Early swelling kinetics of chitosan hydrogels under different acidity conditions for designing controlled-release fertilizers

-

Authors

  • Sinta Ramadhania Putri Maresi Industrial Waste Processing Study Program, Politeknik AKA Bogor, Bogor, West Java 16154, Indonesia
  • Tri Sutanti Budikania Chemical Analysis Study Program, Politeknik AKA Bogor, Bogor, West Java 16154, Indonesia
  • Kartini Afriani Chemical Analysis Study Program, Politeknik AKA Bogor, Bogor, West Java 16154, Indonesia
  • Achmad Nandang Roziafanto Food Nanotechnology Study Program, Politeknik AKA Bogor, Bogor, West Java 16154, Indonesia
  • Ahmad Dzaky Mualim Chemical Analysis Study Program, Politeknik AKA Bogor, Bogor, West Java 16154, Indonesia
  • Fareka Kholidanata Chemical Analysis Study Program, Politeknik AKA Bogor, Bogor, West Java 16154, Indonesia

DOI:

https://doi.org/10.61511/aes.v4i1.2026.3710

Keywords:

biodegradable, chitosan, hydrogel, pH, swelling

Abstract

Background: Nutrient losses from conventional fertilization have increased the need for biodegradable hydrogel matrices that improve water retention and support controlled-release fertilizer (CRF) systems. This study investigated the effects of pH on the early-stage swelling kinetics of chitosan-based hydrogels, identified the most stable formulation, and examined the relationship between the degree of deacetylation (DD) and swelling performance. Methods: A quantitative experimental design was applied to four formulations, namely ChGu, ChG, ChPu, and ChP, under acidic, neutral, and alkaline conditions. Swelling was measured over 120 minutes with replicate measurements. The analysis included the swelling ratio (SR), maximum swelling ratio (Max SR), area under the curve (AUC), net swelling change (ΔSR), means, standard deviations, statistical comparisons, and regression analysis. Findings: pH markedly influenced the swelling behavior of all formulations. Neutral conditions produced the highest average SR values, with ChP showing the best performance (86.4), followed by ChG (67.6), ChGu (63.8), and ChPu (30.4). ChP also recorded the highest Max SR (124) and AUC (11,100), while ChG reached a Max SR of 110 and an AUC of 9,150. These findings indicate that both formulations had greater expansion capacity and more sustained swelling. In contrast, alkaline conditions caused deswelling in most samples, as indicated by negative SR values. The relationship between DD and swelling performance was weak (R² = 0.14), indicating that hydrogel structure, formulation composition, environmental pH, and early kinetic transitions were more influential than DD alone. Conclusion: Neutral pH provided the most favorable swelling conditions, and ChP demonstrated the strongest overall performance. Novelty/Originality of this article: This study proposes Max SR, AUC, ΔSR, and dynamic transition intervals as integrated early-stage indicators for screening biodegradable chitosan hydrogels for CRF applications.

References

Ahmad, D. F. B. A., Wasli, M. E., Tan, C. S. Y., et al. (2023). Eco-friendly cellulose-based hydrogels derived from wastepapers as a controlled-release fertilizer. Chemical and Biological Technologies in Agriculture, 10(36): 1-10. https://doi.org/10.1186/s40538-023-00407-6

Ardean, C., Davidescu, C. M., Nemeş, N. S., Negrea, A., Ciopec, M., Duteanu, N., Negrea, P., Duda-Seiman, D., & Musta, V. (2021). Factors influencing the antibacterial activity of chitosan and chitosan modified by functionalization. International Journal of Molecular Sciences, 22(14), 7449. https://doi.org/10.3390/ijms22147449

Badan Penelitian dan Pengembangan Pertanian. (2020). Location-specific recommendations for N, P, and K fertilizers for rice, maize, and soybean in paddy fields (by district): Book I: Rice. Ministry of Agriculture. Retrieved from: https://repository.pertanian.go.id/server/api/core/bitstreams/6c2d7931-53fa-46ea-ad60-cbfab9181fae/content

Budianto, E., & Amalia, A. (2020). Swelling behavior and mechanical properties of chitosan-poly(N-vinyl-pyrrolidone) hydrogels. Journal of Polymer Engineering, 40(7), 551–560. https://doi.org/10.1515/polyeng-2019-0169

Carpa, R., Remizovschi, A., Culda, C. A., & Butiuc-Keul, A. L. (2022). Inherent and composite hydrogels as promising materials to limit antimicrobial resistance. Gels, 8(2), Article 70. https://doi.org/10.3390/gels8020070

Chandran, V., Shaji, H., & Mathew, L. (2021). Methods for controlled release of fertilizers. In Controlled release fertilizers for sustainable agriculture (pp. 79–93). Academic Press. https://doi.org/10.1016/B978-0-12-819555-0.00005-4

Chiaregato, C. G., França, D., Messa, L. L., Pereira, T. dos S., & Faez, R. (2022). A review of advances over 20 years on polysaccharide-based polymers applied as enhanced efficiency fertilizers. Carbohydrate Polymers, 279, Article 119014. https://doi.org/10.1016/j.carbpol.2021.119014

Dou, Z., Bini Farias, M. V., Chen, W., He, D., Hu, Y., & Xie, X. (2023). Highly degradable chitosan-montmorillonite (MMT) nano-composite hydrogel for controlled fertilizer release. Frontiers of Environmental Science & Engineering, 17, Article 53. https://doi.org/10.1007/s11783-023-1653-9

Eddarai, E. M., El Mouzahim, M., Ragaoui, B., Eladaoui, S., Bourd, Y., Bellaouchou, A., & Boussen, R. (2024). Review of current trends in chitosan based controlled and slow-release fertilizer: From green chemistry to circular economy. International Journal of Biological Macromolecules, 278(Part 4), Article 134982. https://doi.org/10.1016/j.ijbiomac.2024.134982

Firmanda, A., Fahma, F., Syamsu, K., Mahardika, M., Suryanegara, L., Munif, A., Gozan, M., Wood, K., Hidayat, R., & Yulia, D. (2024). Biopolymer-based slow/controlled-release fertilizer (SRF/CRF): Nutrient release mechanism and agricultural sustainability. Journal of Environmental Chemical Engineering, 12(2), Article 112177. https://doi.org/10.1016/j.jece.2024.112177

Flatian, A. N., Rachmadhani, A. F., & Suryadi, E. (2020). Efficiency of nitrogen fertilization in sweet corn due to different urea doses and application timing using the ¹⁵N isotope technique. Journal of Soil and Climate, 44(2), 93–100. https://doi.org/10.21082/jti.v44n2.2020.93-100

Govil, S., Long, N. V. D., Escribà-Gelonch, M., & Hessel, V. (2024). Controlled-release fertiliser: Recent developments and perspectives. Industrial Crops and Products, 219, Article 119160. https://doi.org/10.1016/j.indcrop.2024.119160

Hellmann, M. J., Gillet, D., Trombotto, S., Raetz, S., Moerschbacher, B. M., & Cord-Landwehr, S. (2024). Heterogeneously deacetylated chitosans possess an unexpected regular pattern favoring acetylation at every third position. Nature Communications, 15, Article 6695. https://doi.org/10.1038/s41467-024-50857-1

Hong, F., Qiu, P., Wang, Y., Ren, P., Liu, J., Zhao, J., & Gou, D. (2024). Chitosan-based hydrogels: From preparation to applications, a review. Food Chemistry: X, 21, Article 101095. https://doi.org/10.1016/j.fochx.2023.101095

Irfan, S. A., Azeem, B., Irshad, K., Algarni, S., KuShaari, K., Islam, S., & Abdelmohimen, M. A. H. (2020). Machine learning model for nutrient release from biopolymers coated controlled-release fertilizer. Agriculture, 10(11), Article 538. https://doi.org/10.3390/agriculture10110538

Jariwala, H., Santos, R. M., Lauzon, J. D., Dutta, A., & Chiang, Y. W. (2022). Controlled release fertilizers (CRFs) for climate-smart agriculture practices: A comprehensive review on release mechanism, materials, methods of preparation, and effect on environmental parameters. Environmental Science and Pollution Research, 29, 53967–53995. https://doi.org/10.1007/s11356-022-20890-y

Katchali, M., Richard, E., Tonnang, H. E. Z., Tanga, C. M., Beesigamukama, D., & Senagi, K. (2025). Mathematical and computational modeling for organic and insect frass fertilizer production: A systematic review. PLOS ONE, 20(1), Article e0292418. https://doi.org/10.1371/journal.pone.0292418

Kaya, M., Mujtaba, M., Ehrlich, H., Salaberria, A. M., Baran, T., Amemiya, C. T., Galli, R., Akyuz, L., Sargin, I., & Labidi, J. (2017). On chemistry of γ-chitin. Carbohydrate Polymers, 176, 177–186. https://doi.org/10.1016/j.carbpol.2017.08.076

Klein, M., & Poverenov, E. (2020). Natural biopolymer-based hydrogels for use in food and agriculture. Journal of the Science of Food and Agriculture, 100(6), 2337–2347. https://doi.org/10.1002/jsfa.10274

Kumar, A., Sood, A., Agrawal, G., Thakur, S., Thakur, V. K., Tanaka, M., Mishra, Y. K., Christie, G., Mostafavi, E., Boukherroub, R., Hutmacher, D. W., & Han, S. S. (2023). Polysaccharides, proteins, and synthetic polymers based multimodal hydrogels for various biomedical applications: A review. International Journal of Biological Macromolecules, 247, Article 125606. https://doi.org/10.1016/j.ijbiomac.2023.125606

Lawrencia, D., Wong, S. K., Low, D. Y. S., Goh, B. H., Goh, J. K., Ruktanonchai, U. R., Soottitantawat, A., Lee, L. H., & Tang, S. Y. (2021). Controlled release fertilizers: A review on coating materials and mechanism of release. Plants, 10(2), Article 238. https://doi.org/10.3390/plants10020238

Li, H., Wang, J., Luo, Y., Bai, B., & Cao, F. (2022). pH-responsive eco-friendly chitosan-chlorella hydrogel beads for water retention and controlled release of humic acid. Water, 14(8), Article 1190. https://doi.org/10.3390/w14081190

Lipin, A. A., Lipin, A. G., & Wójtowicz, R. (2023). Modelling nutrient release from controlled release fertilisers. Biosystems Engineering, 234, 81–91. https://doi.org/10.1016/j.biosystemseng.2023.08.015

Liu, H., Huang, Z., Shi, Y., Cai, T., Miao, Q., Gao, Z., & Cui, Z. (2024). Lightweight pH-responsive chitosan hydrogel iron fertilizer: Efficient performance, controlled-release, and tomato application. Journal of Environmental Chemical Engineering, 12(5), Article 113428. https://doi.org/10.1016/j.jece.2024.113428

Márton, P., Szolnoki, B., Nagy, N., Deák, A., Zámbó, D., Szabó, G. S., & Hórvölgyi, Z. (2024). Wetting and swelling behaviour of N-acetylated thin chitosan coatings in aqueous media. Heliyon, 10(1), Article e23201. https://doi.org/10.1016/j.heliyon.2023.e23201

Mikhailidi, A., Ungureanu, E., Tofanica, B.-M., Ungureanu, O. C., Fortună, M. E., Belosinschi, D., & Volf, I. (2024). Agriculture 4.0: Polymer hydrogels as delivery agents of active ingredients. Gels, 10(6), Article 368. https://doi.org/10.3390/gels10060368

Namli, S., Guven, O., Simsek, F. N., Gradišek, A., Sumnu, G., Yener, M. E., & Oztop, M. (2023). Effects of deacetylation degree of chitosan on the structure of aerogels. International Journal of Biological Macromolecules, 250, Article 126123. https://doi.org/10.1016/j.ijbiomac.2023.126123

Nunziata, G., Pollonio, D., Lacroce, E., & Rossi, F. (2025). Smart pH‑responsive polymers in biomedical applications: Nanoparticles, hydrogels, and emerging hybrid platforms. Materials Today Chemistry, 49, 103063. https://doi.org/10.1016/j.mtchem.2025.103063

Piccoli, I., Camarotto, C., Squartini, A., et al. (2024). Hydrogels for agronomical application: From soil characteristics to crop growth: A review. Agronomy for Sustainable Development, 44(22): 1-23. https://doi.org/10.1007/s13593-024-00958-4

Piroonpan, T., Huajaikaew, E., Kurantowicz, N., Potiyaraj, P., & Pasanphan, W. (2024). pH-responsive chitosan nanoparticles for controlled-release nitrogen fertilizer: Template-tampering free radical graft copolymerization under energetic radiation study. European Polymer Journal, 203, Article 112670. https://doi.org/10.1016/j.eurpolymj.2023.112670

Protsak, I. S., & Morozov, Y. M. (2025). Fundamentals and advances in stimuli-responsive hydrogels and their applications: A review. Gels, 11(1), Article 30. https://doi.org/10.3390/gels11010030

Rachmatpour, A., & Alizadeh, A. H. (2024). Biofilm hydrogel derived from physical crosslinking (self-assembly) of xanthan gum and chitosan for removing Cd2+, Ni2+, and Cu2+ from aqueous solution. International Journal of Biological Macromolecules, 266(Part 2), Article 131394. https://doi.org/10.1016/j.ijbiomac.2024.131394

Roas-Escalona, N., Becquart, F., Delair, T., & Dutertre, F. (2024). Chitosan-based hydrogels: Influence of crosslinking strategy on rheological properties. Carbohydrate Polymers, 341, Article 122329. https://doi.org/10.1016/j.carbpol.2024.122329

Rodríguez-Rodríguez, R., Carreón-Álvarez, C., Cruz-Medina, C. A., Knauth, P., López, Z., Fletes-Vargas, G., & Rodríguez Sahagún, M. (2025). A review of pH-responsive chitosan-based hydrogels for drug delivery applications. European Polymer Journal, 237, Article 114173. https://doi.org/10.1016/j.eurpolymj.2025.114173

Strotmann, U., Thouand, G., Pagga, U., Gartiser, S., & Heipieper, H. J. (2023). Toward the future of OECD/ISO biodegradability testing-new approaches and developments. Applied Microbiology and Biotechnology, 107(7–8), 2073–2095. https://doi.org/10.1007/s00253-023-12406-6

Tian, B., & Liu, J. (2023). Smart stimuli-responsive chitosan hydrogel for drug delivery: A review. International Journal of Biological Macromolecules. https://doi.org/10.1016/j.ijbiomac.2023.123902

Thirupathi, K., Raorane, C. J., Ramkumar, V., Ulagesan, S., Santhamoorthy, M., Raj, V., Krishnakumar, G. S., Phan, T. T. V., & Kim, S.-C. (2023). Update on chitosan-based hydrogels: Preparation, characterization, and its antimicrobial and antibiofilm applications. Gels, 9(1), Article 35. https://doi.org/10.3390/gels9010035

VanZanten, A., Chen, S.-Y., Driscoll, M. M., & Szczepanski, C. R. (2024). Unconstrained dynamic gel swelling generates transient surface deformations. Soft Matter, 20, 6742–6753. https://doi.org/10.1039/D4SM00762J

Wang, C., Yu, Y., Chen, H., Zhang, S., Wang, J., & Liu, C. (2019). Construction of cytokine reservoirs based on sulfated chitosan hydrogels for the capturing of VEGF in situ. Journal of Materials Chemistry B, 7(16), 2785–2793. https://doi.org/10.1039/C8TB02895H

Yang, H.-B., Xing, L.-Y., Liu, T.-F., Li, M., Geng, J., Zhang, Y., Zhang, Y.-B., Wang, R.-C., Sarsenbekuly, B., Kang, W.-L., & Zhang, L.-M. (2025). Swelling kinetics of polymer microspheres used for conformance control and their matching mechanisms with oil reservoir fractures. Petroleum Science, 22(12), 5203–5211. https://doi.org/10.1016/j.petsci.2025.11.011

Yıldırım, M., Poyraz, S., Acet, Ö., Önal Acet, B., Karakoç, V., & Odabaşı, M. (2025). Chitosan hydrogels: Versatile platforms for drug delivery in cancer treatment, wound dressing, and 3D bioprinting applications. International Journal of Biological Macromolecules. https://doi.org/10.1016/j.ijbiomac.2025.144367

Zhao, L., Zhou, Y., Zhang, J., Liang, H., Chen, X., & Tan, H. (2023). Natural polymer-based hydrogels: From polymer to biomedical applications. Pharmaceutics, 15(10), Article 2514. https://doi.org/10.3390/pharmaceutics15102514

Žigrayová, D., Mikušová, V., & Mikuš, P. (2024). Advances in chitosan derivatives: Preparation, properties and applications in pharmacy and medicine. Gels, 10(11), Article 701. https://doi.org/10.3390/gels10110701

Published

2026-07-28

How to Cite

Maresi, S. R. P., Budikania, T. S., Afriani, K., Roziafanto, A. N., Mualim, A. D., & Kholidanata, F. (2026). Early swelling kinetics of chitosan hydrogels under different acidity conditions for designing controlled-release fertilizers: -. Applied Environmental Science, 4(1). https://doi.org/10.61511/aes.v4i1.2026.3710

Issue

Section

Articles

Citation Check