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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

Postal Subscription Code 80-973

2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2023, Vol. 17 Issue (5) : 53    https://doi.org/10.1007/s11783-023-1653-9
RESEARCH ARTICLE
Highly degradable chitosan-montmorillonite (MMT) nanocomposite hydrogel for controlled fertilizer release
Zeou Dou1, Maria Vitoria Bini Farias1, Wensi Chen1, Dongjing He2, Yuhang Hu2,3, Xing Xie1()
1. School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332, USA
2. George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA 30332, USA
3. School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA 30332, USA
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Abstract

● A controlled-release fertilizer was developed based on chitosan biopolymer scaffold.

● Chitosan-MMT scaffold achieved a well-controlled nutrient release.

● Highly water-absorbing chitosan-MMT hydrogels enhanced the soil water retention.

● Physically crosslinked chitosan-MMT hydrogels exhibited excellent degradability.

Fertilizer consumption is increasing drastically along with the rapid expansion of farming in response to the ever-growing population. However, a significant portion of the nutrients in traditional fertilizers is lost during leaching and runoff causing economic loss and environmental threats. Polymer-modified controlled-release fertilizers provide an opportunity for mitigating adverse environmental effects and increasing the profitability of crop production. Here, we present a cheap and easy-to-fabricate controlled-release fertilizer excipient based on hydrogels scaffolded by safe and biodegradable chitosan and montmorillonite (MMT) nanoclays. By introducing elastic and flexible physical crosslinking induced by 2-dimensional (2D) MMT nanoflakes into the chitosan hydrogel, highly swellable and degradable chitosan-MMT nanocomposites were fabricated. The addition of MMT into the chitosan hydrogels enhanced the total release of phosphorous (P) and potassium (K), from 22.0 % to 94.9 % and 9.6% to 31.4 %, respectively, compared to the pure chitosan gel. The chitosan-MMT nanocomposite hydrogel achieved a well-controlled overall fertilizer release in soil. A total of 55.3 % of loaded fertilizer was released over 15 d with a daily release of 2.8 %. For the traditional fertilizer podwer, 89.2 % of the fertilizer was washed out during the first irrigation under the same setup. In the meantime, the nanocomposites improved the water retention of the soil, thanks to its excellent water absorbency. Moreover, the chitosan-MMT nanocomposite hydrogels exhibited high degradation of 57 % after swelling in water for 20 d. Such highly degradable fertilizer excipient poses minimal threat to the long-term fertility of the soil. The engineered Chitosan-MMT biopolymer scaffold as a controlled-release fertilizer excipient provides a promising opportunity for advancing sustainable agriculture.

Keywords Biopolymer      Hydrogel      Controlled-release fertilizer      Nanoclay      Nanocomposite     
Corresponding Author(s): Xing Xie   
Issue Date: 22 November 2022
 Cite this article:   
Zeou Dou,Maria Vitoria Bini Farias,Wensi Chen, et al. Highly degradable chitosan-montmorillonite (MMT) nanocomposite hydrogel for controlled fertilizer release[J]. Front. Environ. Sci. Eng., 2023, 17(5): 53.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-023-1653-9
https://academic.hep.com.cn/fese/EN/Y2023/V17/I5/53
Fig.1  Schematics demonstrating the crosslinking of chitosan-montmorillonite (MMT) nanocomposites.
Fig.2  (a–e) SEM images of chitosan-MMT nanocomposites of 0 wt% (a), 3.3 wt% (b), 10 wt% (c), 16.7 wt% (d), and 23.3 wt% (e) MMT nanoclay crosslinked with 2.3 wt% GA. (f) Energy-dispersive X-ray spectroscopy (EDX) mapping images of chitosan-MMT of 16.7 wt% MMT crosslinked with 1.15 wt% GA. (g) Fourier-transform infrared spectroscopy (FTIR) spectra of uncrosslinked chitosan, chemically crosslinked chitosan gel, MMT powder, chitosan-MMT nanocomposite loaded with NPK fertilizer, and NPK fertilizer powder.
Fig.3  Shear modulus (a) and swelling ratio in DI water (b) of chitosan-MMT composites of different MMT contents.
Fig.4  (a, b) Cumulative fertilizer release profile of chitosan-MMT composite hydrogels of different GA contents (a) or MMT contents (b) (total fertilizer loaded in the gel was 300 mg/g). (c) Specific final cumulative release of each nutrient element after 20 d. The dash lines indicate the total NPK loaded, respectively. (d) Degradation ratio of the composites in water after 20 d. Insets are the pictures of the filtered residual gels.
Fig.5  (a) Percentage of fertilizer release of 10 % MMT nanocomposite as a function of time. Korsmeyer-Peppas: n = 0.14; k = 27.56 d–0.14; R2 = 0.995; Peppas-Sahlin: m = 0.11; k1 = 18.87 d–0.11; k2 = 8.56 d–0.11; R2 = 0.995. (b) Fickian release fraction, F, from 10 % MMT nanocomposite hydrogel with m = 0.11, as a function of percentage release, when k1 = 18.87 d–0.11; k2 = 8.56 d–0.11.
Fig.6  Fertilizer release in soil columns from chitosan-MMT (10 wt%) nanocomposite hydrogels and fertilizer powder (30 mg fertilizer loaded).
Controlled-release strategy Method Materials Fertilizer Biodegradable Release rate Ref.
Encapsulation Layered coating with chemical crosslinking Poly(vinyl alcohol) (PVA), chitosan, Polyacrylamide-co-acrylic acid (poly(AA-co-AM)) NPK NA In deionized water (DI):84 % N, 62 % P, 36 % K in 30 d Noppakundilograt et al. (2015)
Rotary drum layered coating with chemical crosslinking Chicken feather protein, AA N NA In soil:80 % in 56 d Yang et al. (2013)
Spray coating MMT clay, chitosan K Yes In DI:100 % in 2 h Angelo et al. (2021)
Immersion crosslinking Starch acetate, glycerol, PVA Diammonium phosphate (DAP) NA In DI:100 % N in 5 h, 100 % P in 4.5 h Sofyane et al. (2021)
Immersion Chitosan-clay composite, paraffin wax DAP NA In DI:100 % P in 16 h;in soil:100 % P in 30 d El Assimi et al. (2020)
Spray coating Chitosan/nanocellulose NPK Yes In DI:100 % NPK in 5 h Messa and Faez (2020)
Rotary drum with spray coating Lignin, carrageenan Triple superphosphate Yes In DI:78 % P in 120 h Fertahi et al. (2019)
Hydrogel scaffold Chemical crosslinking Poly(AA-co-AM), urea-formaldehyde oligomers NPK NA In soil:80 % K, 57 % P,80 % N in 15 d Xiang et al. (2017)
Hydrogel in-situ gelation Chemical crosslinking Chitosan, salicyladehyde N (Urea) NA In DI:75 % Urea in 11 d Iftime et al. (2019)
Hydrogel scaffold Physical and chemical crosslinking Chitosan, MMT clay NPK Yes In water:71 % N, 61 % P, 15 % K in 12 d;in soil:55 % NPK in 15 d This study
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