, we proved that the structural incorporation of different ions in HANPs imparts a significant difference in the agricultural crop yield and controls phosphorus (P) leaching from soil (Sakhno et al., 2022a). Furthermore, methods on P recovery from animal manures, selective purification to enrich P, and precipitation as HANPs were successfully developed (Tosun et al., 2021). The purity and structural parameters of HANPs synthesized from reagents vs P recovered from wastes were found to be quite comparable (Tosun, 2021; Tosun et al., 2021). More importantly, the concentration of toxic heavy metals in HANPs decreased by 3−5 log orders compared to waste during purification and crystallization. This is highly encouraging because other methods and products currently available in the literature have a much higher concentration of residual heavy metals. This means that the waste-sourced HANPs can be a candidate slow-release fertilizer as an innovative solution for improving crop yield and sustainability. This project yielded followings: i) 9 peer-reviewed publications with 3 additional manuscripts under review or ready for submission; ii) 4 keynote talks, 7 invited talks, and 14 volunteered presentations in professional society meetings and conferences. ?Other major accomplishments of the project: Outcomes generated and next set of questions raised enabled a new USDA funding from the same program (A1511: Nanotechnology for Agricultural and Food Systems) in which this project was originally funded. Data generated from this project contributed to new research instrumentation proposal (USDA EGP): Orbitrap mass spectrometer. This instrument- only second to the world--is installed at Environmental Isotope Science (EIS) laboratory at UD. A new set of advanced instrument proposal is submitted to U.S. Department of Defense (DOD). PD Jaisi was awarded the 'Fellow' of International Association of Advanced Materials (IAAM), major credit goes to the outcomes of this project. Incorporation of micronutrients in nanofertilizer is published in the cover page of ACS Agricultural Science and Technology (2021) (volume 1, issue 5). Novel method developed: Flow cell based, no-back reaction micro-dissolution apparatus was developed and employed in the dissolution of HANPs. Two papers out of this apparatus are already published and third one is submitted for peer-review. Advanced methods of characterization refined or used: FTIR-ATR on new diamond cell; He-absorption based SSA; low angle and small step XRD, elemental ratios FE-SEM, temperature program and calorimetry based TGA, and advanced SAED based TEM. A workshop on 'Novel fertilizer development and plant nutrition' is planned (July 2023). Invited speakers are from US and abroad (Morocco, Chile, and Italy). The researchers are from diverse fields including material science, chemical engineering, soil chemistry, and agronomy. It covers various area of stakeholders: scientists from OCP Morocco, local and regional fertilizer producers and distributors, and state (DE and CT) agricultural experimental stations. Significant effort on outreach made through presentations in the stakeholders in the region (commodity groups, poultry and animal husbandry industries, regional fertilizer suppliers), connecting to collaborations, student and postdoc mentoring, publications, and keynote/invited/volunteered presentations in conferences and meetings This project catalyzed unfunded collaborations with: i) Jonas Baltrusaitis (professor at Lehigh University) on characterization and doping of elements in N and P fertilizers; ii) Jason White (director of Connecticut Agricultural Experimentation Station, New Haven, CT) on plant growth using HANPs, iii) Sushil Adhikary (Regent professor at Auburn University) on promotion and co-precipitation of slow-release nutrients in biochar, iv) Ivana Miletto (professor at Università del Piemonte Orientale, Italy) on solid-state NMR based characterization of HANPs, and v) Michele Iafisco (senior scientist at National Research Council, Italy) on the tuning of amorphous phase calcium phosphate synthesis, vi) Mykola Nikolenko (professor at Ukrainian State University of Chemical Technology, Ukraine) on energetics and phase transformation of calcium phosphate materials, and vii) Martin Jemo (professor at Mohammed VI Polytechnic University, Morocco) phosphorus and plant nutrition. Unfunded collaborations have been successful in publishing collaborative papers (Vasylenko et al., 2021; Nikolenko et al., 2023; Sakhno et al., 2022, 23), garnering collaborative grants (two from USDA in 2023), submission of federal grant proposals (NSF, USDA), and industry proposal (OCP Group, Morocco) and visiting students (Youness Sedki and Chaymma Banini) from UM6P. These efforts will be continued and further strengthened in future years.

Publications

  • Type: Journal Articles Status: Published Year Published: 2022 Citation: Sakhno, Y., Ma, C., Borgatta, J., Jin, Y., White, J.C., Jaisi, D.P. (2022). Role of cation substitution and synthesis condition in a calcium phosphate-based novel nanofertilizer on lettuce (Lactuca sativa) yield. ACS Sustainable Chemistry & Engineering 10 (47), 15414-15422.
  • Type: Journal Articles Status: Published Year Published: 2022 Citation: Vasylenko, K.V., Sakhno, Y., Jaisi, D.P., Nikolenko, M. (2022). Determination of the activation energies of phase transition for calcium orthophosphates based on powder X?ray diffraction data. Crystal Research and Technology, 57, 2100215.
  • Type: Journal Articles Status: Submitted Year Published: 2023 Citation: Sakhno, Y., Degliesposito, L., Adamiano, A., Cahill, M., Vaidya, S., White, J., and Jaisi, D.P. Citrate-stabilized amorphous calcium phosphate nanoparticles doped with micronutrients as a highly efficient nanofertilizer for environmental sustainability. Agricultural Science & Technology (submitted).
  • Type: Journal Articles Status: Under Review Year Published: 2023 Citation: Nikolenko, M.V., Myrhorodska-Terentieva, V.D., Sakhno, Y., Jaisi, D.P., Likozar, B., and Kostyniuk, A. Hydrothermal leaching of amylose from native, oxidized and heat-treated starches. MDPI Processes (under review).
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2023 Citation: Jaisi, D.P. Recycling nutrients into novel fertilizer is a new route for sustainable Agriculture. International Conference in Renewable and Sustainable Energy and Resources. Osaka, Japan (Jul 24-26, 2023). [Keynote]
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: Sakhno, Y., Ma, C., Borgatta, J., Jin, Y., White, J.C., and Jaisi, D.P. Changes in cation composition in calcium phosphate based novel nanofertilizer improve crop yield. Atlantic Basin Chemical Society Meeting. Marakech, Morocco (Dec 12-16, 2022). [Invited]
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: Jaisi, D.P. Development of novel nanofertilzers: Concept and current state of achievements. Mohammad Polytechnic University. Ben Guirier, Morocco (Dec 19, 2022). [Invited]
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: Tuoni, S., Gray, K., and Jaisi, D.P. Extraction and characterization of phosphorus in soils treated with synthesized hydroxyapatite fertilizers. Annual meeting of the Soil Science Society of America, Baltimore MD (Nov 3-10, 2022)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: Tuoni, S., Sakhno, Y., White, J., and Jaisi, D.P. Dynamics and speciation of phosphorus pools in soil treated with synthesized hydroxyapatite fertilizers during the growth of lettuce and corn. Undergraduate Research and Service Scholar Celebratory Symposium, University of Delaware, Newark, DE (Aug 13, 2022).


Progress 05/01/21 to 04/30/22

Outputs
Target Audience:Academics; federal, state, and local governments, and stakeholders on the nutrient management; farmers and commodity groups Changes/Problems:Due to prolonged impact of COVID, a second NCE applied for and approved. We will contiinue to unravel new findings on the remaining aspect of the work and fine-tune synthesis based on the feedback from plant growth and wrap up the projects in 2023. What opportunities for training and professional development has the project provided?The major opportunities provided to researchers are as follows: Gulcin Tosun (Ph.D. degree completed in Summer 2021). She completed the project on extraction of agricultural sources of P from manure and poultry litter and fabrication into hydroxyapatite nanofertilizer (Task 4 in the proposal). She successfully completed the dissertation defense and is now a postdoc researcher at the University of Illinois, Urbana-Champaign. Her work is published in ACS Sustainable Chemistry and Engineering (Tosun et al., 2021). She is wrapping up the second manuscript in cation incorporation and dissolution. Yuriy Sakhno (Postdoctoral Associate, since Fall 2018) has made a significant breakthrough in the incorporation of ions and altering the solubility of apatite. He utilizes FTIR, nano-FTIR coupled with AFM, FE-SEM, XRD, and DS-TGA techniques to characterize and differentiate HANPs from different synthesis and modification routes. The outcomes of his efforts are presented in three keynote talks and published in four papers. Sarah Tuoni (undergraduate student) has been making excellent progress on characterization of soils used in crop growth in terms of phosphorus speciation. So far she made two presentations in the internal conferences at UD: one Undergraduate research celebratory symposium (Fall 2021) and other at DENIN symposium (Spring 2022). This year, the project has provided the following opportunities to graduate student and postdoctoral associate supported by this project: Training and experience on isotope biogeochemistry; refined processing of samples and isotope measurements; ii) honing skills by work closely and train to develop their supervisory and interpersonal skills; iii) further develop management skills by working closely on lab/project management; iv) training students and postdocs on manuscript writing, highlighting key scientific findings; they will be trained on reviewing manuscripts and critical thinking skills; v) improving speaking and poster/presentation skills, vi) attending meetings, workshops, and discussion forums to broaden the knowledge and to establish the connection to peers and professionals. Professional development for them included collaboration in 21st century, work-life balance, successful career placement, and job search and negotiations. Following opportunity was provided to undergraduate student: basic training in separation, quantification of phosphorus pools in soils, instrumentation (UV-VIS, HPLC, mass spectrometry) and related measurement for soil leachate and water chemistry. Both PIs are highly committed and have track records of taking additional approaches as needed to achieve these goals. How have the results been disseminated to communities of interest?In the fourth year of the project, we have exciting, impactful results that are significant for achieving or to some extent exceeding the broader objectives of this project. We continue to publish scientific findings in peer-reviewed journals present at national/international meeting and conferences. Key interactions include: Interacted with local stakeholders through DENIN and EPSCoR projects in the state and through giving takes in a major non-profit organization (Center for the Inland Bays, CIB) Published four papers, three manuscripts are under review or submitted, three manuscripts are under preparation (see details in the accomplishment section). Two volunteered talks by a graduate student and a postdoctoral associate in the project (see details in the accomplishment section). What do you plan to do during the next reporting period to accomplish the goals?Series of experiments performed, analyses made, and outcomes generated are quite exciting and provided either fine-tuning some expect of project or dive into other exciting expect of the project. We have applied an NCE for the next year to continue to unravel new findings on the remaining aspect of the work and fine-tune synthesis based on the feedback from plant growth. Therefore having one year of NCE will be sufficient for us to complete three iterations of plant growth and response. Research findings will continue to be disseminated via publication, presentations at professional society meetings, stakeholders at the state and regional level. PIs and collaborators are dedicated scientists and are generating a highly skilled workforce.

Impacts
What was accomplished under these goals? The fourth year of the project focused mostly on Task 5 (Identify selective and sufficient P uptake by plants from HANPs) but continued to spread on other tasks partly to tune the properties that are based on the feedback obtained from Task 5. Major activities include: Testing efficacy and efficiency of HANPs (against conventional fertilizer) for the growth of lettuce plant (as a model plant) was performed at collaborator's lab at CT Agricultural Experiment Station. The P mass balance (applied, plant taken up, remained in soil, and eluted) was calculated and efficient HANPs were identified. A manuscript is under review. Plant attributes (biomass, P content, and other micro- and macro-nutrients) were compared with the crystal chemistry of HANPs types and the structure-function relationship developed. A manuscript is being drafted. Modification and optimization of incorporation of soluble metals into the HANP structure are continued. Efforts are made to test possible incorporation when P is present with a series of other metals present in waste extracts. Continued efforts on proton (H+) incorporation (as HPO42- instead of PO43-) in the HANPs structure have made a scientific breakthrough! A manuscript is being written and submitted for peer review. Advanced methods of characterization are employed for understanding the details of the chemistry of HANPs. These included: FTIR (Nicolet 380 spectrometer with Attenuated Total Reflectance (ATR) cell for the infrared spectra); SSA (Micromeritics ASAP 2020 by nitrogen adsorption at 77 K following the BET method); ICP-OES (Liberty 200, Varian), XRD (Bruker D8 equipped with a high-speed X'Celerator detector powder diffractometer using CuKa radiation), FE-SEM (AURIGA 60 Crossbeam), TGA (SDT Q 600, a TA Instruments) A novel method of dissolution was developed and employed in the dissolution of HANPs. This method avoids the back-reaction so that the dissolution rate constant can be calculated accurately. A manuscript is being drafted based on the outcome of this work. Significant effort on outreach made through presentations in the stakeholders in the region, connecting to collaborations, student and postdoc mentoring, publications, and keynote/invited/volunteered presentations in conferences and meetings Key accomplishments: The PI was awarded Fellow of International Association of Advanced Materials (IAAM), major credit goes to the outcomes of this project. ACS Agricultural Science and Technology (2021) (volume 1, issue 5) published a cover page on lattice parameters change due to the incorporation of foreign ions in apatite. In the third project year, a breakthrough was made in the incorporation of two soluble ions (sodium and potassium) into the HANPs structure. In the fourth year, continuing research on soluble ion incorporation in HANPs from waste-derived P sources provided comparable results but the effects of other (unwanted) ions are significant (a manuscript is being drafted). Method for the recovery of P from agricultural wastes and incorporation into HANPs finalized. The HANPs synthesized from waste are pure and comparable to HANPs synthesized from pure chemicals (Unal et al., 2021). Testing of novel nanofertiizer (HANPs) for plant growth continued. One test is completed that utilized lettuce as a model plant. The results confirmed that the HANPs are better than conventional fertilizers. The incorporation of soluble cations is found to enhance both biomass content and yield. Fertilization of lettuce using HANPs showed the leaching of P was significantly low in the presence of HANPs. This is a highly encouraging result because, for the first time, we showed the double benefits of using HANPs for crop growth as well as limiting nutrient loss. (Sakhno et al., 2022, submitted). Another field testing on comparative analysis of crystalline HANPs and amorphous calcium phosphate (ACP) started (Feb 2022). A new research instrumentation proposal was submitted to U.S. Department of Defense (DOD). The proposal utilized the preliminary data generated from this project. The past submission of instrument proposal to USDA was not funded. Three peer-reviewed papers have been published, and four are submitted or are under review. New collaborations initiated from this project are continued, and the list is still growing: i) Jonas Baltrusaitis, Associate professor of physical chemistry and material science at Lehigh University on characterization and doping of elements in N and P fertilizers; ii) Jason White (director of Connecticut Agricultural Experimentation Station, New Haven, CT) on plant growth using HANPs, iii) Sushil Adhikary, Regent professor, Auburn University (promotion and co-precipitation of slow-release nutrients in biochar), iv) Ivana Miletto (Università del Piemonte Orientale, Italy) on solid-state NMR based characterization of HANPs, and v) Michele Iafisco (National Research Council, Italy) on the tuning of amorphous phase calcium phosphate synthesis. These five fronts of collaborations are significant and have enhanced the quality of science outcomes on synthesis, characterization, and testing and overall diversifying the use of nano-based fertilizer. We will continue to tap our collaborative expertise in this and future projects.

Publications

  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Anatolii, S., Sakhno, T., Olena, H., and Sakhno, Y. (2021). Presowing treatment of vetch hairy seeds (vi?ia villosa) by UV irradiation. Global Journal of Environmental Science and Management DOI: 10.22034/gjesm.2021.04.05
  • Type: Journal Articles Status: Submitted Year Published: 2022 Citation: Sakhno, Y., Miletto, I., Paul, G., and Jaisi, D.P. A novel route to enhance the solubility of apatite: Structural incorporation of protons. ACS Interface Science and Chemistry (submitted).
  • Type: Journal Articles Status: Under Review Year Published: 2022 Citation: Sakhno, Y., Ma, C., Jin, Y., White, J., and Jaisi, D.P. Role of cation substitution and synthesis condition in calcium phosphate based novel nanofertilizer on lettuce (Lactuca sativa) yield. ACS Sustainable Chemistry & Engineering (under review).
  • Type: Theses/Dissertations Status: Published Year Published: 2021 Citation: Tosun, G. (2021). Recovery of phosphorus from animal wastes and synthesis into hydroxyapatite nanoparticles. University of Delaware, 144 pp
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Jaisi, D.P. Development and tuning of slow-release phosphorus nanofertilizer. European Advanced Material Congress, Stockholm, Sweden (Aug 2325, 2021). [Keynote and IAAM Fellow lecture]
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Tosun, G., Sakhno, Y., and Jaisi, D. (2021). Synthesis of hydroxyapatite nanoparticles from phosphorus recovered from animal wastes. ACS Sustainable Chemistry & Engineering, 9, 45, 1511715126
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Vasylenko, K.V., Sakhno, Y., Jaisi, D.P., Nikolenko, M. (2022). Determination of the activation energies of phase transition for calcium orthophosphates based on powder X?ray diffraction data. Crystal Research and Technology, 57, 2100215.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Sakhno, Y., and Jaisi, D.P. (2021). Novel route to enhance the solubility of apatite, a potential nanofertilizer, through structural incorporation of sodium and potassium ions, ACS Agricultural Science & Technology, 1, 488-498.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: Jaisi, D.P. Recycling nutrients from agricultural waste: Routes and efficiency of recycling. RenewableMeet 2022, Dubai, United Arab Emirates (Mar 2123, 2022). [Keynote talk]
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: Jaisi, D.P. Crystal chemistry of apatite: Role of ions on solubility. International Conference on Material Sciences, Lisbon, Portugal (Mar 2325 2022). [Keynote talk]
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: Jaisi, D.P. Holistic view of nutrient cycling in agroecosystem. Department of Fishery sciences, Auburn University, Auburn, AL (Apr 8, 2022) (Departmental seminar)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: Tuoni, S., Sakhno, Y., Gray, K., Jaisi, D. Extraction and characterization of phosphorus in soils treated with synthesized hydroxyapatite fertilizers for plant growth. Delaware Environmental Institute Research Symposium, Newark, DE. April 13, 2022.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Tuoni, S., Tosun, G., Jaisi, D. Phosphorus release from hydroxyapatite nanoparticles in the presence of organic acids. University of Delaware Unique Strengths Symposium, Newark, DE. August 13, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Tosun, G., Sakhno, Y., and Jaisi, D.P. Recovery and purification of phosphorus from agricultural wastes for the synthesis of a hydroxyapatite nanofertilizer. Soil Science Society of America Annual Meeting, San Antonio. Nov, 2021.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Sakhno, Y., and Jaisi, D.P. A novel route to enhance the solubility of apatite: Structural incorporation of protons. 2021 Fall ACS Meeting, Atlanta, GA.


Progress 05/01/20 to 04/30/21

Outputs
Target Audience:Academics; federal, state, and local governments, and stakeholders on the nutrient management; farmers and commodity groups Changes/Problems:A NCE for one year applied for and approved. Given the novelty of the outcomes, we expect to ask for an additional 6-months of NCE as well as plan for a new proposal to identify gaps in the field and controlled experiments. What opportunities for training and professional development has the project provided?The major opportunities provided to researchers are as follows: 1. Gulcin Tosun (Ph.D. student, intake Fall 2016) is a full-time Ph.D. student in this project. Her project is on the extraction of agricultural sources of P from manure and poultry litter and fabrication into nanofertilizer. Her employs conventional and advanced analytical chemistry methods. She presented her work in SSSA meeting in 2020 and her manuscript on ACS Sustainable Chemistry and Engineering is under review. She is wrapping up the dissolution experiments, the final portion before she completes her degree this summer. 2. Yuriy Sakhno (Postdoctoral Associate, start date Fall 2018) has made a significant breakthrough in the incorporation of ions, which are not known before to be present in the lattice structure of apatite minerals. His alteration of crystal chemistry to enhance the solubility of the apatite has yielded significant outcomes. He is a highly skilled instrumentalist who employs FTIR, nano-FTIR coupled with AFM, FE-SEM, XRD, and DS-TGA techniques to characterize and differentiate HANPs from different synthesis and modification routes. The outcomes were presented in PanNano meeting and going to be presented in the Fall ACS meeting. One manuscript is published, three are submitted/under review and working on one manuscript. He continues to further tune the solubility method in the upcoming first NCE year. Given the novelty of this work, we expect to ask for an additional 6-months of NCE as well as plan for a new proposal to identify gaps in the field and controlled experiments. This year, the project has provided the following opportunities to a graduate student and a postdoctoral associate supported by this project: Training and experience on isotope biogeochemistry; refined processing of samples and isotope measurements; ii) honing skills by work closely and train to develop their supervisory and interpersonal skills; iii) further develop management skills by working closely on lab/project management; iv) training students and postdocs on manuscript writing, highlighting key scientific findings; they will be trained on reviewing manuscripts and critical thinking skills; v) improving speaking and poster/presentation skills, vi) attending meetings, workshops, and discussion forums to broaden the knowledge and to establish the connection to peers and professionals. Gulcin is preparing to wrap up and defend her dissertation this summer and plan to graduate this summer. Both PIs are highly committed and have track records of taking additional approaches as needed to achieve these goals. How have the results been disseminated to communities of interest?In the third year of the project and we have exciting, impactful results that are significant for achieving or to some extent exceeding the broader objectives of this project. We continue to publish scientific findings in peer-reviewed journals, present at the national/international meeting and conferences. Key interactions include: Published three papers, three manuscripts are under review or submitted, two manuscripts are under preparation (see details in the accomplishment section). Two volunteered talks by a graduate student and a postdoctoral associate in the project (see details in the accomplishment section). What do you plan to do during the next reporting period to accomplish the goals?Series of experiments performed, analyses made, and outcomes generated are quite exciting and provided either fine-tuning some expect of project or dive into other exciting expect of the project. We have an approved NCE for the next year and continue to unravel new findings in these directions. Research findings will be disseminated via publication, presentations at professional society meetings, stakeholders at the state and regional level. Both PIs are dedicated to training a highly skilled workforce and continue to do training and activities.

Impacts
What was accomplished under these goals? A breakthrough was made in the incorporation of two soluble ions (sodium and potassium) into the HANPs structure. Enhanced solubility of the HANPs due to the incorporation of these two ions is being tested using the newly devised dissolution method. Proof of concept on resource recovery from agricultural wastes and incorporation into HANPs confirmed. The HANPs from waste are highly pure and quite comparable to HANPs synthesized from pure chemicals (a manuscript is under revision). Field testing of novel nanofertiizer (HANPs) is completed in the lettuce plant. The results confirmed that the HANPs are better than conventional fertilizers. The incorporation of soluble cations is found to enhance both the biomass and yield (a manuscript is under draft stage of preparation). Fertilization of lettuce using HANPs showed the leaching of P was significantly low in the presence of HANPs. This is a highly encouraging result because, for the first time, we showed the double benefits of using HANPs for crop growth as well as limiting nutrient loss. A major research instrumentation (EGP) proposal (Orbitrap quadrupole MS/MS) submitted to USDA in March 2021. The proposal utilized the preliminary data generated from this project. Three peer-reviewed papers published and four are submitted or are under review. Four new collaborations initiated: i) Jason White (director of Connecticut Agricultural Experimentation Station, New Haven, CT) on plant growth using HANPs, ii) Sushil Adhikary, Regent professor, Auburn University (promotion and co-precipitation of slow-release nutrients in biochar), iii) Ivana Miletto (Università del Piemonte Orientale, Italy) on solid-state NMR based characterization of HANPs, and iv) Michele Iafisco (National Research Council, Italy) on the tuning of amorphous phase calcium phosphate synthesis. These four fronts of collaborations are significant and have enhanced the quality of science outcomes on synthesis, characterization, and testing and overall diversifying the use of nano-based fertilizer.

Publications

  • Type: Journal Articles Status: Accepted Year Published: 2021 Citation: Sakhno, Y., Iafisco, M., and Jaisi, D.P. (2021). Role of maturation temperature on structural substitution of carbonate in hydroxyapatite nanoparticles. JOM: Minerals, Metals & Materials Society. DOI: 10.1007/s11837-021-04587-02021.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Wang, P., Sakhno, Y., Adhikari, S., Peng, H, Jaisi, D., Soneye, T., Higgins, B., and Wang, Q. (2021). Effect of ammonia removal and biochar detoxification on anaerobic digestion of aqueous phase from municipal sludge hydrothermal liquefaction. Bioresource Technology, 326, 124730
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: Oginni, O., Yakaboylu, G.A., Singh, K., Sabolsky, E.M., Unal-Tosun, G., Jaisi, D.P., Khanal, S.K., and Shah, A. (2020). Phosphorus adsorption behaviors of MgO modified biochars derived from waste woody biomass resources. Journal of Environmental Chemical Engineering, 8, 103723.
  • Type: Journal Articles Status: Under Review Year Published: 2021 Citation: Unal-Tosun, G., Sakhno, Y., and Jaisi, D.P. Synthesis of hydroxyapatite nanoparticles from phosphorus recovered from animal wastes. ACS Sustainable Chemistry & Engineering (In review).
  • Type: Journal Articles Status: Submitted Year Published: 2021 Citation: Vasylenko, K.V., Sakhno, Y., Jaisi, D.P. and Nikolenko, M.V. Determination of the activation energies of phase transition for calcium orthophosphates based on powder X-ray diffraction data. Nature Scientific Reports (Submitted).
  • Type: Journal Articles Status: Submitted Year Published: 2021 Citation: Sakhno, Y., and Jaisi, D.P. (2021). A novel route to enhance the solubility of apatite: Structural incorporation of sodium and potassium. ACS Agricultural Science and Technology (submitted).
  • Type: Journal Articles Status: Submitted Year Published: 2021 Citation: Anatolii, S., Sakhno, T., Olena, H., and Sakhno, Y. Presowing treatment of vetch hairy seeds (vi?ia villosa) by UV irradiation. Global Journal of Environmental Science and Management (submitted)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Tosun, G., Sakhno, Y., and Jaisi, D.P. Recovery and purification of phosphorus from agricultural wastes for the synthesis of a hydroxyapatite nanofertilizer. Soil Science Society of America Annual Meeting, San Antonio. Nov, 2020.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2021 Citation: Sakhno, Y., and Jaisi, D.P. A novel route to enhance the solubility of apatite: Structural incorporation of protons. 2021 Fall ACS Meeting, Atlanta, GA (abstract accepted).


Progress 05/01/19 to 04/30/20

Outputs
Target Audience:Academics; federal, state, and local governments, and stakeholders on the nutrient management; farmers and commodity groups; for-profit companies for products of commercial interests. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The major opportunities provided to researchers are as follows: Gulcin Tosun (Ph.D. student, intake Fall 2016) is continuing the portion of this project on the extraction of agricultural sources of P from manure and poultry litters and undertaking various wet chemical methods on separation and purification and precipitation into HANPs. She applies conventional and advanced analytical chemistry methods to characterize products (third bullets both in tasks and accomplishments are her outcomes). She presented a talk in SSSA meeting in Nov 2019. Preliminary tests for the dissolution of HANPs with different crystal chemistry are being undertaken. She will continue on the dissolution aspect of this research next year. Yuriy Sakhno (Postdoctoral Associate, start date Fall 2018) is an inorganic chemist and his research focuses on structural modification in apatite to alter the crystal-chemical environment to enhance the solubility of the apatite. He completed research on the cationic substation and now moving into cationic substitution to complete the array of crystal-chemical changes proposed in this project. He is an expert on an array of advanced analytical methods including FTIR, nano-FTIR coupled with AFM, FE-SEM, XRD, and DS-TGA techniques and utilized them to characterize the HANP products. He presented the outcomes in the Fall ACS meeting San Francisco in Aug 2019 and another in PanNano meeting in Brazil 2020. A manuscript is under review in American Mineralogist and the second one is submitted to Physical Chemistry C. He continues to work on this project on various ways to enhancing solubility that is guided from dissolution results. This year, the project has provided the following opportunities to a graduate student and a postdoctoral associate supported by this project: Training and experience on isotope biogeochemistry; refined processing of samples and isotope measurements; ii) honing skills by work closely and train to develop their supervisory and interpersonal skills; iii) further develop management skills by working closely on lab/project management; iv) training students and postdocs on manuscript writing, highlighting key scientific findings; they will be trained on reviewing manuscript and critical thinking skills; v) improving speaking and poster/presentation skills, vi) attending meetings, workshops and discussion forums to broaden the knowledge and to establish connection to peers and professionals. Gulcin successfully completed Ph.D. candidacy exam in Oct 2020. She is excelling on her sills on developing research questions and research hypotheses and testing through experimentations. She received a highly prestigious Doctoral Degree Fellowship from Graduate College of the university- a testament to her quality research and outputs. PIs are highly committed and have track records of taking additional approaches as needed to achieve these goals. How have the results been disseminated to communities of interest?In the second year of the project, outcomes are immerging and the scientific community has recognized the scientific outcomes. As we continue, we will continue to publish scientific findings in peer-reviewed journals, present at the national/international meeting and the conferences. Key interactions include: Three manuscripts prepared: One manuscript under review, second submitted, and the third one in the early stage of preparation (see details in the accomplishment section). One keynote talk, two invited talks, and three volunteered talks delivered in professional society meetings and conferences (see details in the accomplishment section). What do you plan to do during the next reporting period to accomplish the goals?The project is in full swing and a series of experiments and analyses are being done and continue to achieve results to meet the research objectives listed in the third year. Research findings will be disseminated via publication, presentations at professional society meetings, stakeholders at state and regional levels. More training and activities planned in the proposed research will be done as the project continues.

Impacts
What was accomplished under these goals? The second year of the project spread on all three tasks: Task 1 (Synthesis of nano-hydroxyapatite ( HANPs) as a P nano fertilizer), Task 2 (Characterization of HANPs) and Task 3 (Extraction and purification of agricultural waste-derived P and HANP synthesis). Task 4 (Testing efficacy of HANPs as fertilizer) is in the early stage of testing. Major activities include: In Task 1 (and 2). This year the research activities emphasized the cation substation on HANPs. It included the incorporation of sodium or potassium cations as well as carbonate anions in HANP crystallites with an aim to enhance the solubility properties. Three series of sodium/carbonate or potassium/carbonate were doped in HANPs with different extent of substitution in HANPs. A series of advanced characterizations were used including Fourier transform infrared (FTIR) and Raman spectroscopy, differential and gravimetric thermal analysis (DTA-GTA), X-ray diffraction (XRD), and field emission scanning electron microscopy (FE-SEM). A comparison of the shift in (002) reflection in X-Ray diffractograms were made to identify contraction/expansion along the C-axis occurs in the presence of K or Na in the lattice. Relationship of the concentration of carbonate ions in A or B sites as well as selectivity to the number of incorporated K or Na ions developed. Further, the difference in crystal radii between Ca and Na and related chemistry were investigated to develop the probability of incorporating these ions in the lattice. Furthermore, thermal stability was investigated and their conversation temperature to tricalcium phosphate (TCP) - the extent of which increases with higher K/Na incorporation. In Task 3 (and 2): Recovery of P from five different agricultural wastes, particularly from broiler litter and cattle manure, were tested and the feasibility of fabricating into HANPs. The major task was identifying a better method to purify P recovered from these wastes. Among two strategies: i) removing contaminants (partially precipitation of contaminants, cation resin exchange), and selectively recover P (precipitation of P at acidic and alkaline pH, anion resin exchange), alkaline pH precipitation appears more promising. HANPs synthesized from partially purified P were tested for crystal chemistry, crystallinity, and morphology using XRD, FTIR, TGA, and SSA. Methods are being revised for finding the optimal method of purity needed for the acceptable HANP. The major research findings include: Key research findings of this project year include: Clear evidence that carbonate incorporation in the crystal lattice by saturation of phosphoric acid with CO2, prior to the precipitation. The extent of carbonation depends mainly on the temperature of maturation rather than on the concentration of carbonate present in the reaction. A manuscript is submitted for peer review from this research. Cation substitutions of highly soluble monovalent atoms (Na and K) are possible. Even though crystal radii Na and K are larger than Ca they still can enter the P63/M lattice; thus, increasing the number of defects and potentially promoting higher dissolution properties. A manuscript draft is being prepared. Among various preprocessing methods, ammonium phosphomolybdate precipitate is the single-step reaction to best remove contaminants. HANPs could be synthesized using P extracted from broiler litter, but the purity of the product is strongly controlled by the composition of impurities, which is directly related to the P recovery method. A manuscript is under preparation from the outcomes obtained from this research. New collaborations established: Dr. Jason White, Director of Connecticut Agricultural Experimentation Station The collaborative research established is for the comparative analyses of HANPs with different crystal chemistry (Tasks 1 and 2). Preliminary plant growth experimentation is being undertaken in CT. Drs. Weiming Shi and Shenqiang Wang, Professors at Institute of Soil Sciences, Chinese Academy of Sciences, Nanjing, China Collaborative research initiated on the controlled release fertilizers and testing on field plots. Two representative abstracts, one from the submitted manuscript and other from conference presentation are included below: Carbonated Hydroxyapatite: Effect of temperature of crystallization on carbonate uptake (In revision to: American Mineralogist) Hydroxyapatite nanoparticles (HANPs) have been recently advocated as a potential novel fertilizer that could be modified to nutrient need dynamics of plants through a controlled release of phosphorus (P). To increase P release efficiency, the solubility of HANPs can be tuned by doping carbonate into the crystal lattice. In the present study, we aimed to enhance the carbonate content in the HANP structure. To achieve this goal, we synthesized HANPs from an aqueous solution of calcium hydroxide and CO2 enriched phosphoric acid followed by subsequent maturation at three different temperatures. The FTIR, nano-FTIR coupled with AFM, FE-SEM, XRD, and DS-TGA techniques were used to characterize the products. Maturation at 45 oC leads to the replacement of all columnar hydroxyls by carbonate (A-type) in HANPs, while B-type is dominant at higher temperatures. These results provide clear evidence that carbonate incorporation in the crystal lattice by saturation of phosphoric acid with CO2, prior to the precipitation, depends mainly on the temperature of maturation rather than on the concentration of carbonate present in the reaction. The ability to vary carbonate content facilitates enhancing the dissolution rate of P, a needed change for optimizing HANPs as potential controlled-release fertilizers. Nutrient use efficiency: Current challenge and promise of controlled-release fertilizers Keynote talk in International Conference on Agriculture & Food Technology, Bangkok, Thailand, Sept 14-17, 2019. Modern agriculture has arrived at the crossroad of conflicting problems of keeping up of supplant food production and yet protecting water quality. Intensive agriculture and multiple cropping systems have significantly increased annual productivity but drastically decreased the nutrient use efficiency. The lost nutrient in the soil is partly leached to open water and caused a series of environmental problems, including eutrophication and dead zone. Slow and controlled release fertilizers are developed as efforts towards minimizing the usage of natural resources and maximizing plant uptake. My research team undertakes the fundamental research that includes tuning the chemical properties of potential fertilizers to control the rate of release of nutrients and track transfer and transformation in soils and waters. For phosphate fertilizer, struvite and apatite are candidate minerals, which are synthesized from phosphorus recovered from agricultural wastes and wastewater. Various surface properties, including size, shape, and surface morphologies and crystal-chemical and structural properties, including cation/anion substitutions and structural defects, are studied and control of these factors on phosphorus release kinetics is being evaluated. Optimizing these properties to tune the temporal need of phosphorus during plant growth is the ultimate key to the development of ideal controlled-release fertilizer and improved nutrient use efficiency. These efforts will eventually contribute to agricultural sustainability.

Publications

  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2019 Citation: Invited talk: Sakhno, Y., Iafisco, M., Martra, G., Unal-Tosun, G., Jaisi, D. Synthesis and characterization of nanoapatite: a promising controlled-release fertilizer. PanNano 2020 meeting, Sao Paolo, Brazil, Mar 2020.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2019 Citation: Invited talk: Shi, W., Min, J., Yan, T., Qiao, Q., Ma, Y., Jaisi, D.P., and Hu, H. Emission flux of fertilizer nitrogen to the environment and its control technology in the lower Yangtze region of China. Soil Science Society of America Annual Meeting, San Antonio. Nov 10-14, 2019.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2020 Citation: Sakhno, Y., Unal-Tosun, G., Iafisco, M., Martra, G., Jaisi, D. Incorporation of sodium and potassium into carbonated apatite crystals. PanNano 2020 meeting, Sao Paolo, Brazil, Mar 2020.
  • Type: Journal Articles Status: Under Review Year Published: 2020 Citation: Sakhno, Y., Iafisco, M., and Jaisi, D.P. Carbonated hydroxyapatite: Effect of temperature of crystallization on carbonate uptake. American Mineralogist (In review).
  • Type: Journal Articles Status: Submitted Year Published: 2020 Citation: Sakhno, Y., Gianmario, J., Iafisco, M., and Jaisi, D.P. Cation sustiutution and changes in until cell in A- and B-type carbonated hydroxyapatite. Crystal Chemsitry C (Submitted).
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2019 Citation: Keynote talk: Jaisi, D.P. Nutrient use efficiency: Current challenge and promise of controlled-release fertilizers. International Conference on Agriculture & Food Technology, Bangkok, Thailand, Sept 14-17, 2019
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2019 Citation: Tosun, G., Sakhno, Y., and Jaisi, D.P. Recovery and purification of phosphorus from agricultural wastes for the synthesis of a hydroxyapatite nanofertilizer. Soil Science Society of America Annual Meeting, San Antonio. Nov, 2019.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2019 Citation: Sakhno, Y., Tosun, G., and Jaisi, D.P. Carbonated hydroxyapatite: Effect of crystallization temperature on carbonate content. 2019 Fall ACS Meeting, San Diego, CA Aug, 2019.


Progress 05/01/18 to 04/30/19

Outputs
Target Audience:Academics; federal, state, and local governments, and stakeholders on the nutrient management; farmers and commodity groups Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The major opportunities provided to researchers are as follows: 1. Gulcin Tosun (Ph.D. student, intake Fall 2016) undertaking the portion of this project on the extraction of agricultural sources of P from manure and poultry litter and fabricate into nanofertilizer. She applies conventional and advanced analytical chemistry methods. She submitted an abstract in another aspect of her research outcomes and is going to be presented in the in SSSA meeting in Nov 2019. She will continue on the dissolution aspect of this research next year. 2. Yuriy Sakhno (Postdoctoral Associate, start date Fall 2018) is an inorganic chemist and his research focuses on structural modification in apatite to alter crystal chemical environment to enhance the solubility of the apatite. He employs a series of advanced analytical methods including FTIR, nano-FTIR coupled with AFM, FE-SEM, XRD, and DS-TGA techniques to characterize the products. The outcome of his research is going to be presented at the Fall ACS meeting in Aug 2019. A manuscript was submitted to Physical Chemistry C. He continues to work on this project on various ways to enhancing solubility in the next project year. This year, the project has provided the following opportunities to a graduate student and a postdoctoral associate supported by this project: Training and experience on isotope biogeochemistry; refined processing of samples and isotope measurements; ii) honing skills by work closely and train to develop their supervisory and interpersonal skills; iii) further develop management skills by working closely on lab/project management; iv) training students and postdocs on manuscript writing, highlighting key scientific findings; they will be trained on reviewing manuscript and critical thinking skills; v) improving speaking and poster/presentation skills, vi) attending meeting, workshops and discussion forums to broaden the knowledge and toestablish connection to peers and professionals. Gulcin is undergoing a Ph.D. candidacy exam and is being trained on developing research questions and research hypotheses and writing the research proposal. Both PIs are highly committed and have track records of taking additional approaches as needed to achieve these goals. How have the results been disseminated to communities of interest?This is the first year of the project and the early outcome of the research are beginning to immerge. As we continue, we will continue to publish scientific findings in peer-reviewed journals, present at the national/international meeting and the conferences. Key interactions include: One manuscript submitted for review (in Physical Chemistry C) (see details in the accomplishment section). Two volunteered talks by a graduate student and a postdoctoral associate in the project (see details in the accomplishment section). What do you plan to do during the next reporting period to accomplish the goals?The project has taken momentum and a series of experiments and analyses are being done and continue to achieve results to meet the research objectives listed in the second and future years. Research findings will be disseminated via publication, presentations at professional society meetings; stakeholders at state and regional level. Both PIs are dedicated to training a highly skilled workforce. More training and activities planned in the proposed research will be done as the project continues.

Impacts
What was accomplished under these goals? The first year project worked partly on Task 1 (Synthesis of HANPs as a P nanofertilizer), Task 2 (Characterization of HANPs) and Task 3 (Extraction and purification of agricultural waste-derived P and HANP synthesis). Major activities include: In Task 1 (and 2). Three types of pure HANP were synthesized using reagents and maturated individually at 45, 95, 150 oC for 24 h with the presence of CO2. All products were washed at the isoelectric point of apatite (8.2). Analyses included FTIR in Nicolet 380 spectrometer with Attenuated Total Reflectance (ATR) cell for the infrared spectra; specific surface area (SSA) was measured with a Micromeritics ASAP 2020 by nitrogen adsorption at 77 K following the BET method, Ca/P ratio was determined by inductively coupled plasma-optical emission spectrometry (ICP-OES, Liberty 200, Varian). X-ray diffraction (XRD) patterns of the HANP powders were recorded by Bruker D8 equipped with a high-speed X'Celerator detector powder diffractometer using CuKa radiation and surface morphology was studied by the field emission scanning electron microscopy (AURIGA 60 Crossbeam FE-SEM). Similarly, carbonate content was estimated using a Thermal Analysis SDT Q 600 (TA Instruments). In Task 3 (and 2): Recovery of P from agricultural wastes, particularly from broiler litter and cattle manure were tested and the possibility of fabricating into HANPs. Three different wastes were extracted with four different methods and three different methods of treatments to remove/minimize contaminant. The HANP synthesized from partially purified P was tested for crystal chemistry, crystallinity, and morphology using XRD, FTIR, TGA, and SSA. Methods are being revised for finding the optimal method of purity needed for the acceptable HANP. The major research findings include: Two representative abstracts from the submitted manuscript and professional society meeting are included below: Carbonated Hydroxyapatite: Effect of temperature of crystallization on carbonate uptake (Submitted to: Physical Chemistry C) Hydroxyapatite nanoparticle (HANP) have been studied as a novel fertilizer that could potentially provide increased efficiency through controlled release of phosphorus (P). To increase P release efficiency, the solubility of HANP particles can be tuned by doping carbonate to the crystal lattice. In present studies, we synthesized carbonated HANPs by chemical precipitation method through an aqueous solution of calcium hydroxide and phosphoric acid at different temperatures at a constant CO2 gas bubbling. The FTIR, nano-FTIR coupled with AFM, FE-SEM, XRD, and DS-TGA techniques were used to characterize the products. Our results show that crystallization of HANP from the same reactant mixture over different temperatures affects both, morphology and carbonate content in the crystal structure. Relative preference for forming A-type of carbonates in HANP was stimulated by crystallization at 45 oC while at 95 and 150 oC lead to the formation of hydroxyls instead. This work provides new insights into the role of the temperature of crystallization on carbonate uptake and morphology of particles. Recovery and purification of phosphorus from agricultural wastes for the synthesis of a hydroxyapatite nanofertilizer (Abstract submitted to Soil Science Society of America Annual Meeting, Nov 2019). When phosphorus (P) is applied to crop plants as fertilizers and animal wastes or supplied as foods to poultry and cattle, a significant fraction is lost to the environment. The lost P impairs agroecosystems and water bodies. To minimize the ecosystem damage, there is a renewed call on devising new approaches that have higher efficiency to recover P. In this study, we aimed to recover P from agricultural wastes, particularly from broiler litter and cattle manure, and fabricate it into a potential nano-fertilizer: hydroxyapatite nanoparticles [HANPs: Ca10(PO4)6(OH)2]. The novelty of HANPs arises from the unique structure with tunable properties such as crystal chemistry, crystallinity, and morphology. Our preliminary results suggest that HANPs could be synthesized using P extracted from broiler litter but the purity of the product is strongly controlled by the P recovery method. Direct precipitation of HANPs without concentrating P or removing contaminant ions compromises the yield and purity. However, if P is selectively concentrated and contaminants are decreased, both the yield and the purity of the HANPs improves. Furthermore, properties of HANPs such as crystallinity and morphology are controlled by experimental conditions during the synthesis (undergoing experiments). Overall, these encouraging results suggest that the recovery of P from agricultural wastes and recycling as a potential P nanofertilizer is feasible and could make a contribution to environmental stewardship.

Publications

  • Type: Journal Articles Status: Submitted Year Published: 2019 Citation: Sakhno, Y., Iafisco, M., and Jaisi, D.P. Carbonated Hydroxyapatite: Effect of temperature of crystallization on carbonate uptake. Physical Chemistry C (submitted).
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2019 Citation: Sakhno, Y., Tosun, G., and Jaisi, D.P. Carbonated hydroxyapatite: Effect of crystallization temperature on carbonate content. 2019 Fall ACS Meeting, San Diego, CA Aug, 2019 (accepted abstract).
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2019 Citation: Tosun, G., Sakhno, Y., and Jaisi, D.P. Recovery and purification of phosphorus from agricultural wastes for the synthesis of a hydroxyapatite nanofertilizer. Soil Science Society of America Annual Meeting, San Antonio. Nov, 2019 (accepted abstract).