A simple and robust on-line sequential injection system based on solid phase extraction (SPE) coupled to a flow injection hydride generation atomic absorption spectrometer (FI-HGAAS) with a heated quartz tube atomizer (QTA) was developed and optimized for the determination of As(III) in groundwater without any kind of sample pretreatment. The method was based on the selective retention of inorganic As(V) that was carried out by passing the filtered original sample through a cartridge containing a chloride-form strong anion exchanger. Thus the most toxic form, inorganic As(III), was determined fast and directly by AsH3 generation using 3.5 mol L-1 HCl as carrier solution and 0.35% (m/v) NaBH4 in 0.025% NaOH as the reductant. Since the uptake of As(V) should be interfered by several anions of natural occurrence in waters, the effect of Cl-, SO42-, NO3-, HPO42-, HCO3- on retention was evaluated and discussed. The total soluble inorganic arsenic concentration was determined on aliquots of filtered samples acidified with concentrated HCl and pre-reduced with 5% KI-5% C6H8O6 solution. The concentration of As(V) was calculated by difference between the total soluble inorganic arsenic and As(III) concentrations. Detection limits (LODs) of 0.5 mu g L-1 and 0.6 mu g L-1 for As(III) and inorganic total As, respectively, were obtained for a 500 mu L sample volume. The obtained limits of detection allowed testing the water quality according to the national and international regulations. The analytical recovery for water samples spiked with As(III) ranged between 98% and 106%. The sampling throughput for As(III) determination was 60 samples h(-1). The device for groundwater sampling was especially designed for the authors. Metallic components were avoided and the contact between the sample and the atmospheric oxygen was carried to a minimum. On-field arsenic species separation was performed through the employ of a serial connection of membrane filters and anion-exchange cartridges. Advantages derived from this approach were evaluated. HPLC-ICPMS was employed to study the consistency of the analytical results. (C) 2011 Elsevier B.V. All rights reserved.