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While biopolymers have the potential to enhance agrochemical delivery and mitigate environmental impacts such as runoff, previous plant studies have often been limited to examining single biopolymers in isolation. This approach has hindered effective comparisons of plant outcomes due to variations in plant type, growth duration, and soil characteristics. The current study addresses this gap by incorporating six separate milled biopolymers: pectin, starch, chitosan, polycaprolactone (PCL), polylactic acid (PLA), or polyhydroxybutyrate (PHB) into soil and directly comparing their impacts on tomato (Solanum lycopersicum) plants cultivated under identical environmental parameters. Plant outcomes were also studied when biopolymers were modified via the inclusion of two phosphorus (P) salts, forming two types of Polymer-P-containing salt composites with amorphous CaPO4 (CaP) and CaHPO4 (DCP). Our results revealed that chitosan-based treatments significantly improved tomato root and shoot biomass, with increases of 200–300% compared to the control plants. Chitosan-CaP and Chitosan-DCP also enhanced P uptake, though the effect was significantly more pronounced in the former, suggesting a synergy between chitosan and CaP. Neither Chitosan-P-containing salt treatment, however, mitigated P leaching from soil when compared to CaP or DCP applied in isolation. The two most hydrophilic biopolymers, pectin and starch, as well as their P-salt-containing counterparts, showed the most substantial reductions in biomass (∼80%) with respect to control plants, while similarly lowering P uptake and P retention in soil compared to CaP- and DCP-only plants. PCL- and PHB-based treatments also adversely influenced biomass and plant P, though these effects were not as drastic as those observed with pectin and starch. PLA-based soil amendments had no effect on any plant performance metric, though PLA-CaP, specifically, was the only treatment to appreciably mitigate P leaching (−63%). Based on these findings, subsequent tomato growth experiments were conducted over a longer 8-week period with CaP, DCP, Chitosan, Chitosan-CaP, and Chitosan-DCP. While all chitosan-treated plants showed similar enhancements in biomass, plants treated with Chitosan-CaP and Chitosan-DCP were the only ones to fruit, demonstrating the benefit of using chitosan in conjunction with a P source as compared to either treatment in isolation. These findings contribute to an expanding body of evidence that biopolymer carriers can offer a more sustainable approach to improving the precision of nutrient delivery, while also highlighting the pivotal role of biopolymer and nutrient type in the development of these carriers. 

Phosphorus (P) is critical for crop production but has a high nutrient use inefficiency. Tomato was grown in soil amended with five P-sources, used as-is, or embedded within a biodegradable polymer, polyhydroxyalkanoate (PHA). Correlation analysis identified treatments that maintain plant growth, improve bioavailable soil P, and reduce P loss. Three performance classes were identified: (i) micro- and nanohydroxyapatite, which did not increase bioavailable P, plant P-uptake, or change P in runoff/leaching compared to controls; (ii) monocalcium phosphate (MCP), dicalcium phosphate (DCP), calcium pyrophosphate nanoparticles (CAP), and PHA-MCP that increased P-uptake and/or bioavailable P but also increased P loss in runoff/leaching; and (iii) PHA-DCP and PHA-CAP, where increased bioavailable P and plant P-uptake were achieved with minimal P loss in runoff/leaching. In addition to identifying treatments that maintain plant growth, increase bioavailable P, and minimize nutrient loss, correlation plots also revealed that (i) bioavailable P was a good indicator of plant P-uptake; (ii) leached P could be predicted from water solubility; and (iii) P loss through runoff versus leaching showed similar trends. This study highlights that biopolymers can promote plant P-uptake and improve bioavailable soil P, with implications for mitigating the negative environmental impacts of P loss from agricultural systems. 

Enhancing the delivery efficiency of NPK fertilizers benefits both crops and the environment through moderating the supplied dosage of nutrients in the soil, avoiding side reactions, maximizing absorption by the plant, and minimizing leaching and runoff. Bio-based materials such as cellulose are ideal scaffolds for nutrient delivery due to their inherent biocompatibility, biodegradability, and significant water uptake. In this work, nanocellulose-based hydrogels were regenerated from mixed softwood in acidic media and loaded with NPK by immersion in varied concentrations of an NPK-rich fertilizer solution. High loading of NPK was achieved within the hydrogel, but immersion in the matrix provided only slight slowing of nutrient release compared to rapid solubility of conventional formulations. Densification, crosslinking, and coating of the hydrogels with beeswax were ineffective strategies to further slow NPK release. Following these results, both gas and solution-phase esterification reactions of the cellulosic matrix with hexanoyl chloride were performed after NPK loading to introduce a hydrophobic surface layer. While solution-phase modification led to phosphorus leaching and was overall ineffective in altering nutrient release, the gas-phase modification slowed the release of P and K by more than an order of magnitude. Moreover, it was found that varying both the properties of the hydrophobic surface layer and the nutrient loading provide a means to tune release rates. Overall, this work demonstrates the potential of nanocellulose-based hydrogels to be used as an environmentally safe and sustainable vehicle for the controlled release of nutrients in agricultural applications.