Metal accumulation in cacao (Theobroma cacao L.) cultivation represents an important agronomic and food-safety concern, particularly in acidic tropical soils where cadmium (Cd) and other trace metals can become bioavailable and translocate to plant tissues. Green magnetic nanomaterials offer a potential strategy for reducing metal mobility in agricultural substrates, but their performance depends on surface chemistry, dose, and plant genotype. In this study, we synthesized and evaluated MCRES, defined here as a maghemite–Citrus reticulata extract system, a biofunctionalized γ-Fe2O3-based nanosystem prepared by coupling iron oxide nanoparticles (NPs) with a 3% (w/v) Citrus reticulata peel extract. The objective was to determine whether citrus-mediated biofunctionalization could produce a scalable magnetic nanoamendment capable of modifying Cd and naturally occurring Ni partitioning in cacao seedlings. MCRES was recovered magnetically and dried, yielding 8.44 g of product from 10 g of precursor. Rietveld analysis performed in X ray diffractograms confirmed phase-pure cubic γ-Fe2O3 with a lattice parameter of 0.8332 nm, a crystallite size of 11.3(1) nm, and satisfactory refinement quality (χ2 ≈ 1.34). Transmission electron microscope images showed quasi-spherical NPs with a log-normal size distribution centered at 7.5 nm. Magnetic measurements showed superparamagnetic-like behavior at 300 K, high saturation magnetization values of 62 emu g−1 at 300 K and 71 emu g−1 at 5 K, and elevated effective anisotropy values obtained from the Law of Approach to Saturation fitting. MCRES was applied at 0, 1, 2, 4, and 6 g pot−1 to cacao seedlings containing Cd-amended Ultisol with naturally occurring Ni. Plant responses were genotype and dose dependent: TSH-1188 genotype showed limited dose sensitivity for most biometric variables, whereas ICS-95 genotype showed significant dose effects, with maximum growth at the 2 g pot−1 treatment. Metal-partitioning results indicated that Cd remained comparatively mobile toward shoots, whereas Ni was preferentially retained in roots. In TSH-1188 genotype, the Ni translocation factor decreased from 3.07 in the control to 0.85–1.00 at higher MCRES doses. Compared with previous work on non-biofunctionalized nanomaghemite, these results suggest that citrus-mediated biofunctionalization produces a distinct Cd/Ni partitioning response. Overall, MCRES is recommended as a promising nursery-scale green nanoamendment for reducing metal mobility in cacao cultivation, but its agronomic use should be optimized according to genotype and dose. Future work should include side-by-side comparisons with unfunctionalized γ-Fe2O3, Citrus reticulata extract alone, and non-contaminated controls under field conditions to validate its long-term effectiveness and environmental safety.
Ramos-Guivar et al. (Sun,) studied this question.