Closed-Loop Valorization of Annatto Seed Waste into Biochar: A Sustainable Platform for Phosphorus Adsorption and Safe Nutrient Recycling in Agro-Industries

Abstract

Valorizing agro-industrial waste into functional materials for environmental remediation and resource recovery is essential for advancing circular economy models. This study presents a novel closed-loop strategy to convert annatto (Bixa orellana) seed residues into biochar for phosphate recovery from aqueous solutions and real agro-industrial wastewater. A novel ternary modification with Fe, Zn, and Mn metals was applied to enhance the phosphate adsorption performance of the biochar. Materials were synthesized via pyrolysis at 600 °C and 700 °C, with ABC-M700 exhibiting the highest performance. Comprehensive characterization (FTIR, SEM-EDS, and XRF) confirmed the successful incorporation of metal (oxy)hydroxide functional groups, which facilitated phosphate binding. Adsorption studies revealed that ABC-M700 achieved a maximum phosphate removal capacity of 6.19 mg·g^-1, representing a 955% increase compared to unmodified ABC-N700 (0.59 mg·g^-1), and a 31% increase relative to ABC-M600 (4.73 mg·g^-1). Physicochemical characterization indicated increased surface area, well-developed mesoporosity, and the formation of metal (oxy)hydroxide functionalities. ABC-M700 achieved a maximum adsorption capacity of 73.22 mg·g^-1 and rapid kinetics, removing 95% of phosphate within 10 min and reaching equilibrium at 30 min. The material exhibited notable pH flexibility, with optimal performance in the range of pH 6-7. Performance evaluations using real wastewater from the same agro-industry confirmed its high selectivity, achieving 80% phosphate removal efficiency despite the presence of competing ions and organic matter. Phosphate fractionation revealed that 78% of adsorbed phosphate was retained in stable, metal-associated fractions. Although the material showed limited reusability, it holds potential for integration into nutrient recycling strategies as a slow-release fertilizer. These findings demonstrate a low-cost, waste-derived adsorbent with strong implications for circular economy applications and sustainable agro-industrial wastewater treatment. This study establishes a scalable model for agro-industries that not only reduces environmental impact but also addresses phosphorus scarcity and promotes resource-efficient waste management.

Keywords: annatto; circular economy; metal-modified biochar; nutrient recovery; waste valorization; wastewater treatment.

Figure 1

Phosphate adsorption capacity (q) of biochar derived from annatto seed waste, calcined at 600 °C and 700 °C in its natural forms (ABC-N600, ABC-N700) and metal-modified forms (ABC-M600 and ABC-M700).

Figure 2

XRD patterns of natural (ABC-N700) and metal-modified annatto biochar (ABC-M700).

Figure 3

SEM image of (a) natural (ABC-N700) and (b) metal-modified annatto biochar (ABC-M700) at 50 µm and 5 µm scales.

Figure 4

FTIR spectrum of natural ABC-N700 and modified annatto biochar ABC-M700.

Figure 5

Phosphate adsorption capacity (q) of metal-modified annatto biochar (ABC-M700) as a function of pH.

Figure 6

Phosphate adsorption kinetics of metal-modified annatto biochar (ABC-M700). Experimental data are presented as mean ± standard deviation from triplicate measurements.

Figure 7

(a) SEM image at 50 µm and 5 µm scales and (b) FTIR spectrum of metal-modified annatto biochar saturated with phosphate (ABC-M700-P).

Figure 8

Phosphate fractionation of metal-modified annatto biochar saturated with phosphate (ABC-M700-P).

Figure 9

Phosphate adsorption capacity of metal-modified annatto biochar (ABC-M700) and desorption capacity from metal-modified annatto biochar saturated with phosphate (ABC-M700-P).