Source: LEHIGH UNIVERSITY submitted to NRP
MECHANOCHEMICAL SYNTHESIS OF NITROGEN EFFICIENT FERTILIZER MATERIALS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
AFRI COMPETITIVE GRANT
Reporting Frequency
Annual
Accession No.
1022563
Grant No.
2020-67022-31144
Cumulative Award Amt.
$434,809.00
Proposal No.
2019-06407
Multistate No.
(N/A)
Project Start Date
Jun 1, 2020
Project End Date
May 31, 2025
Grant Year
2020
Program Code
[A1531]- Biorefining and Biomanufacturing
Recipient Organization
LEHIGH UNIVERSITY
526 BRODHEAD AVE
BETHLEHEM,PA 18015
Performing Department
Chemical Engineering
Non Technical Summary
Stringent environmental regulations and population growth are necessitating a significant increase in crop production while minimizing applied nitrogen (N) fertilizer reactive loss in the environment. This work will synthesize multifunctional N-efficient ionic urea and ammonium carbonate co-crystals using green mechanochemical methods based on abundant minerals and inorganic salts to achieve a symbiotic relationship between N fertilizer use and farming using minerals as a nutrient source. In particular, the proposed work will synthesize urea and ammonium carbonate cocrystals using macronutrient Mg- and Ca-salts, such as the corresponding chlorides, nitrates, sulfates and phosphates. It will further synthesize cocrystals of micronutrient Cu and Zn with urea using chloride, nitrate, sulfate and phosphate Cu and Zn salts as well as Cu and Zn-bearing minerals. It will utilize mechanochemistry to obtain soluble potassium (K) from insoluble K-bearing minerals. Finally, it will synthesize urea cocrystals with abundant drywall gypsum waste. NH3 emission properties will be tested in the lab while suitability of these cocrystals as fertilizer materials will be tested for N-efficiency followed by the greenhouse experiments. The ultimate goal is to reduce nitrogen gas loss from the non-point sources (agricultural fields) into the air and watershed while also avoiding the use of synthetic organophosphorus compounds currently used to inhibit soil enzymes. The societal benefits realized will be (a) reducing nutrient runoff from agricultural nonpoint sources thus (b) decreasing energy requirements needed for treatment of such wastewater and consequentially (c) significantly improving and simplifying management practices of nonpoint sources with up to 30% more nutrients becoming more available to the crops.
Animal Health Component
10%
Research Effort Categories
Basic
80%
Applied
10%
Developmental
10%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
40252102020100%
Knowledge Area
402 - Engineering Systems and Equipment;

Subject Of Investigation
5210 - Fertilizers;

Field Of Science
2020 - Engineering;
Goals / Objectives
The major goal is to advance farming with rocks and minerals concept by combining prevalent nitrogen fertilizer - urea - with the widely available raw minerals using sustainable and scalable mechanochemical methods. We posit that a paradigm shift from organophosphorus synthetic urease and nitrification inhibitors towards natural mineral derived urea and NH4+ co-crystals synthesized using green mechanochemical methods will decrease N losses into sensitive air, inland and marine water bodies while also enhancing other macronutrient (Ca, Mg, S) and micronutrient availability and solubility.Objective 1 is to develop a library of urea cocrystal materials containing all macro nutrients (N, P, K, Ca, Mg and S) and some micro nutrients, such as Zn and Cu among them, known to inhibit urease activity performed in Tasks 1, 2, 3 and 4.Under Task 1 we will perform Ca, Mg, K containing urea and NH4+ cocrystal synthesis from salts. Task 1 deliverables will be conversion degree of particular mineral, crystalline patterns, solubility and thermal stability properties of MgCl2*x urea, CaCl2*x urea, Mg(NO3)2*x urea, Ca(NO3)2*x urea, MgSO4*x urea, CaSO4*x urea, MgHPO4*x urea and CaHPO4*x urea where x-varying stoichiometry. Additionally, the same properties for (NH4)2CO3 milled materials.Under Task 2 we will perform micronutrient containing urea cocrystal synthesis from salts. Task 2 deliverables will be synthesized cocrystals and corresponding crystalline patterns, solubility and thermal stability properties of ZnCl2*x urea, CuCl2*x urea, Zn(NO3)2*x urea, Cu(NO3)2*x urea, ZnSO4*x urea, CuSO4*x urea, ZnHPO4*x urea and CuHPO4*x urea synthesized from salts.Under Task 3 we will extract potassium from siliceous matrix using mechanochemistry to synthesize potassium containing urea cocrystals. Task 3 deliverables will be quantified extracted (soluble) K amount and optimized extraction conditions using mica and K-feldspar as K-source.Under Task 4 we will perform urea cocrystal synthesis from nutrient containing minerals (non salts) using mechanochemistry. Deliverables will be mineral conversion degree, crystalline patterns, solubility and thermal stability properties of ZnCl2*x urea, CuCl2*x urea, Zn(NO3)2*x urea, Cu(NO3)2*x urea, ZnSO4*x urea, CuSO4*x urea, ZnHPO4*x urea and CuHPO4*x urea derived from minerals (non salts).Objective 2 is to determine their agricultural performance on a mesocosm scale and N-emission properties in the lab performed in Task 5 and 6.Under Task 5 we will engineer and scale up CaSO4*4urea cocrystals using drywall gypsum waste. Deliverables will be optimized extrusion parameters (T, P, moisture content) for obtaining CaSO4*4urea pellets via extrusion.Under Task 6 we will measure nitrogen compound emission and agrochemical testing of urea cocrystals. Deliverables will be quantified data of NH3 and N2O emissions from cocrystals compared to pure urea and biomass, soil and leachate measurements for N content and mass balance. Co-crystal urea will be evaluated based on total biomass produced and mass of N leached.
Project Methods
Mechanochemistry and crystal structure testing. In a typical procedure, a total of 200 mg to 400 mg sample of Ca or Mg precursor (oxide, hydroxide or carbonate) and urea with the corresponding molar ratios will be loaded into a 15 mL stainless steel jar together with three individual 8 mm stainless steel balls and grounded for up to 10 mins at 26 Hz in a Retsch MM300 mixer mill. Liquid assisted grinding (LAG) will be utilized due to the high crystalline water content in the products. All samples will be air dried before pXRD analysis.We will obtain pelletizing extruder equipped with a rotary cutter.It will be used to mix and extrude drywall gypsum and urea powder into a cocrystal.The final die configuration will be determined in conjunction with final formulation of powder urea to gypsum 4:1 molar ratio, to be determined moisture content to initiate the reaction at the crystalline boundary and temperature. The latter will be capped at ~70 oC to minimize any urea decomposition. Trials with few different dies with varying thickness, open area and hole diameter will be performed to obtain CaSO4*4urea cocrystal 4 mm diameter pellets. Extruder will produce 50 g batches but can achieve upwards of 40 lb/hr output on a continuous basis as well.Powder X-ray diffraction (pXRD) analysis. To determine the crystalline identity of the mechanochemical product and the overall conversion of the reactants (MAP, Ca- and Mg-hydroxides, oxides, carbonates and water), pXRD analysis (Empyrean, PANalytical B.V.) will be performed. The applied current will be 40 mA and the applied voltage was 45 kV. The X-ray mirror that will be used is a graded, flat Bragg-Brentano HD mirror, and the step size that used for the measurements is 0.0131 degrees.Thermal analysis. Simultaneous measurement of weight change (TGA) and differential heat flow (DSC) will be assessed using SDT-Q600, TA Instruments. During TG/DSC measurements, heating rate of 10 oC/min will be used under N2 flow of 100 ml/min.Dynamic vapor sorption analysis. The DVS Intrinsic (Surface Measurement Systems Ltd, USA) equipped with SMS UltrabalanceTM with a mass resolution of ±0.1 µg will be used to obtain ramping and equilibrium water vapor sorption isotherms. Approximately 5 mg of powder will be placed in an aluminum pan in the apparatus and initially dried over 600 minutes with a stream of dry nitrogen to establish a dry mass at 25 oC. The dry mass will be calculated after the end of first drying stage (~0 % RH). The sorption cycle experiments will be performed from 0 % relative humidity (RH) to 90 % RH in a step of 10 % in a preprogrammed sequence, before decreasing to 0 % RH in a reverse order. The instrument maintained a constant target RH until the moisture content change per minute (dm/dt) was less than 0.002 % per minute over a 10 minute period. DVS curves will be obtained in at least triplicate from three independent samples.We will evaluate the propensity of urea cocrystals towards decreased NH3 emissions using NH3 scrubbing with boric acid. Urea experiments will be used as a benchmark, applied with 1 mg N/gram soil to normalize the data. We will perform said experiments using controlled relative humidity (RH) to be able to assess NH3 emission kinetics using natural soil samples under simulated conditions from 20 to 95 % RH at room temperature. The absorbed NH3 will form aqueous NH4+ ion and will be measured using an existing ion chromatograph via procedures well established in the lab. The data measured will be used to build a library of urea co-crystal stability in soil under simulated environmental conditions.Agrochemical testing will be performed in 2 phases. The phase 1 experiment will measure N-dynamics and urease activity. The phase 2 measure the ability for the co-crystals to supply adequate N while reducing N loss, the experiments will also measure N-dynamics, urease activity and fertilizer efficacy as compared to urea, slow release urea and no fertility at all. The polymer coated urea will provide sufficient N throughout the growth cycle and will be the positive control to see if the co-crystals are as good or better.Phase 1. Initial screening will be conducted for all co-crystals, urea and polymer coated urea according to the following procedure. Co-crystals will be mixed at a rate of 200 ppm N with field moist soils at 1/3 bar and incubated at 23 oC for 24 hours. After incubation the soil will be packed into a glass column. The column will be uniformly packed with 2 cm of clean washed silica sand followed by the incubated soil and urea and 2 cm of washed silica sand. The column will then be leached with DI water to which NaCl and CaCl2 have been added to achieve an EC of 1 and an SAR of 2. Solution will be applied to maintain a constant linear flux. A total of 10 pore volumes will be leached and column leachate will be collected in a fraction collector. Samples will be analyzed for total N, NH4-N, NO3-N and urease activity. Total N will be determined using chem luminescence. Ammonium and NO3 will be determined using segmented flow and urease activity will be determined using ELISA. Data will be fit to a breakthrough model for all N species. Nitrogen species will be normalized by dividing total N leached by pore volumes required for breakthrough multiplied by total urease concentration in the leachate. The normalization will allow for the comparison of all co-crystals produced against commercially available urea sources. In addition, the incubation followed by flow through measurement will provide an environmentally relevant surrogate to assess urea stability.Phase 2. The best performing urea co-crystals will be further evaluated as a fertilizer. Fertilizer evaluation will be conducted in a greenhouse. Native soils will be collected from the University of Arizona Maricopa Agricultural research station. Forage Bermuda grass will be grown in 9" pots with 5 replicates per treatment. Fertilizer treatments will be applied once at sewing. Fertilizer treatments will include all 5 urea co-crystals, urea (positive control), polymer coated urea (positive stabilized control), and no added N (negative control). Nitrogen application rates will be equivalent to the cooperative extension recommended rate (1X), half the recommended rate (0.5x) and twice the recommended rate (2X). Bermuda grass will be grown for 3 months with a leaching fraction of 0.5 to ensure significant N leaching losses from the positive control. All leachate will be collected and analyzed for N loss. After 3 months the grass will be harvested, and total biomass measured. Biomass, soil and leachate will be measured for N content and mass balance will be determined. Co-crystal urea will be evaluated based on total biomass produced and mass of N leached. The statistical design will be a completely randomized comparing the urea co-crystals to urea, slow release polymer coated urea and no fertilizer. The statistical analysis will be a multivariate analysis of variance with post hoc tests to compare means.Efforts will focus on extension and outreach towards mineral fertilizer producing facilities as well as Pennsylvania farmers to introduce the urea cocrystal concept into the production chain.Evaluation plan will include assessing the nitrogen gas emissions of urea cocrystals and proposing new designs in Tasks 1, 2 and 4. Evaluation studies will include: NH3 and N2O emission measurements of the cocrystal materials using infrared spectroscopy. The measurable target will be min 30% emission reduction from pure urea at high (>75 %) relative humidity.

Progress 06/01/24 to 05/31/25

Outputs
Target Audience:-the academic audience reached within the conferences and publications described under Accomplishments. Briefly, 9 publications, 2seminar presentations. -industrial entities including ICL Group Ltd (formerly Israel Chemicals Ltd.) that entered a testing agreement on the developed urea cocrystals. -broader audience inInternational conference on Fertilizers from waste: Recovering and reusing nutrients via circular processing of agricultural residues, Lincoln, Nebraska, US -international audience in Embrapa Instrumentacao (Sao Carlos, Brazil), University of Ribeirão Preto (Brazil), Federal University of Sao Carlos (Brazil) and USDA ARSvia newly established collaborations Changes/Problems:Rather than the extruder granulator as initially thought, we procured a double roller granulator to make cocrystal granules via force which can also be replicated on a small scale in the laboratory. What opportunities for training and professional development has the project provided?Three early career postdoc students at Lehigh finalized this project and obtained training in the synthesis and characterization of agricultural fertilizer materials and their laboratory and field testing. How have the results been disseminated to communities of interest?The academic audience reached within the conferences and publications.Briefly, 9 publications, 2seminar presentations. With colleagues at Nebraska University Lincoln and USDA ARS we organized and obtained funding from USDA NIFA and OECD forNebraska Water Center and USDA-ARS co-hosted Fertilizers from Waste conference (https://watercenter.unl.edu/news/nebraska-water-center-and-usda-ars-co-hosted-fertilizers-waste-conference/). What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Objective 1 Task 1. A series of Mg and Zn-containing urea salts were synthesized mechanochemically in the form of a solid solution of ZnSO4*x urea andCuSO4*x urea. Extensive physicochemical characterization was performed including XRD, elemental analysis, BET, Raman, TGA/DSC as well as nitrogen emission experiments in soil and bactericidal evaluation. Task 2. ZnSO4*x urea, CuSO4*x urea cocrystals made from pure salts (ZnSO4 and CuSO4) using solid-state mechanochemistry. Physicochemical characterization was performedas well as N emission tests. Task 3. nothing to report Task 4. ZnSO4*x urea, CuSO4*x urea cocrystals were made from CuO, CuCO3 and ZnO, ZnCO3 using urea*H2SO4 cocrystals using solid-state mechanochemistry. Physicochemical characterization and N emission tests were performed. Task 5+Task 6. Several 100-gram batches were synthesized. ZnSO4*x urea, CuSO4*x was sent to the USDA ARS for plant biomas production and respiration testing. These resulted in the manuscriptACS Sustainable Resour. Manage. 2024, 1, 7, 1363-1376. We also delivered several review articles to describe current status of the nitrogen efficient materials and cocrystals for agriculture in particular (DOI10.1088/2977-3504/adc0a8;doi.org/10.1016/j.scenv.2025.100209;?DOI:10.1039/D4SU00635F)

Publications

  • Type: Peer Reviewed Journal Articles Status: Published Year Published: 2025 Citation: J�lia Farias, Matthew Conley, Matthew Herritt, et al. Assessment of engineered sustainable nitrogen fertilizers on lettuce development using physical sampling and image-based phenotyping. ESS Open Archive . April 22, 2025. DOI: 10.22541/essoar.174534253.32974943/v1
  • Type: Peer Reviewed Journal Articles Status: Published Year Published: 2025 Citation: Katarzyna Chojnacka and Jonas Baltrusaitis 2025 Sustain. Sci. Technol. 2 022001 DOI 10.1088/2977-3504/adc0a8
  • Type: Peer Reviewed Journal Articles Status: Published Year Published: 2025 Citation: Mohamed Eisa, Mariana Brondi, Clinton Williams, Reagan Hejl, Jonas Baltrusaitis, From urea to urea cocrystals: A critical view of conventional and emerging nitrogenous fertilizer materials for improved environmental sustainability, Sustainable Chemistry for the Environment, Volume 9, 2025, 100209, ISSN 2949-8392, https://doi.org/10.1016/j.scenv.2025.100209.
  • Type: Peer Reviewed Journal Articles Status: Published Year Published: 2024 Citation: ACS Sustainable Resour. Manage. 2024, 1, 7, 13631376
  • Type: Conference Papers and Presentations Status: Published Year Published: 2024 Citation: 2. Jonas Baltrusaitis, Solid nitrogen fertilizer recovery from liquid biogenic waste: from new concepts to new technology, OECD Fertilizers to waste conference, University of Nebraska-Lincoln, Lincoln, Nebraska, September 9-12, 2024 (keynote).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2025 Citation: 24. Mohamed Ammar, Jonas Baltrusaitis, Effect of biochar on the thermal stability and storage conditions optimization of magnesium ([NH4]2Mg[CO3]2?4H2O), copper ([NH3]2Cu(CO3)) and zinc ((NH3)Zn(CO3)), Lehigh Institute of Functional Materials 2025 symposium, 05/05/2025.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2024 Citation: 32. Reagan Hejl, Dovile Ragauskaite, Julia Farias, Clinton F Williams, Jonas Baltrusaitis, Production and Characterization of a New N-Efficient Fertilizer Recovered from Solid Waste, 2024 ASA, CSSA, SSSA International Annual Meeting, November 10-13, 2024, San Antonio, Texas. USA.
  • Type: Peer Reviewed Journal Articles Status: Published Year Published: 2025 Citation: RSC Sustainability,2025,3,781803 | 781
  • Type: Peer Reviewed Journal Articles Status: Published Year Published: 2025 Citation: DOI: 10.1039/D4VA00197D (Critical Review) Environ. Sci.: Adv., 2025, 4, 77-89
  • Type: Peer Reviewed Journal Articles Status: Published Year Published: 2024 Citation: Ammar, M., Dambrauskas, T., Parvin, S. et al. In situ analysis of magnesium ([NH4]2Mg[CO3]2�4H2O), copper ([NH3]2Cu(CO3)), and zinc ((NH3)Zn(CO3)) ammonium carbonate thermal properties. J Therm Anal Calorim 150, 15571569 (2025). https://doi.org/10.1007/s10973-024-13878-y
  • Type: Peer Reviewed Journal Articles Status: Published Year Published: 2024 Citation: Ammar, M.; Yousef, E.; Ashraf, S.; Baltrusaitis, J. Removal of Inorganic Pollutants and Recovery of Nutrients from Wastewater Using Electrocoagulation: A Review. Separations 2024, 11, 320. https://doi.org/10.3390/separations11110320
  • Type: Peer Reviewed Journal Articles Status: Published Year Published: 2024 Citation: Hejl, R. W., Farias, J., Baltrusaitis, J., Williams, C. F., Eisa, M., Ragauskait?, D., & Serba, D. D. (2024). Urea Cocrystals as a Potential Fertilizer for Turfgrass: Responses of Tifway Hybrid Bermudagrass and Nitrogen Release Behavior. HortTechnology, 34(4), 474-480. Retrieved May 27, 2025, from https://doi.org/10.21273/HORTTECH05423-24


Progress 06/01/20 to 05/28/25

Outputs
Target Audience:-the academic audience reached within the conferences and publications described under Accomplishments. Briefly, 30 publications, 17seminar presentations were used to reach out to the academic audience during the duration of the project. We were very productive during our project and are grateful for this funding since 2020 -industrial entities including ICL Group Ltd (formerly Israel Chemicals Ltd.) that entered a testing agreement on the developed urea cocrystals. -broader audience in International conference on Fertilizers from waste: Recovering and reusing nutrients via circular processing of agricultural residues, Lincoln, Nebraska, US -international audience in Embrapa Instrumentacao (Sao Carlos, Brazil), University of Ribeirão Preto (Brazil), Federal University of Sao Carlos (Brazil) and USDA ARS via newly established collaborations, Kaunas University of Technology in Lithuania. -other industrial entities were also a target audience, including Harrell's in the USA, OCP in Morocco and SABIC chemical product company. A pivotal patent was grantedUS20250042823A1that allowed for commercialization inquiesfrom the above mentioned industrial entities Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?These primarily focused on training graduate students and postdocs at Lehigh University in novel synthesis methods of urea and ammonium salt cocrystal synthesis and characterization. The synthesized materials were tested in multitude of field locations, USDA ARS or New Mexico State University where graduate students, postdocs and scientists developed procedures for novel nitrogen efficient material testing. On a broader note in a unique training opportunity, with the help of additional USDA NIFA and OECD funding, we organized together with the Nebraska Water Center and USDA-ARS co-hosted Fertilizers from Waste conference.On September 10-12, 2024, the Nebraska Water Center and the United States Department of Agriculture's Agricultural Research Service (USDA-ARS) co-hosted a conference titledFertilizers from waste: Recovering and reusing nutrients via circular processing of agricultural residues.This conference was sponsored byOrganisation for Economic Co-operation and Development(OECD)Co-operative Research Programme: Sustainable Agricultural and Food Systems and by theUSDA National Institute of Food and Agriculture (USDA-NIFA)Engineering for Agricultural Production and Processing program (grant no. 2024-67021-43747). An interdisciplinary team of researchers Prof.Chittaranjan Rayand Dr.Lisa Durso(University of Nebraska), ProfessorJonas Baltrusaitis(Lehigh University), Drs.Clinton WilliamsandJulia Stiles(USDA ARSWater Management) secured the funding and organized the meeting. The Fertilizers from Waste conference catalyzed collaboration between professionals developing technology and those building the infrastructure that will support the adoption and implementation of the new fertilizer products, technologies, and processes. The conference was designed to share expertise and further advance on research of the following topics: Engineering and new fertilizer technologies Prospects and applications on nutrients recovery Risk assessment and fertilizer management Mineral nutrition, soil health, and environmental sustainability The Fertilizers from Waste conference included presentations from more than fifteen experts from eight countries. Speakers and attendees were a mix of engineers, agricultural scientists, practitioners, stakeholders, such as farmers or biogas producers, and mineral and organic fertilizer producers. The conference discussed the potential and implications of opportunities, challenges, and timeline of transitioning, partially or fully, from mineral derived fertilizers to waste derived fertilizers. The focus of the conference was to bring together innovative yet applied problem solvers in the realms of policy, engineering, sustainability, microbiology, and soil health. The three-day conference included presentations from experts around the globe, brainstorming and collaborative sessions, and a half-day visit to Husker Harvest Days, a unique experience for the international visitors. How have the results been disseminated to communities of interest?30 publications and 17seminar presentations were used to reach out to the academic audience during the duration of the project. Plenty of industrial interactions also occurred with broad interest from ICL Inc, OCP, Herrell's SABIC and smaller US based and internation companies were engaged. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Briefly, 30 publications and 17seminar presentations were used to reach out to the academic audience during the duration of the project. To summarize: -we developed under Objective 1 a series of urea and ammonium containing cocrystals from (a) nutrient containing salts and urea or ammonium carbonate and (b) nutrient containing minerals, such as oxides, carbonate and hydroxide and urea or ammonium carbonate. The latter was achieved using urea acids, e.g. urea sulfate or urea phosphate, as raw materials. As proposed in the original proposal, the family of cocrystals we developed contains N, P, K, Mg, Ca and S and includes such popular inorganic materials cocrystalized with urea as gypsum andtriple superphosphate, among others. All the synthesis procedures developed relied on dry mechanochemical milling thus fundamentally changing how novel fertilizer compounds are synthesized. -additionally, we explored and developed under Objective 1 a series of urea containing cocrystals with micronutrients that also can act as mild urease inhibitors. Those included Zn and Cu salt sulfates as well as minerals, such as the corresponding carbonates. All the synthesis procedures developed relied on dry mechanochemical milling thus fundamentally changing how novel fertilizer compounds are synthesized, to convert Zn and Cu carbonates we used urea acid precursors which are commercially available, such as urea phosphate, but have little direct applicability due to their corrosive properties. We dedicated our efforts on non-Cl containing cocrystals since in consultation with out USDA ARS colleagues found out that large amount of chlorine will negatively affect the plants. -under Objective 2, we performed scale up of many cocrystal formulation in planetary and large conventional ball mill which eliminated the need for extrusion (although extrusion experiments were also performed). This was an important milestone to generate 100s of gram batchesfor pot and field experiments, nitrogen emission testing, soil metabolization experiments and, most importantly, overall mass and quality of the variety of crops produced. For example, our recent scaled up materials were tested at collaborators from USDA ARS on lettuce growth since lettuce is nutrient intensive materials. A comprehensive description of the experiments in the filed with our scaled up materials and results can be found in our recent work listed among products includingDOI:https://doi.org/10.21273/HORTTECH05423-24 andhttps://doi.org/10.1021/acssusresmgt.4c00013.

Publications


    Progress 06/01/23 to 05/31/24

    Outputs
    Target Audience:-the academic audience reached within the conferences and publications described under Accomplishments. Briefly, 8publications were published and 5 presentations invited and the collaborator list was expanded to Auburn UniversityBioenergy & Bioproducts, Biosystems Engineering -industrial entities including ICL Group Ltd (formerly Israel Chemicals Ltd.) that entered a testing agreement on the developed urea cocrystals. -broader audience in Cedar Crest college, Allentown, PA during Earth day symposium -international audience in Embrapa Instrumentacao (Sao Carlos, Brazil), University of Ribeirão Preto (Brazil), Federal University of Sao Carlos (Brazil) via newly established collaborations Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training of 1 in-house PhD student (Mohamed Eisa) as well as Damilola Aowtoye who contributed to urea application reviews. One more PhD student was trained at the Kaunas University of Technologywhile performing a urea slow-release property review. Two postdocs at Lehigh were engaged as well as one at USDA ARS. How have the results been disseminated to communities of interest?Eight publications and five presentations. We also paved way via publications to evaluate the environmental stability of urea in a broader sense (see for example ACS Earth Space Chem.2023, 7, 10, 2139-2153) with the currently proceeding work on performing direct comparison of environmental stability of urea compared to our cocrystals What do you plan to do during the next reporting period to accomplish the goals?-kinetics of mechanochemical synthesis of urea cocrystals using conventional laboratory scale ball mill -comparison of urea environmental stability kinetics with those of urea cocrystals via Dynamic Vapor Sorption experiments -potassium extraction from silicates via milling to form nutrient-containing cocrystals -field testing with Regean Hejl and Clinton Williams at USDA ARS of our cocrystals under various environmental conditions with various crops. Work is submitted as an abstract to"Symposium--Organomineral Fertilizers: Innovative Manure-Based Fertilizer Products for Agricultural and Environmental Sustainability, and Crop Production"for this year's Crop Science meeting in November.

    Impacts
    What was accomplished under these goals? Task 1.A series of Mg and Zn-containing NH4 salts were synthesized mechanochemically in the form of a solid solution of MgxZn(1-x)NH4CO3. Extensive physicochemical characterization was performed including XRD, elemental analysis, BET, Raman, TGA/DSC as well as nitrogen emission experiments in soil and bactericidal evaluation. Manuscript published. Task 2. Work was combined with that described in Task 4. Cocrystals ofCuSO4·3CO(NH2)2·H2O and ZnSO4·CO(NH2)2·2H2O were successfully synthesized from parent CuSO4 and ZnSO4 sulfates mechanochemically. Task 3. We have explored preliminary hydroxyapatite as natural mineral to host nutrients via mechanochemical synthesis with two manuscripts published. Task 4. CuSO4*urea and ZnSO4*urea cocrystals are synthesized from basic Cu and Zn carbonates via reactive milling. A manuscript in preparation.Combining urea and mineral-derived zinc and copper carbonates into a cocrystal may result in novel fertilizer materials with decreased reactive nitrogen loss in moist soil. In this work, urea cocrystals were synthesized with Zn and Cu sulfates in a single crystalline cell (as opposed to state-of-the-art multicomponent fertilizers that retain their distinct crystalline phases). Mechanochemical synthesis was utilized whereby Zn- and Cu-carbonates were reacted with solid commercially available urea-sulfuric acid cocrystals to form CuSO4·3CO(NH2)2·H2O and ZnSO4·CO(NH2)2·2H2O cocrystals. The resulting crystalline structure was confirmed using powder X-ray diffraction, thermogravimetric analysis was used to investigate their thermal stability while X-ray photoelectron spectroscopy measured their surface structure and composition. Sparx Romaine lettuce was cultivated in pots to investigate the initial efficacy of the materials as well as residual soil nitrate and soil respiration properties. Importantly, pot experiments showed that not only did CuSO4·3CO(NH2)2·H2O and ZnSO4·CO(NH2)2·2H2O cocrystals efficiently provided nitrogen to the plants, but also did that in a slow-release manner. The approach described here resulted in materials exhibiting reduced nitrogen losses and has the potential to unlock nutrients confined in low-solubility minerals and rocks for more sustainable development. Task 5. A rotary ball mill was purchased and kinetics of CaSO4*urea and TSP*urea cocrystal synthesis are being determined. This is by far our largest scale attempts that are very timely and milling parameters approach those of industrial mills.

    Publications

    • Type: Journal Articles Status: Published Year Published: 2024 Citation: https://doi.org/10.3390/batteries10020045
    • Type: Journal Articles Status: Published Year Published: 2024 Citation: https://doi.org/10.1021/acssuschemeng.3c07785
    • Type: Journal Articles Status: Published Year Published: 2024 Citation: https://doi.org/10.1016/j.chemosphere.2024.142130
    • Type: Journal Articles Status: Published Year Published: 2023 Citation: https://doi.org/10.3390/ceramics6030110
    • Type: Journal Articles Status: Published Year Published: 2023 Citation: https://doi.org/10.1016/j.heliyon.2023.e19830
    • Type: Journal Articles Status: Published Year Published: 2023 Citation: https://doi.org/10.1021/acsearthspacechem.3c00210
    • Type: Journal Articles Status: Published Year Published: 2023 Citation: https://doi.org/10.3390/su16010188
    • Type: Journal Articles Status: Published Year Published: 2024 Citation: https://doi.org/10.1039/D3MR00012E
    • Type: Conference Papers and Presentations Status: Published Year Published: 2024 Citation: Jonas Baltrusaitis, From Concept to Prototype: Sustainable Engineering for global Nitrogen Cycle Management, Oregon State University, Department of Chemical Engineering, April 22nd , 2024 (invited seminar).
    • Type: Conference Papers and Presentations Status: Published Year Published: 2024 Citation: Jonas Baltrusaitis, Addressing challenges in nitrogen sustainability via crystal design, University of Adelaide, March 20, 2024. (invited seminar).
    • Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: Jonas Baltrusaitis, Nitrogen efficient by design: the story of urea cocrystal fertilizer materials, Workshop on Novel Fertilizers and Plant Nutrition, University of Delaware, July 5, 2023. (invited seminar).
    • Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: Jonas Baltrusaitis, Mechanochemistry for sustainable nitrogen management, 27th Annual Green Chemistry & Engineering Conference, Long Beach, CA, June 13-15, 2023.
    • Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: Mohamed Eisa, D Jonas Baltrusaitis, Nitrogen Fertilizer Synthesis and Use for Sustainable Agriculture, 27th Annual Green Chemistry & Engineering Conference, Long Beach, CA, June 13-15, 2023.


    Progress 06/01/22 to 05/31/23

    Outputs
    Target Audience:-the academic audience reached within the conferences and publications described under Accomplishments. Briefly, 4 publications, 2 invited seminars at Iowa State University and the University of Delawareand 2 national conferences. -industrial entities including ICL Group Ltd (formerly Israel Chemicals Ltd.) that entered a testing agreement on the developed urea cocrystals. -broader audience in Cedar Crest college, Allentown, PA during Earth day symposium. -international audience in Embrapa Instrumentacao (Sao Carlos, Brazil),University of Ribeirão Preto (Brazil),Federal University of Sao Carlos (Brazil),Universität Hohenheim (Germany) via newly established collaborations Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training of 1 in-house PhD student (Mohamed Eisa), and 2 visiting PhD students (Dovile Ragauskaite from Kaunas University of Technology and Mariana Brondi from Brazil). One more PhD student was trained at the University of New Mexico while performing field experiments using our cocrystals. Please refer to the publication list for the comprehensive training results How have the results been disseminated to communities of interest? Jonas Baltrusaitis, New fertilizer materials for sustainable development, Cedar Crest college, Earth Day symposium, April 22nd, 2023. Jonas Baltrusaitis, Nitrogen efficient materials and technologies, Iowa State University Mechanical Engineering departmental seminar, January 31st, 2023. Jonas Baltrusaitis, Addressing Challenges in Nitrogen Sustainability: From Molecular Design To Process Design, College of Agriculture and Natural Resources, University of Delaware, September 23rd, 2022. Mohamed Eisa, Dovile Ragauskaite, Manoj Silva and Jonas Baltrusaitis, Engineered urea cocrystals for sustainable nitrogen management in the environment, ACS Fall 2022 meeting, August 21-25, 2022, Chicago, Il. Hejl, R., Williams, C. F., Baltrusaitis, J., & Serba, D. D., 2022, Evaluation of Urea Co-Crystals As a Potential Slow-Release Fertilizer on 'Tifway' Bermudagrass. ASA, CSSA, SSSA International Annual Meeting, Baltimore, MD. https://scisoc.confex.com/scisoc/2022am/meetingapp.cgi/Paper/146035. What do you plan to do during the next reporting period to accomplish the goals?1. Develop a comprehensive result database under Task 1 of ammonium bicarbonate-based cocrystals. The importance of these crystals in agriculture is tremendous since ammonium bicarbonate can be extracted from biomass digestion wastewater (https://doi.org/10.3390/agriculture13040909). Our preliminary results showed enhanced stability of Zn and Mg ammonium carbonate cocrystals. Our initial tests also showed they can be granulated. We will fully explore this chemistry, N emission testing, patent filing and another USDA NIFA report writing. 2. Develop K dissolution experiments under Task 3 to measure the potential and capacity of potassium extraction from silcaeous materials. 3. Task5+6 testing of cocrystal N emissions using pot and field experiments in collaboration with University of New Mexico and colleagues in USDA ARS.

    Impacts
    What was accomplished under these goals? Objective 1 Task 1. A series of Mg and Zn-containing NH4 salts were synthesized mechanochemically in the form of a solid solution of MgxZn(1-x)NH4CO3. Extensive physicochemical characterization was performed including XRD, elemental analysis, BET, Raman, TGA/DSC as well as nitrogen emission experiments in soil and bactericidal evaluation. Patent application in preparation and 2 publications with colleagues from Brazil. USDA NIFA proposal in preparation using these preliminary data. Also seehttps://www.mdpi.com/2077-0472/13/4/909 Task 2.ZnSO4*x urea, CuSO4*x urea cocrystals made from pure salts (ZnSO4 and CuSO4)using solid-state mechanochemistry. Physicochemical characterization is underway as well as N emission tests. Task 3. nothing to report Task 4.nSO4*x urea, CuSO4*x urea cocrystals made fromCuO, CuCO3 and ZnO, ZnCO3 using urea*H2SO4 cocrystals using solid-state mechanochemistry. Physicochemical characterization is underway as well as N emission tests. Task 5+Task 6. Several 100-gram batches were synthesized. URCASU (CaSO4*4urea) was sent to the University of New Mexico testing station where N2O and N measurements were assessed in the field (https://www.mdpi.com/2071-1050/15/10/8010). Another batch of URCASU and Ca(H2PO4)2*4urea cocrystals was sent out to the University of Hohenheim, Germany, Reiner Ruser, for another field test round.

    Publications

    • Type: Journal Articles Status: Published Year Published: 2022 Citation: https://doi.org/10.1021/acssuschemeng.2c03972
    • Type: Journal Articles Status: Published Year Published: 2023 Citation: https://doi.org/10.3390/su15108010
    • Type: Journal Articles Status: Published Year Published: 2023 Citation: https://doi.org/10.3390/agriculture13040909
    • Type: Journal Articles Status: Published Year Published: 2023 Citation: https://doi.org/10.1021/acs.energyfuels.2c04193
    • Type: Journal Articles Status: Published Year Published: 2023 Citation: https://doi.org/10.1016/j.fuproc.2023.107753
    • Type: Conference Papers and Presentations Status: Published Year Published: 2022 Citation: Hejl, R., Williams, C. F., Baltrusaitis, J., & Serba, D. D. (2022) Evaluation of Urea Co-Crystals As a Potential Slow-Release Fertilizer on Tifway Bermudagrass [Abstract]. ASA, CSSA, SSSA International Annual Meeting, Baltimore, MD. https://scisoc.confex.com/scisoc/2022am/meetingapp.cgi/Paper/146035
    • Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: Jonas Baltrusaitis, New fertilizer materials for sustainable development, Cedar Crest college, Earth Day symposium, April 22nd, 2023.
    • Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: Jonas Baltrusaitis, Nitrogen efficient materials and technologies, Iowa State University Mechanical Engineering departmental seminar, January 31st, 2023.
    • Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: Jonas Baltrusaitis, Addressing Challenges in Nitrogen Sustainability: From Molecular Design To Process Design, College of Agriculture and Natural Resources, University of Delaware, September 23rd, 2022.
    • Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: Mohamed Eisa, Dovile Ragauskaite, Manoj Silva and Jonas Baltrusaitis, Engineered urea cocrystals for sustainable nitrogen management in the environment, ACS Fall 2022 meeting, August 21-25, 2022, Chicago, Il.


    Progress 06/01/21 to 05/31/22

    Outputs
    Target Audience:Target audiences were members of the wide range of the scientific community which was reached via publications and conference presentations (see Products) as well as field professionals in fertilizer production and formulation area. In particular: -development of our synthesis procedures and results presented fostered very heavy interest among academics in chemistry, chemical engineering, crystal design and environmental engineers. This was highlighted very recently by a recent research highlight on "Agrichemicals" in Nature Reviews Chemistry entitle "Solid state synthesis sustains"https://www.nature.com/articles/s41570-022-00401-w. -we presented 5 conference talks in the past year at American CHemical Society, American Institute of Chemical Engineers, ACS Green and Sustainable Chemistry and Pacifichem. -we had significant inquiries on the potential of the materials we are creating from the industry including Harrel's (Jeffrey Atkinson, director of agronomy at Harrell's and ICL Inc. (Robert Steinekes from ICL). ICL Inc is considering patentability, sustainability and profitability of our fertilizer materials and we are engaged in weekly meetings. https://www.icl-group.com/sustainability/ https://www.harrells.com/ -heavy media coverage of our recent scale up technology developments is recent https://www.desy.de/news/news_search/index_eng.html?openDirectAnchor=2292&two_columns=0 -finally, last weekAmarjit S. Basra, PhD,Director, Chief Scientist ofOCPNorth America, Inc. engaged us and suggested I apply for theirFFAR-OCP Disruptive Technology Fellowship due to the nature of my work (unfortunately I am past 10 years after my PhD so I am not eligible). Changes/Problems:The major problems were due to the COVID pandemic when no PhD students entered the country in 2020-2021 cycle and I was not able to hire any. However, I hired a new PhD student in Winter 2022 and will hire another one in Fall 2022. The project, nevertheless, persisted strongly due to the multiple collaborative efforts and visiting students and postdocs. I strongly hope that we can submit an extension to the project when the time comes since we demonstrated strong progress even during the COVID years. What opportunities for training and professional development has the project provided?One postdoc, two PhD students and one undergraduate worked at Lehigh on this project. Multiple conference presentations at ACS, AICHE and Pacifichem. Currently, 1 MSc student at Arizona State working with Clinton Williams from USDA ARS who is testing for this project. A large international collaboration with 11 researchers including from Ruder Boskovic Institute in Zagreb, Croatia, Lehigh and ICL Inc was initiated and resulted in a well-publicized publication on CaSO4*x urea scaleup (see Products). How have the results been disseminated to communities of interest?Academically, via multiple conference presentations at ACS, AICHE and Pacifichem and scientific publications (see the Products). Professionally, via interactions with ICL Inc and Harrell's, e.g. fertilizer manufacturers. ICL Inc in particular are engaged testing our materials in Wageningen University, NL. What do you plan to do during the next reporting period to accomplish the goals?-obtain results from Wageningen university pot experiments usingMgSO4*x urea, CaSO4*x urea, MgHPO4*x urea and CaHPO4*x urea granulated (this is due to the ICL Inc commercial interest) -obtain results from USDA ARS on N washout using column experiments onMgSO4*x urea, CaSO4*x urea, MgHPO4*x urea and CaHPO4*x urea (Task 6) -obtain results from USDA ARS onwhether the co-crystals actually provide for slow release of urea in plant growth systems. Our proposed experiment will be to use co-crystals and traditional slow-release urea (sulfur and polymer-coated) to grow Bermudagrass in small pots in the greenhouse. We will do two different N fertilizer rates and four reps for each N source(Task 6)? -K extraction via milling with organic acids from siliceous minerals (Task 3)

    Impacts
    What was accomplished under these goals? Task 1: this task has largely been accomplished. Important developments in the past year have focused on scale-up of the materials synthesized from salts using a rotary ball mill. 200-gram quantities have easily been synthesized ofMgSO4*x urea, CaSO4*x urea, MgHPO4*x urea and CaHPO4*x urea and sent out to (a) partners at ICL Inc for field testing at Wageningen University, NL, (b) partners at USDA ARS (Clinton Williams) for column testing and (c) granulator manufacturers at Eirich Machines in Illinois for granulation testing. Wageningen researchers also need granulated material. We are happy to report thatEirich Machines returned granulatedCaSO4*x urea of high granule crushing strength proving it is possible to granulateCaSO4*x urea (at least) while still maintaining cocrystal structure as analyzed using XRD.(NH4)2CO3 also yielded a cocrystal which properties need to be determined. A large scale modeling experiments for(NH4)2CO3 production from digestate performed and published in 2021 Task 2: accomplished and tested forZnCl2*x urea with KCl - first cocrystal of its kind, other cocrystals are under development, planned for year 4 Task 3: preliminary results obtained that release 20% of K from siliceous minerals via milling with citric acid. This will be one of the focus of the upcoming year Task 4: planned for year 4 Task 5: accomplished, tested and published in 2020 and 2021, granulation recently finished with Eirich Machines Task 6: under testing at USDA ARS

    Publications

    • Type: Journal Articles Status: Published Year Published: 2022 Citation: https://doi.org/10.1021/acssuschemeng.2c02019
    • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Jonas Baltrusaitis, Mechanochemical ionic urea cocrystal synthesis and mechanisms for sustainable nitrogen management, Pacifichem 2021, December 16 - 21, 2021, Honolulu, Hawaii, USA
    • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Jonas Baltrusaitis, Improving Global Nitrogen Cycle Management Via Mechanochemical High Efficiency Urea Cocrystal Fertilizer Material Synthesis and Utilization, 2021 AIChE Annual Meeting (Sustainable Engineering Forum), November 7-19, 2021, Boston, MA.
    • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Donata Drapanauskaite, Karolina Barcauskaite, Jonas Baltrusaitis, Reducing Agricultural Nitrogen Losses via Mechanochemically Synthesized Urea Cocrystals, ACS Fall 2021 meeting, August 22-26, 2021, Atlanta, GA.
    • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Jonas Baltrusaitis, and Robert Handler, Transformation of Liquid Digestate from the Solid-Separated Biogas Digestion Reactor Effluent into a Solid NH4HCO3 Fertilizer, 25th Annual Green Chemistry & Engineering Conference, June 14-18, 2021.
    • Type: Journal Articles Status: Published Year Published: 2022 Citation: https://doi.org/10.1021/acssuschemeng.2c00914
    • Type: Journal Articles Status: Published Year Published: 2022 Citation: https://doi.org/10.3390/land11040521
    • Type: Journal Articles Status: Published Year Published: 2021 Citation: https://doi.org/10.1021/acssuschemeng.1c05410
    • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: Jonas Baltrusaitis, Nitrogen-efficient urea ionic cocrystal mechanochemical synthesis, 25th Annual Green Chemistry & Engineering Conference, June 14-18, 2021.


    Progress 06/01/20 to 05/31/21

    Outputs
    Target Audience:The academic audience reached withint the conferences described under Accomplishments. We enjoyed the attention from general audience as well as the companies. News outlets: https://engineering.lehigh.edu/news/article/nitrogen-efficient-fertilizer-research-could-have-lasting-impact https://sciencex.com/wire-news/352439200/nitrogen-efficient-fertilizer-research-could-have-lasting-impact.html https://axial.acs.org/2020/05/26/congratulations-to-the-2020-recipients-of-the-acs-sustainable-chemistry-engineering-lectureship-awards/ We are also happy to report that 4 cocrystal formulations from our patent US2020189987A1 SOLVENT FREE METHOD OF PRODUCING UREA ADDUCT attracted industrial attention. At the time of the submission of this report, we entered a testing agreement with ICL Group Ltd (formerlyIsrael ChemicalsLtd.) under the information below. Project: Synthesis and testing of Urea co-crystals using Lehigh technology LU-050317-01 "Solvent free method of producing calcium and magnesium salt - urea crystalline compounds" Lehigh Lab: Dr. Jonas Baltrusaitis - Chemical & Biochemical Engineering Overview: The goal of this four phase project is to synthesize a co-crystal of Urea with 4 selected inorganic compounds mechanochemically, test the co-crystals with Urea for solubility, dissolution rate and volatility as well as characterize these co-crystals using powder X-ray Diffraction analysis. In addition, Synthesis of co-crystals of ICL's Polysulphate (Polyhalite) and Phosphogypsum materials and Urea using Lehigh's Solvent-free Method of Producing Calcium and Magnesium Salt - Urea Crystalline Compounds technology. These co-crystals will have the same tests performed as the other 4 selected inorganic compounds. Scale from 200 milligrams up to larger quantities of 100 grams will be performed followed by the same tests. Finally, granulation and/or compaction of the co-crystal powder will be the final phase of the project. Phases I, II, and III will be performed concurrently, with Phase IV following the successful milestone of the previous phases. Deliverables: Three solid co-crystal formulations 100 gram each of existing cocrystals, results of Urea co-crystal solubility, dissolution rate and crystal characterization data. Formulations of cocrystals with polysulphate and phosphogypsum. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?While pandemic stopped us early, we have been very productive afterwards. In particular, we have engaged into multiple collaborations that provided training, exchange possibilities: Donata Drapanauskaite, Kristina Buneviciene - visiting researchers from Lithuania, collaborative projects on Ca- and Mg- recovery and release from solid waste Clinton Williams from USDA ARS - a collaborator on this grant on analyzing volatilization losses, collaborated on several other projects which resulted in wastewater treatment related publications https://doi.org/10.1016/j.jece.2021.105589 and https://doi.org/10.1039/D0EW01035A How have the results been disseminated to communities of interest? Jonas Baltrusaitis, and Robert Handler, Transformation of Liquid Digestate from the Solid-Separated Biogas Digestion Reactor Effluent into a Solid NH4HCO3 Fertilizer, 25th Annual Green Chemistry & Engineering Conference, June 14-18, 2021. Jonas Baltrusaitis, Nitrogen-efficient urea ionic cocrystal mechanochemical synthesis, 25th Annual Green Chemistry & Engineering Conference, June 14-18, 2021. Jonas Baltrusaitis, Conversion of Recycled Drywall into Nitrogen Efficient Fertilizers, Conversion of Solid Wastes to Energy and/or Products, 2020 Virtual AIChE Annual Meeting, November 20, 2020. Jonas Baltrusaitis, 3rd Annual ACS Sustainable Chemistry & Engineering Lectureship Awardee keynote, 24th Annual Green Chemistry & Engineering (GC&E) Virtual Conference, June 19, 2020. What do you plan to do during the next reporting period to accomplish the goals?Under Objective 1, Tasks 1 and 2 explore synthesis of NH4+ containing cocrystals, analyze their underlying physicochemical properties using TGA, Raman, XRD and their volatilization. In particular, we are interested in creating stoichiometric MgNH4(CO3)2*4H2O cocrystal from MgCO3 and NH4HCO3 and patenting, if successful. Additionally, we developed a new in silico methodology to understand why and how these cocrystals possess improved volatilization properties. We are utilizing USDA SCINET supercomputers to perform DFT calculations of urea and urea cocrystal surface reactions under moist environments.

    Impacts
    What was accomplished under these goals? Under Objective 1 Task, we have performed a large volume research that culminated in https://doi.org/10.1016/j.jece.2020.103965. In particular, we designed and mechanochemically synthesized CaSO4·4urea from both pure salts and waste drywall gypsum and provide a physicochemical basis for the observed agricultural CaSO4·4urea cocrystal efficiency. Thermal data have shown unique cocrystal properties with delayed or avoided melting transition in DSC. Similarly,in situRaman combined with DVS data showed less propensity of the cocrystal to interact with water as relative humidity, while lower N losses were measured in sand leaching experiments. Anab initioframework was devised to explain the apparent stability of the cocrystal. It was found that a large apparent thermodynamic barrier is present for the cocrystal decomposition into the parent compounds. Finally, an added nutrient availability in soil was measured as opposed to the conventional urea fertilizers for the same nutrient loadings. We explored recovery of possible NH4+ source for our cocrystals from anaerobic digestion liquid. This work was published in https://doi.org/10.1021/acssuschemeng.0c08374. This is important since urea in liquid quickly decomposes into NH4+ and large quantities of this ion are needed for cocrystal synthesis. We developed a process in silico whereby NH4HCO3 solid can be obtained from biomass digestion waste. In particular, as the generation of biogas increases because of the transition to a circular economy, amounts of generated liquid digestate will increase. Considering that a typical biogas plant with 1 MWe produces a few tens of tons of digestate daily, the importance of its storage, reuse, and nutrient recovery options will only increase. Currently, liquid digestate can be recycled into the digester, reused as a fertilizer on the farm fields, or discharged to wastewater treatment plants. These options have their limitations, especially if not enough farmland is available to adequately transport and disperse the liquid. Current emerging technologies are developed to recover the nutrients from the digestate and create concentrated solid products, such as struvite (magnesium ammonium-phosphate hexahydrate) and ammonium sulfate fertilizers. In this work, we further utilize the concept of engineering solid materials and propose a design of NH4HCO3fertilizer materials. In particular, we design a distillation-based process operating at 3.3 bar to result in 99.9% utilization of nitrogen from the liquid digestate. Sustainability metrics are provided for this process when compared with other scenarios, such as direct digestate application to the fields or (NH4)2SO4process. A life cycle assessment of the proposed NH4HCO3process indicates that it performs as same as or better than the baseline digestate handling method, and further improvements in energy efficiency could drive further improvements in comparison to the simple land application or other more energy-intensive valorization routes. A significant impact on ecotoxicity observed stemmed purely from the use of defoaming agents. Environmentally friendly defoaming agents that substitute a large fraction of organic silica compounds with inorganic ones, such as loess, will be critical in obtaining more beneficial ecotoxicity parameters. Site-specific field trials to assess the dynamics of C and N fate during their current usage would help to provide more certainty on the potential for improvement when transitioning to this method of solid fertilizer production and use. Further, to better understand Ca and Mg containing feedstock sources derived from any industrial or agricultural waste, we explored the chemical composition, release properties in soil and the resulting soil pH of lime kiln dust (LKD) and biomass combustion bottoms ash (BA). In some cases, green waste compost (GWC) was used for complexation purposes. In this work, BA combined with GWC was used as nutrient-containing materials to test their synergistic properties towards wheat and triticale growth. In particular, BA and GWC were applied thoroughly mixed. The resulting mixtures were analyzed for their chemistry towards their propensity to release nutrients. The experimental design focused on (1) the control; (2) BA; (3) GWC; (4) GWC + BA1.5; (5) GWC + BA3.0; and (6) GWC + BA4.5. The results obtained in this work showed that the highest increase in spring wheat grain yield was achieved by fertilization with the GWC + BA4.5 mixture, i.e., spring wheat yield was obtained at 4.61 t ha−1. The content of heavy metals (Cd, Zn, and Cr) in the soil increased significantly compared to the control. Total P increased in grain and K, Ca, and Mg in straw. Only three heavy metals (Cd, Zn, and Cu) were detected in grain and straw. The results obtained show that the application of BA together with GWC results in less heavy metal transfer to the crops. This work has been published in https://doi.org/10.3390/agronomy11040641 Similarly, recovery of nutrients from biomass combustion ash was explored as it is of great importance for sustainable bioenergy waste use. In this work, granulated fertilizer materials were engineered from biofuel bottom ash, lime kiln dust and water, analysed for their chemical complexity and tested in pot experiments for their propensity to release nutrients. The results obtained in this work showed that spring barley yield was observed to be the highest for granulated biomass ash with 30% of ash in the granule. The yield increased 3.99 t ha−1per 100 kg ha−1potassium oxide (K2O) in 2017 and 1.23 t ha−1per 100 kg ha−1K2O in 2018. Straw yield varied between 1.39-5.08 t ha−1/100 kg ha−1in 2017 and 0.36-1.23 t ha−1/100 kg ha−1. Calcium concentration significantly increased in soil. No significant changes in soil mobile phosphorus (P) were obtained as well as for the heavy metal concentrations in soil. This suggests that biofuel ash can be a significant source of certain major nutrients for crops that can also beneficially affect soil pH. The results of this work can provide policy-makers with the information needed to diversify existing and enable new biomass bottom ash utilization routes which currently vary significantly between the countries. This work was published in https://doi.org/10.1177/0734242X20948952

    Publications

    • Type: Journal Articles Status: Published Year Published: 2020 Citation: https://doi.org/10.1016/j.jece.2020.103965
    • Type: Journal Articles Status: Published Year Published: 2021 Citation: https://doi.org/10.1021/acssuschemeng.0c08374
    • Type: Journal Articles Status: Published Year Published: 2021 Citation: https://doi.org/10.3390/agronomy11040641
    • Type: Journal Articles Status: Published Year Published: 2020 Citation: https://doi.org/10.1177/0734242X20948952