title: Spectroelectrochemical sensing based on multimode selectivity simultaneously achievable in a single device. 11. Design and evaluation of a small portable sensor for the determination of ferrocyanide in Hanford waste samples.
abstract: A portable spectroelectrochemical sensor has been designed, evaluated, and demonstrated on a complex sample of radioactive waste. The sensor consisted of a black delrin sample compartment with a total internal sample volume of 800 microL, attached to an indium tin oxide coated glass multiple internal reflection optical element. Detection was by total internal reflection of light from a blue light emitting diode source. After a 10 min uptake for each standard, the sensor showed a linear response in absorbance change for 5 x 10(-5) to 5 x 10(-3) M ferrocyanide with electrochemical modulation by scanning at 20 mV/s from -0.30 V to +0.55 V vs a Ag/AgCl reference electrode. Due to the complex nature of Hanford radioactive tank waste samples containing ferrocyanide, a standard addition method was developed for analysis. The spectroelectrochemical sensor determined a concentration of 9.2 mM ferrocyanide for U-Plant-2 simulant solution containing 9.38 mM ferrocyanide that was prepared according to Hanford process flowsheets. A radioactive tank waste sample from Hanford Tank 241-C-112 was determined to be 1.0 mM in ferrocyanide using the spectroelectrochemical sensor. A value for the ferrocyanide concentration in the sample of 0.61 mM was determined by FTIR spectroscopy.
authors.affiliation: Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, Ohio 45221-0172, USA.
authors.forename: Michael L
authors.initials: ML
authors.lastname: Stegemiller
authors.forename: William R
authors.initials: WR
authors.lastname: Heineman
authors.forename: Carl J
authors.initials: CJ
authors.lastname: Seliskar
authors.forename: Thomas H
authors.initials: TH
authors.lastname: Ridgway
authors.forename: Samuel A
authors.initials: SA
authors.lastname: Bryan
authors.forename: Tim
authors.initials: T
authors.lastname: Hubler
authors.forename: Richard L
authors.initials: RL
authors.lastname: Sell
mesh_terms: D004563:Electrochemistry; D004784:Environmental Monitoring / Q000295:instrumentation*; D005295:Ferrocyanides / Q000032:analysis*; D011850:Radioactive Waste / Q000032:analysis*; D017550:Spectroscopy, Fourier Transform Infrared
chemical_list: D005295:Ferrocyanides; D011850:Radioactive Waste; C020354:hexacyanoferrate II