RESUMO
A novel bifunctional magnetic sorbent with mercapto and amino groups and ion imprinting (MBII) was synthesized using a one-step aqueous sol-gel process for preconcentration and determination of Cd(II) ions. MBII was employed as a microcolumn (MC) filler in a flow-through system coupled to GFAAS. The magnetic properties of the solid allowed microcolumn magnetic solid-phase extraction (MCMSPE) to be performed by simply including a single circular magnet around the MC. This assembly enabled complete attachment of the solid to the MC wall leaving a central void to facilitate higher sample flow rates without blockage or material loss. For comparison, a bifunctional magnetic solid without imprinting (MBNI) was also synthesized and evaluated. Both MBII and MBNI were characterized by FTIR, SEM, EDX, BET and magnetization measurements. The results showed the preservation of the magnetic core, its superparamagnetism and the functional groups in the solid. Batch studies revealed a maximum adsorption capacity for both materials at pH around 6 with equilibrium reached within 5 minutes. The advantages were reflected in the maximum adsorption capacity of MBII, which was found to be 2.5 times greater than that of MBNI. Both adsorbents were compared as MC fillers for dynamic preconcentration in MCMSPE systems. Under optimized conditions, MBNI showed a PCF of 125 and MBII of 250. The higher selectivity of MBII was corroborated by interfering ion studies. The analytical performance parameters for the proposed method using MBII as an adsorbent showed a detection limit of 0.05 ng L-1, a linear range of 2.0-80 ng L-1, an RSD% of 2.2 (n = 7; 20 ng L-1) and a lifetime of more than 300 preconcentration-elution cycles without loss of sensitivity or need for refilling. The method was successfully applied to the determination of trace Cd(II) in osmosis, lake and tap water with recoveries ranging from 98 to 105%. Comparison of these results with those of similar reported methods showed a considerable improvement primarily attributed to the combined effect of MBII's higher retention capacity and its magnetic properties that allowed higher sample flow rates and, thus, enhanced figures of merit.
