title: Exhaustive thin-layer cyclic voltammetry for absolute multianalyte halide detection.
abstract: Water analysis is one of the greatest challenges in the field of environmental analysis. In particular, seawater analysis is often difficult because a large amount of NaCl may mask the determination of other ions, i.e., nutrients, halides, and carbonate species. We demonstrate here the use of thin-layer samples controlled by cyclic voltammetry to analyze water samples for chloride, bromide, and iodide. The fabrication of a microfluidic electrochemical cell based on a Ag/AgX wire (working electrode) inserted into a tubular Nafion membrane is described, which confines the sample solution layer to less than 15 μm. By increasing the applied potential, halide ions present in the thin-layer sample (X(-)) are electrodeposited on the working electrode as AgX, while their respective counterions are transported across the perm-selective membrane to an outer solution. Thin-layer cyclic voltammetry allows us to obtain separated peaks in mixed samples of these three halides, finding a linear relationship between the halide concentration and the corresponding peak area from about 10(-5) to 0.1 M for bromide and iodide and from 10(-4) to 0.6 M for chloride. This technique was successfully applied for the halide analysis in tap, mineral, and river water as well as seawater. The proposed methodology is absolute and potentially calibration-free, as evidenced by an observed 2.5% RSD cell to cell reproducibility and independence from the operating temperature.
authors.affiliation: Department of Inorganic and Analytical Chemistry, University of Geneva , Quai Ernest-Ansermet 30, CH-1211 Geneva, Switzerland.
authors.forename: Maria
authors.initials: M
authors.lastname: Cuartero
authors.forename: Gastón A
authors.initials: GA
authors.lastname: Crespo
authors.forename: Majid
authors.initials: M
authors.lastname: Ghahraman Afshar
authors.forename: Eric
authors.initials: E
authors.lastname: Bakker