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The biosorption of As(V) from aqueous solutions by pine sawdust chemically modified with iron in batch systems was investigated. The loading process of Fe in this biomaterial was achieved by hydrolysis of two different ferric salts. This modification of sawdust is an attempt to improve As(V) biosorption for practical applications. The kinetics and maximum biosorption capacities of the unmodified and modified pine sawdust were evaluated. It was found that the pseudo-second order model described the As(V) biosorption kinetic data and the Langmuir-Freundlich equation described the arsenate sorption equilibrium. These results indicated that the sorption mechanism was chemisorption on a heterogeneous material. The pH effects governing biosorption capacities were also evaluated, showing a decrease as pH value rises, indicating that this biosorption process is highly pH-dependent. The estimated maximum biosorption capacities of As(V), based on the Langmuir-Freundlich fit to the data were, at pH 4, 4.4 mg/g of untreated sawdust, (UN-SW), 12.85 mg/g of ferric chloride modified sawdust (FeCl-SW), and 6 mg/g of ferric nitrate modified sawdust (FeNit-SW); and at pH 7, 2.6 mg/g of UN-SW, 5.9 mg/g of FeCl-SW, and 4.6 mg/g of FeNit-SW. Sorption capacities of iron-modified pine sawdust were evidently higher than other similar biosorbents previously reported.