Online column preconcentration for speciation and selective determination of Cr(III) in natural water samples using flow injection with chemiluminescence detection

Abstract

A simple, rapid, sensitive and inexpensive approach is described in this work based on a combination of solid-phase extraction of 8-hydroxyquinoline (8HQ), for speciation and preconcentration of Cr(III) and Cr(VI) in river water, and the direct determination of these species using a flow injection system with chemiluminescence detection (FI-CL) and a 4-diethylamino phenyl hydrazine (DEAPH)-hydrogen peroxide system. At different pH, the two forms of chromium [Cr(III) and Cr(VI)] have different exchange capacities for 8HQ, therefore two columns were constructed; the pH of column 1 was adjusted to pH 3 for retaining Cr(III) and column 2 was adjusted to pH 1 for retaining of Cr(VI). The sorbed Cr(III) and Cr(VI) species were eluted from columns using 3.0 ml of 0.1 N of HCl and 3.0 ml of 0.1 N of NaOH, respectively. The flow injection-chemiluminescence (FI-CL) method is based on light emitted due to the oxidation of DEAPH by the H₂ O₂ in the presence of Cr(III), which catalyzes the reaction. The flow cell is a transparent coiled tube made from glass (2.0 × 4.0, inner and outer diameter) and located close to the photodetector. The flow parameters: flow rate, sample volume, flow cell length, and distance to the CL detector were studied and optimized. Under optimum flow conditions, the Cr(III) concentration can be determined over the range 5-350 μg L^-1 with a limit of detection of 1.2 μg L^-1 , as the Cr(III) concentration is proportional to the intensity of the CL signal. The relative standard deviations (%) for 10 and 50 μg L^-1 Cr(III) were 1.2% and 3.2%, respectively. The effects of Al(III), Cd(II), Zn(II), Hg(II), Pb(II), Co(II), Cu(II), Ni(II), Mn(II), Ca(II), and Fe(III) were investigated. The proposed method is highly selective and sensitive, enabling a rapid determination of the Cr(III) amount in the presence of other interfering metals. Finally, the FI-CL method was examined in five river water samples with excellent recoveries.

Keywords: Cr(III); chemiluminescence; flow injection; preconcentration; river water.