title: Cloud Point Extraction for Electroanalysis: Anodic Stripping Voltammetry of Cadmium.
abstract: Cloud point extraction (CPE) is a well-established technique for the preconcentration of hydrophobic species from water without the use of organic solvents. Subsequent analysis is then typically performed via atomic absorption spectroscopy (AAS), UV-vis spectroscopy, or high performance liquid chromatography (HPLC). However, the suitability of CPE for electroanalytical methods such as stripping voltammetry has not been reported. We demonstrate the use of CPE for electroanalysis using the determination of cadmium (Cd(2+)) by anodic stripping voltammetry (ASV). Rather than using the chelating agents which are commonly used in CPE to form a hydrophobic, extractable metal complex, we used iodide and sulfuric acid to neutralize the charge on Cd(2+) to form an extractable ion pair. This offers good selectivity for Cd(2+) as no interferences were observed from other heavy metal ions. Triton X-114 was chosen as the surfactant for the extraction because its cloud point temperature is near room temperature (22-25 °C). Bare glassy carbon (GC), bismuth-coated glassy carbon (Bi-GC), and mercury-coated glassy carbon (Hg-GC) electrodes were compared for the CPE-ASV. A detection limit for Cd(2+) of 1.7 nM (0.2 ppb) was obtained with the Hg-GC electrode. ASV with CPE gave a 20x decrease (4.0 ppb) in the detection limit compared to ASV without CPE. The suitability of this procedure for the analysis of tap and river water samples was demonstrated. This simple, versatile, environmentally friendly, and cost-effective extraction method is potentially applicable to a wide variety of transition metals and organic compounds that are amenable to detection by electroanalytical methods.
authors.affiliation: †Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States.
authors.forename: Cory A
authors.initials: CA
authors.lastname: Rusinek
authors.affiliation: ‡Department of Chemistry, Xavier University, Cincinnati, Ohio 45207-4221, United States.
authors.forename: Adam
authors.initials: A
authors.lastname: Bange
authors.affiliation: §BioMicrosystems Lab, Department of Electrical Engineering and Computing Systems, University of Cincinnati, Cincinnati, Ohio 45221-0030, United States.
authors.forename: Ian
authors.initials: I
authors.lastname: Papautsky
authors.affiliation: †Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States.
authors.forename: William R
authors.initials: WR
authors.lastname: Heineman
mesh_terms: D002104:Cadmium / Q000032:analysis*; D055664:Electrochemical Techniques; D004566:Electrodes; D007454:Iodides / Q000737:chemistry; D059625:Liquid-Liquid Extraction; D017830:Octoxynol; D011092:Polyethylene Glycols / Q000737:chemistry; D013464:Sulfuric Acids / Q000737:chemistry; D013501:Surface-Active Agents / Q000737:chemistry; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D007454:Iodides; D013464:Sulfuric Acids; D013501:Surface-Active Agents; D014874:Water Pollutants, Chemical; D002104:Cadmium; D011092:Polyethylene Glycols; D017830:Octoxynol; C010615:Nonidet P-40; C033158:sulfuric acid