Head-space flow injection for the on-line determination of iodide in urine samples with chemiluminescence detection

Abstract

A simple head-space (HS) flow injection (FI) system with chemiluminescence (CL) detection for the determination of iodide as iodine in urine is presented. The iodide is converted to iodine by potassium dichromate under stirring in the closed HS vial, and the iodine is released from urine by thermostatting and is carried in a nitrogen flow through an iodide trapping solution. The concomitant introduction of aliquots of iodine, luminol and cobalt(II) solutions by means of a time-based injector into an FI system allowed its mixing in a flow-through cell in front of the detector. The emission intensity at 425 nm was recorded as a function of time. The salting-out of the standard solutions affected the gas-liquid distribution coefficient of iodine in the HS vial. The typical analytical working graphs obtained under the optimized experimental conditions were rectilinear from 0 to 5 mg l−1 iodine, achieving a precision of 2.3 and a relative standard deviation of 1.8 for ten replicate analyses of 50 and 200 μg l−1 iodine. However, a second-order process becomes significant at higher iodine concentrations (from 10 to 40 mg l−1). The detection limit of the method is 10 μg l−1 (80 ng) iodine when 8 ml samples are taken. Data for the iodide content of 10 urine samples were in good agreement with those obtained by a conventional catalytic method, and recoveries varied between 101 and 103% for urine samples spiked with different amounts of iodide. The analysis of one sample takes less than 20 min. In the present study the iodide levels found for 100 subjects were 86.8 ± 19.0 (61–125) μg l−1, which is lower than the WHO's optimal level (150–300 μg per day).