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There are several methods for agrochemicals application. Most often agrochemicals are sprayed by water solutions. This method is associated with high loss during application and short duration of action. Less than 5 % of pesticidesPesticides are products and agents designed to eliminate plant and animal pests, to protect plants, to protect supplies and products, to protect premi… More target the pest1, 2 and only 30–50 % of fertilizers is used by the crops.3
Controlled-release systems (CRSs) enable agrochemicals last longer, thus elevate its effectiveness.4-7
CRSs advantages | CRSs impact |
Higher effectivity Lower agrochemicals consumption Lower agrochemicals mobility | Lower costs Lower mechanization and energy demand Higher agrochemicals stability Lower toxicity Lower health risk Better safety – lower occupation risk of exposure to agrochemicals Lower risk for resistance development Lower phytotoxicity |
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Particles of agrochemicals are encapsulated into polymerA polymer is a substance or material consisting of very large molecules, or macromolecules, composed of many repeating subunits. shell. Microcapsules protect the agrochemicals from degradation and allow slow and continuous release of the active agent. Polymers can be both natural (starchNatural polymer (carbohydrate) consisting of amylose and amylopectin, gained from maize, potatoes, wheat, tapioca etc. When glucose is connected to po… More, gelatin, celluloseCellulose is the principal component of cell walls in all higher forms of plant life, at varying percentages. It is therefore the most common organic … More) and synthetic (polystyrene, polyurethan, polyacrylamide).8-10
When non-biodegradable polymers are used, capsule suspension formulations are source of primary microplasticsMicroplastics is a general term for plastic fragments of various origins up to 5mm in size. Their existence is mainly associated with their presence i… More. ECHA plans to ban primary microplasticsMicroplastics is a general term for plastic fragments of various origins up to 5mm in size. Their existence is mainly associated with their presence i… More in agriculture. Thus, novel bio-degradable materials for microencapsulation are needed.
Nanomaterials are at least in one dimension of size 1-100 nm. Nanoformulations include: nanoparticles, encapsulated nanoparticles, nanoporous materials, nanocoating and nanoemulsions.11 These formulations allow slow release and better targeting (see Fig. 2). However, comprehensive knowledge about nanoformulated chemicals, their safety and behavior in natural ecosystems is missing.12-14 As well as microplasticsMicroplastics is a general term for plastic fragments of various origins up to 5mm in size. Their existence is mainly associated with their presence i… More, also nanoplastics are dangerous in the environment.
The active agent is in mixture with carrier (polymerA polymer is a substance or material consisting of very large molecules, or macromolecules, composed of many repeating subunits.) in the form of macroscopic pellets or granules. Agrochemicals release from the matrix is based on diffusion or biodegradability of the matrix. It can be used only for agrochemicals applied to soil.
PolymerA polymer is a substance or material consisting of very large molecules, or macromolecules, composed of many repeating subunits. coating can prolong active agent effect. Typically, coating is used for granulated fertilizer or to protect seeds. BiodegradableBiodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi. polymers like PHAs are of high interest for this application.
There is a high demand for biodegradableBiodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi. and non-toxic polymers for novel agrochemicals formulation. PHAsPolyhydroxyalkanoates (PHA) or the polyhydroxy fatty acids, are a family of biodegradable polyesters. As in many mammals, including humans, that hold … More are fully biodegradableBiodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi., biocompatibleBiocompatibility is a general term describing the property of a material being compatible with living tissue. Biocompatible materials do not produce a… and non-toxic. They do not accumulate in soil environment. Moreover, they can be a source of organic carbon and positively impact soil microorganisms.15
In laboratory conditions, microencapsulation of pesticidesPesticides are products and agents designed to eliminate plant and animal pests, to protect plants, to protect supplies and products, to protect premi… More into PHBVPolyhydroxy butyrate (PHB) is a Polyhydroxyalkanoates (PHA), a polymer belonging to the polyesters class that are o… More and P34HB co-polymers led to slower release of chemicals, higher photostability and higher effectivity compared to standard formulations.16-18 However, due to high demands of microencapsulation process and, so far, limited research results, we haven’t considered microencapsulation for further formulations development.
PHAs has been tested for degradable matrix slow-release formulations solo or in combination with other natural materials in laboratory conditions. The release of metribuzin from the P3HB matrix lasted for weeks or months (depending on the size of the matrix).3, 19-22 Effectivity of fungicide tebuconazole used in P3HBPolyhydroxy butyrate (PHB) is a Polyhydroxyalkanoates (PHA), a polymer belonging to the polyesters class that are o… More matrix formulation was comparable with commercial formulation even after 8 weeks of incubation.23 After 12 weeks, slow-release formulation of ammonium nitrate fertilizer was more effective than commercial formulation.3
P(3HB)/clay
P(3HB)/wood flour
P(3HB)/peat
Fig. 3: P3HB-based granules and pellets – formulations of agrochemicals with slow-release. Adopted from ref.24
Murugan et al. used PHBHPoly(3-hydroxybutyrate-co-3-hydroxyvalerate) is a Polyhydroxyalkanoates type polymer. It is biodegradable, nontoxic, biocompatible plastic produced … More co-polymer, palm fiber and NPK fertilizer in pellets. This fertilizer formulation improved growth of oil palms. Pellets elevated protebacteria population which might be beneficial for crops.15
PHBVPolyhydroxy butyrate (PHB) is a Polyhydroxyalkanoates (PHA), a polymer belonging to the polyesters class that are o… More co-polymer extruded pellets were also tested as CRS for DCD nitrification inhibitor. The slow release was based on precise engulfment of the active agent in the polymerA polymer is a substance or material consisting of very large molecules, or macromolecules, composed of many repeating subunits. and further biodegradability of the polymer.25
1 Pimentel, D. Amounts of pesticidesPesticides are products and agents designed to eliminate plant and animal pests, to protect plants, to protect supplies and products, to protect premi… More reaching target pests: Environmental impacts and ethics. Journal of Agricultural and Environmental Ethics. 1995, 8(1): 17-29. doi: 10.1007/BF02286399.
2 Miller, G. T. Sustaining the Earth: An Integrated Approach: Brooks/Cole, 2004. 9780534496722.
3 Volova, T., E. Shishatskaya, N. Zhila, et al., Eds. New Generation Formulations of Agrochemicals. New York: Apple Academic Press, 2020.
4 Dhananjayan, V., S. Jayakumar and B. Ravichandran. Conventional Methods of Pesticide Application in Agricultural Field and Fate of the PesticidesPesticides are products and agents designed to eliminate plant and animal pests, to protect plants, to protect supplies and products, to protect premi… More in the Environment and Human Health. In: R. K. R, Thomas, S., Volova, T. and K, J. Controlled Release of PesticidesPesticides are products and agents designed to eliminate plant and animal pests, to protect plants, to protect supplies and products, to protect premi… More for SustainableAn attempt to provide the best outcomes for the human and natural environments both now and into the indefinite future. One famous definition of susta… More Agriculture. Cham: Springer International Publishing, 2020: 1-39. 978-3-030-23396-9.
5 Tian, C., X. Zhou, Q. Liu, et al. Effects of a controlled-release fertilizer on yield, nutrient uptake, and fertilizer usage efficiency in early ripening rapeseed (Brassica napus L.). Journal of Zhejiang University. Science. B. 2016, 17(10): 775-786. doi: 10.1631/jzus.B1500216.
6 Li, Z., Z. Liu, M. Zhang, et al. Long-term effects of controlled-release potassium chloride on soil available potassium, nutrient absorption and yield of maize plants. Soil and Tillage Research. 2020, 196: 104438. doi: https://doi.org/10.1016/j.still.2019.104438.
7 Sikora, J., M. Niemiec, A. Szeląg-Sikora, et al. The Impact of a Controlled-Release Fertilizer on Greenhouse GasGaseous constituent of the atmosphere, both natural and anthropogenic, that absorbs and emits radiation at specific wavelengths within the spectrum of… More Emissions and the Efficiency of the Production of Chinese Cabbage. Energies. 2020, 13: 2063. doi: 10.3390/en13082063.
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9 Cao, L., Y. Liu, C. Xu, et al. BiodegradableBiodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi. poly(3-hydroxybutyrate-co-4-hydroxybutyrate) microcapsules for controlled release of trifluralin with improved photostability and herbicidal activity. Materials Science and Engineering: C. 2019, 102: 134-141. doi: https://doi.org/10.1016/j.msec.2019.04.050.
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11 Chhipa, H. Nanofertilizers and nanopesticides for agriculture. Environmental Chemistry Letters. 2017, 15(1): 15-22. doi: 10.1007/s10311-016-0600-4.
12 Vryzas, Z. Pesticide fate in soil-sediment-water environment in relation to contamination preventing actions. Current Opinion in Environmental Science & Health. 2018, 4: 5-9. doi: https://doi.org/10.1016/j.coesh.2018.03.001.
13 Zhao, X., H. Cui, Y. Wang, et al. Development Strategies and Prospects of Nano-based Smart Pesticide Formulation. Journal of Agricultural and Food Chemistry. 2018, 66(26): 6504-6512. doi: 10.1021/acs.jafc.7b02004.
14 Garrigou, A., C. Laurent, A. Berthet, et al. Critical review of the role of PPE in the prevention of risks related to agricultural pesticide use. Safety Science. 2020, 123: 104527. doi: https://doi.org/10.1016/j.ssci.2019.104527.
15 Murugan, P., S. Y. Ong, R. Hashim, et al. Development and evaluation of controlled release fertilizer using P(3HB-co-3HHx) on oil palm plants (nursery stage) and soil microbes. Biocatalysis and Agricultural Biotechnology. 2020, 28: 101710. doi: https://doi.org/10.1016/j.bcab.2020.101710.
16 Lobo, F. A., C. L. de Aguirre, M. S. Silva, et al. Poly(hydroxybutyrate-co-hydroxyvalerate) microspheres loaded with atrazine herbicide: screening of conditions for preparation, physico-chemical characterization, and in vitro release studies. PolymerA polymer is a substance or material consisting of very large molecules, or macromolecules, composed of many repeating subunits. Bulletin. 2011, 67(3): 479-495. doi: 10.1007/s00289-011-0447-6.
17 Grillo, R., N. F. S. de Melo, R. de Lima, et al. Characterization of Atrazine-Loaded BiodegradableBiodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi. Poly(Hydroxybutyrate-Co-Hydroxyvalerate) Microspheres. Journal of Polymers and the Environment. 2010, 18(1): 26-32. doi: 10.1007/s10924-009-0153-8.
18 Suave, J., E. C. Dall’Agnol, A. P. T. Pezzin, et al. BiodegradableBiodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi. microspheres of poly(3-hydroxybutyrate)/poly(ε-caprolactone) loaded with malathion pesticide: Preparation, characterization, and in vitro controlled release testing. Journal of Applied PolymerA polymer is a substance or material consisting of very large molecules, or macromolecules, composed of many repeating subunits. Science. 2010, 117(6): 3419-3427. doi: https://doi.org/10.1002/app.32082.
19 Volova, T. G., N. O. Zhila, O. N. Vinogradova, et al. Constructing herbicide metribuzin sustained-release formulations based on the natural polymerA polymer is a substance or material consisting of very large molecules, or macromolecules, composed of many repeating subunits. poly-3-hydroxybutyrate as a degradable matrix. J Environ Sci Health B. 2016, 51(2): 113-125. doi: 10.1080/03601234.2015.1092833.
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21 Zhila, N., A. Murueva, A. Shershneva, et al. Herbicidal activity of slow-release herbicide formulations in wheat stands infested by weeds. Journal of Environmental Science and Health, Part B. 2017, 52(10): 729-735. doi: 10.1080/03601234.2017.1356668.
22 Kiselev, E. G., A. N. Boyandin, N. O. Zhila, et al. Constructing sustained-release herbicide formulations based on poly-3-hydroxybutyrate and natural materials as a degradable matrix. Pest Management Science. 2020, 76(5): 1772-1785. doi: 10.1002/ps.5702.
23 Volova, T. G., S. V. Prudnikova, N. O. Zhila, et al. Efficacy of tebuconazole embedded in biodegradableBiodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi. poly-3-hydroxybutyrate to inhibit the development of Fusarium moniliforme in soil microecosystems. Pest Manag Sci. 2017, 73(5): 925-935. doi: 10.1002/ps.4367.
24 Volova, T., S. Prudnikova, A. Boyandin, et al. Constructing Slow-Release Fungicide Formulations Based on Poly(3-hydroxybutyrate) and Natural Materials as a Degradable Matrix. J Agric Food Chem. 2019, 67(33): 9220-9231. doi: 10.1021/acs.jafc.9b01634.
25 Levett, I., M. Liao, C. Pratt, et al. Designing for effective controlled release in agricultural products: new insights into the complex nature of the polymer–active agent relationship and implications for use. Journal of the Science of Food and Agriculture. 2020, 100(13): 4723-4733. doi: https://doi.org/10.1002/jsfa.10531.
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