A bifunctional sorbent, (NH(2) + SH)silica, containing both amine and mercapto functionalties was prepared by modification of silica gel with 3-(triethoxysilyl)propylamine and (3-mercaptopropyl)trimethoxysilane. In addition to the bifunctional sorbent, silica gel was modified individually with the functional mercapto- and amino-silanes, and the mono-functional sorbents, namely (SH)silica and (NH(2))silica, were also mechanically mixed ((NH(2))silica +(SH)silica) for the sake of comparison of sorption performances. It has been demonstrated that (SH)silica shows quantitative sorption only to As(III) at two pH values, 1.0 and 9.0, while (NH(2))silica displays selectivity only towards As(V) at pH 3.0. On the other hand, the bifunctional (NH(2) + SH)silica possesses the efficient features of the two mono-functionalized sorbents; for example, it retains As(III) at a wider pH range, from 1.0 to at least 9.0 with the exception at pH 2.0, and it also shows quantitative sorption to As(V) at pH 3.0. This property gives the bifunctional (NH(2) + SH)silica a better flexibility in terms of sorption performance as a function of solution pH. The mechanically mixed (NH(2))silica +(SH)silica exhibits a similar but less efficient sorption behavior compared to the bifunctional sorbent. Desorption of both As(III) and As(V) species can be realized using 0.5 M NaOH. The validity of the proposed method was checked through the analysis of a standard reference material and a good correlation was obtained between the certified (26.67 mu g L(-1)) and determined (27.53 +/- 0.37 mu g L(-1)) values. Spike recovery tests realized with ultrapure water (93.0 +/- 2.3%) and drinking water (86.9 +/- 1.2%) also confirmed the applicability of the method. (C) 2011 Elsevier B.V. All rights reserved.