Determination of nanomolar concentrations of phosphate in freshwaters using flow injection with luminol chemiluminescence detection

A simple and rapid flow injection (FI) method is reported for the determination of phosphate (as molybdate reactive P) in freshwaters based on luminol chemiluminescence (CL) detection. The molybdophosphoric heteropoly acid formed by phosphate and ammonium molybdate in acidic conditions generated chemiluminescence emission via the oxidation of luminol. The detection limit (3 x standard deviation of blank) was 0.03 mug P l(-1) (1.0 nM), with a sample throughput of 180 h(-1). The calibration graph was linear over the range 0.032-3.26 mug P l(-1) (r(2) = 0.9880) with relative standard deviations (n = 4) in the range 1.2-4.7%. Interfering cations (Ca(II), Mg(II), Ni(II), Zn(II), Cu(II), Co(II), Fe(II) and Fe(III)) were removed by passing the sample through an in-line iminodiacetate chelating column. Silicate interference (at 5 mg Si l(-1)) was effectively masked by the addition of tartaric acid and other common anions (Cl(-), SO(4)(2-), HCO(3)(-), NO(3)(-) and NO(2)(-)) did not interfere at their maximum admissible concentrations in freshwaters. The method was applied to freshwater samples and the results (26.1 +/- 1.1-62.0 +/- 0.4 mug P l(-1)) were not significantly different (P = 0.05) from results obtained using a segmented flow analyser method with spectrophotometric detection (24.4 +/- 4.45-84.0 +/- 16.0 mug P l(-1)). (C) 2004 Elsevier B.V. All rights reserved.