Hybridize magnesium-iron layered double hydroxide with biopolymers to develop multiple pathways for phosphate sorption and release: A potential slow release phosphorus fertilizer

Abstract

The intensive use of chemical fertilizers presents a dilemma for sustaining food production or causing soil degradation and posing agricultural contamination. The reduction of phosphorus (P) fertilizer usage is particularly crucial because it is a limited resource. This situation calls for the development of efficient P fertilizers to address the impending P deficiency. Mg-Fe layered double hydroxides (LDH) with 0.5 and 2.5 M metal precursors were hybridized with chitosan (CTS) and carboxymethyl cellulose (CMC) to design alternatives of slow release P fertilizers. While phosphate (PO4) sorption capacities were in the order of Mg-Fe LDH > 2.5LDH-CTS/CMC > 0.5LDH-CTS/CMC, PO4 release from 0.5LDH-CTS exhibited a rate constant ∼2.6–7.6 times lower than that of other samples, which had not reached equilibration even after 2688 h. Fe-EXAFS data implied the greatest degree of isomorphic substitution into LDH interlayer of 0.5LDH-CTS. In addition to intercalated PO4, P-XANES data also suggested the organic-P and Fe(III)-P on 0.5LDH-CTS, causing versatile retention processes. After 2688 h of PO4 release, LDH structure gradually weathered and transformed primarily into a structure dominated by ferric (oxyhydrox)oxides. On 0.5LDH-CTS, however, 14.3% of Fe inventory was contributed by Fe(II) species. The Fe(II) domains in conjunction with the likely remaining Mg-Fe LDH structure and amorphous Mg(OH)2 provided bonding sites for PO4, serving as the key factor for the continuous PO4 release beyond 2688 h. Such extended duration of PO4 release warrants the use of LDHs hybridized with biopolymers as promising substitutes for slow release P fertilizers.