Removal of Arsenic(III) from water using magnetite precipitated onto Douglas fir biochar

Magnetic Fe₃O₄/Douglas fir biochar composites (MBC) were prepared with a 29.2% wt. Fe₃O₄ loading and used to treat As(III)-contaminated water. Toxicity of As(III) (inorganic) is significantly greater than As(V) and more difficult to remove from water. Removal efficiency was optimized verses pH, contact time and initial concentration. Column sorption and regeneration were also studied. Adsorption kinetics data best fitted the pseudo second order model (R² > 0.99). Adsorption was analyzed with three isotherm models at 20, 25 and 40 °C. The Sips isotherm showed the best fit at 25 °C with a 5.49 mg/g adsorption capacity, which is comparable with other adsorbents. MBC gave faster kinetics (~1-1.5 h) at pH 7 and ambient temperature than previous adsorbents. The Gibbs free energy (ΔG) of this spontaneous As(III) adsorption was -35 kJ/mol and ΔH = 70 kJ/mol was endothermic. Experiments were performed on industrial and laboratory wastewater samples in the presence of other co-existing contaminants (pharmaceutical residues, heavy metals ions and oxi-anions). The composite reduced the arsenic concentrations below the WHO's safe limit of 0.2 mg/L for waste water discharge. X-ray photoelectron spectroscopy (XPS) studies found As(III) and less toxic As(V) on Fe₃O₄ surfaces indicating adsorbed (or adsorbing) As(III) oxidation occurred upon contact with O₂ and possibly dissolved Fe(III) or upon drying under oxic conditions. Under anoxic conditions magnetite to maghemite transformation drives the oxidation. A pH-dependent surface chemisorption mechanism was proposed governing adsorption aided by XPS studies vs pH.