Nanosized Calcium Phosphates as Novel Macronutrient Nano-Fertilizers

The need for qualitatively and quantitatively enhanced food production, necessary for feeding a progressively increasing World population, requires the adoption of new and sustainable agricultural protocols. Among them, limiting the waste of fertilizers in the environment has become a global target. Nanotechnology can offer the possibility of designing and preparing novel materials alternative to conventional fertilizers, which are more readily absorbed by plant roots and, therefore, enhance nutrient use efficiency. In this context, during the last decade, great attention has been paid to calcium phosphate nanoparticles (CaP), particularly nanocrystalline apatite and amorphous calcium phosphate, as potential macronutrient nano-fertilizers with superior nutrient-use efficiency to their conventional counterparts. Their inherent content in macronutrients, like phosphorus, and gradual solubility in water have been exploited for their use as slow P-nano-fertilizers. Likewise, their large (specific) surfaces, due to their nanometric size, have been functionalized with additional macronutrient-containing species, like urea or nitrate, to generate N-nano-fertilizers with more advantageous nitrogen-releasing profiles. In this regard, several studies report encouraging results on the superior nutrient use efficiency showed by CaP nano-fertilizers in several crops than their conventional counterparts. Based on this, the advances of this topic are reviewed here and critically discussed, with special emphasis on the preparation and characterization approaches employed to synthesize/functionalize the engineered nanoparticles, as well as on their fertilization properties in different crops and in different (soil, foliar, fertigation and hydroponic) conditions. In addition, the remaining challenges in progress toward the real application of CaP as nano-fertilizers, involving several fields (i.e., agronomic or material science sectors), are identified and discussed.