Analytical Methods for the Determination of Traces of Cr(VI) in Water Samples with Suppressed Ion Chromatography

Abstract

A rapid and sensitive method for the direct determination of hexavalent chromium in natural waters has been developed. Anion exchange chromatography was used for the fast separation of chromates from matrix anions, within 15 minutes, using a 35 mM KOH eluant. Mobile phase suppression was employed prior to direct conductivity (CD) detection, comparing two different electrolytic suppressor models and achieving a 10 times lower detection limit. Post column derivatization of Cr(VI) with diphenylcarbazide was used for further selective diode array (PDA) detection. Possible Cr(III) interference was evaluated with the addition of concentrations up to 10 mg/L of Cr(III) in a Cr(VI) positive natural water sample resulting in negligible interference. Both detection techniques gave instrumental LOD of 0.05 µg/L and method LOD of 0.08 µg/L for CD and 0.05 µg/L for PDA detection in underground water. Average repeatability and reproducibility (%RSD) was 1.3% and 5.4% for CD and 1.3% and 6.1% for PDA detection for two concentration levels. Recovery ranged from 70% to 103% for CD and from 90% to 100% for PDA. Method accuracy was additionally confirmed by analyzing positive samples with LC-ICP-MS. The method was successfully applied to the determination of Cr(VI) in several tap, spring and groundwater samples from the wider area of Asopos River, Greece. High concentrations where confirmed to the majority of the analyzed samples, revealing the serious and expanded problem of industrial pollution.

Keywords:

• ıon chromatography
• Asopos River
• Chromium speciation
• Conductivity detection
• DPC
• Large volume injection
• PDA
• Post column reaction
• SRS 300
• Water

Acknowledgments

This paper is part of a special issue organized by Dr. Nikolaos Thomaidis and Dr. Antony C. Calokerinos from research presented at the Aegean Analytical Chemistry Days Conference in Lesvos, Greece on 29 September–3 October 2010.

Notes

^a Calculated from a calibration curve in the range 1 to 20 µg/L Cr(VI) for both suppressor devices.

^b Calculated in the retention time window of Cr(VI) after the injection of a blank solution.

^a LC-ICP-MS measurements (n = 2) were performed in UT2A laboratory, University of Pau, France.