Enzymatic Synthesis of 100% Lignin Biobased Granules as Fertilizer

Jun 27, 2019 - In an attempt to reduce the loss of fertilizer due to leaching, this study ... granules as fertilizer storage and controlled slow relea...
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Research Article Cite This: ACS Sustainable Chem. Eng. 2019, 7, 12621−12628

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Enzymatic Synthesis of 100% Lignin Biobased Granules as Fertilizer Storage and Controlled Slow Release Systems Domitille Legras-Lecarpentier,†,‡ Karina Stadler,† Renate Weiss,† Georg M. Guebitz,†,‡ and Gibson S. Nyanhongo*,† †

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Institute of Environmental Biotechnology, University of Natural Resources and Life Sciences (BOKU), Konrad Lorenz Strasse 22, Vienna, Tulln 3430 Austria ‡ Austrian Centre for Industrial Biotechnology (ACIB), Konrad Lorenz Strasse 22, Vienna, Tulln 3430 Austria ABSTRACT: In an attempt to reduce the loss of fertilizer due to leaching, this study investigates for the first time the possibility of synthesizing lignosulfonate-based fertilizer slow release granules by using laccases as green catalysts. Trametes hirsuta laccases (THL) extensively oxidized and polymerized lignosulfonates resulting in 62 and 54% decrease in phenolic groups from 52 g l−1 in samples incubated at pH 6 and 7, respectively, and as evidenced by the formation insoluble polymers at pH 6 and 7 in less than 2 h. Preliminary attempts to synthesize 100% lignosulfonate granules resulted in highly brittle randomly breaking particles with most particles 30 °C > 23 °C (RT). Synthesis of Lignin-Based Granules and Incorporation of Fertilizer. Preliminary attempts to synthesize 100% lignosulfonate granules resulted in the formation of highly brittle, randomly breaking particles with most particles being 2 nm), alginate was incorporated into the polymerized lignosulfonates by simply dropping it into a solution containing calcium ions which led to the precipitation and formation of granules. As shown in Figure 3, perfect granules could only be obtained with a minimum alginate content of 1% below which the polymerized lignosulfonates were simply stuck together. An increase in alginate concentration beyond 2% led to an increased kicking out of lignin (less lignosulfonates) in the matrix (Figure 3). A microscopic analysis of the dried granules showed a more compact structure with increasing alginate concentration as shown in Figure 3, attributed to the increased calcium

alaginate. A minimum alginate content of 1% was observed as the most appropriate content to obtain perfect granules. The granules made with lignosulfonates are slightly bigger (2−3 mm diameter) in size than the ones made only with alginate (1.5−2 mm diameter). It should also be noted that preliminary trials aimed at mixing THL polymerized lignosulfonates with alginate and then incorporating potassium nitrate and phosphate made it difficult to obtain granules. Water Absorption Studies. The highest water holding capacity was obtained with 100% lignosulfonate granules resulting in a water uptake exceeding 600% after 45 min of incubation in water. The lowest water absorption was observed with pure alginate granules (Figure 4). Generally, the water uptake decreased with increasing alginate concentration. Thus, although alginate is important for the formation of polymerized lignosulfonate granules, an increase in its concentration decreases the water absorption properties. This may be attributed to the formation of a more compact structure as evidenced by the microscopic images. The more compact structure may prevent expansion and hence the accumulation of water in the lignosulfonates. These studies show that the laccase polymerized lignosulfonates can also be beneficial to plants by absorbing, storing, and providing water for the plants. Potassium Nitrate and Potassium Phosphate Release Studies. The initial potassium nitrate and phosphate concentrations in the various granules decreased with increasing alginate concentration used for the synthesis of the granules (Figure 5). The highest concentrations of potassium nitrate (3.9 mg mL−1) and phosphate (2.8 mg mL−1) were recorded in 100% lignosulfonate granules with the least being in 100% alginate (Figure 5). This is probably due to the increasing compactness of the granules as evidenced by 12625

DOI: 10.1021/acssuschemeng.9b02689 ACS Sustainable Chem. Eng. 2019, 7, 12621−12628

Research Article

ACS Sustainable Chemistry & Engineering

Figure 5. Release profiles of potassium phosphate and potassium nitrate in lignosulfonate-based granules made with different alginate concentrations as compared to pure lignosulfonates and pure alginate granules.

lignin lowered its water-solubility and is independent of pH. This shows that the careful optimization of the concentrations of calcium and alginate being used could provide beneficial effects in the design of lignosulfonate-based fertilizer slow release systems.40 Further, the increase in the compactness of the granules, as shown in the microscopic images in this study (Figure 3), along with microscopy, infrared spectroscopy, and accessible surface studies by Sipponen et al.40 suggest that the alginate and calcium helped to increase the compactness of the granules and hence decreased the pore size that affected the release of the fertilizers. However, in line with the observed fast initial fertilizer release studies, alginate is known to exhibit a burst release followed by a slow-release of the remaining nutrients.9 These results suggest that the laccase polymerized lignosulfonate controlled water-solubility of lignin precipitated by using calcium and alginate may lead to the production of a viable fertilizer controlled release system. Despite the relatively fast release of fertilizer in 100% lignosulfonate granules, this study shows the potential of synthesizing fertilizer-impregnated lignosulfonate rather than using lignin as coating material. This is because many studies have demonstrated that the use of lignosulfonates, kraft lignin,

microscopic observation. Generally, a fast release occurred during the first day of incubation followed by a steady and slow decrease over the 5 days of incubation. Release studies showed that 100% lignosulfonate granules released approximately 51% of potassium nitrate and 56% potassium phosphate in 94% during the first 10 days of incubation (Figure 5). The release decreased with increasing alginate concentration in the lignosulfonate granules as shown in Figure 5 going beyond 25 days. This could be attributed to the swelling behavior of the coatings in agreement with findings by Samanta and Ray,39 who noted that the release kinetics of the fertilizer loaded beads are directly influenced by the swelling behavior. The alginate granules were the least efficient in both uptaking and releasing both fertilizers. Increasing alginate concentration during the synthesis of the granules, though good for producing perfect granules, reduced both uptake and release of potassium nitrate and phosphate concentration (Figure 5). Even the performance of release studies at different pH values of 4, 7, and 8 had no effect on the amount of fertilizer released. When the granules were crushed, it was clear that most of the fertilizer was still trapped inside the granules. This may be attributed to a similar phenomenon observed by Sipponen et al.,40 who found that the addition of calcium to 12626

DOI: 10.1021/acssuschemeng.9b02689 ACS Sustainable Chem. Eng. 2019, 7, 12621−12628

Research Article

ACS Sustainable Chemistry & Engineering acetylated kraft lignin, or soda flax lignin as coatings led to complete fertilizer release less in 2−24 h.16,41,42 Although the irreversible release of both potassium nitrate and potassium phosphate is unexpected, a similar effect was also observed when granulated simple superphosphate fertilizer, consisting of calcium phosphate monobasic and gypsum, was coated with hydroxymethylated modified kraft lignins subsequently crosslinked with phenol-formaldehyde resin.43 The authors observed that 80−50% remained irreversibly bound inside the modified lignin coatings.43 In comparison with other similar biobased coatings, lignosulfonates alginate granules were able to retard the release of fertilizers better than poly(vinyl alcohol)/chitosan coatings that released up to 70% of the fertilizer in 4 days,44 alginate coatings that released 90% of potassium in 6 days,45 potato starch-based coatings that completely released the fertilizer in 96 h,46 and starch/ polylactic acid coatings that retarded urea release for 24 h.47 The observation that the release of the fertilizer is affected by the concentration of alginate and presence of calcium is highly encouraging as it allows the possibility of engineering these parameters in order to produce an efficient controlled release system.

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CONCLUSION Laccase polymerization of lignosulfonates produced insoluble water absorbing granules when alginate was incorporated. Despite the relatively fast release of fertilizer in 100% lignosulfonate granules and the trapping of fertilizers in lignosulfonate/alginate granules, simple soaking rather than the use of lignosulfonates as a coating shows great promise as a fertilizer storage and slow release system. The fact that increasing alginate concentration and presence of calcium in polymerized lignosulfonates during the synthesis of granules decrease the release of both potassium nitrate and potassium phosphate suggests that optimizing the concentrations of alginate and calcium could help produce a viable and efficient fertilizer controlled release system. The presence of abundant COOH and OH groups in lignosulfonates may also allow lignosulfonate granules to act as soil buffering systems that promote plant growth.

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AUTHOR INFORMATION

Corresponding Author

*Tel: (+43) 1 47654 97401. Fax: +43 1 47654-97409. E-mail: [email protected] or [email protected]. ORCID

Gibson S. Nyanhongo: 0000-0002-5379-8971 Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the government of Lower Austria [NÖ Forschungs- und Bildungsges.m.b.H. (NFB)]. REFERENCES

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