Abstract: Three flow injection systems with potentiometric detection were developed for speciation of fluoride using a fluoride ion-selective electrode with a single flow-through detector. Among systems with (i) splitting of the sample zone and confluence point, (ii) flow reversal and (iii) resampling, the latter was most suitable. Its application was demonstrated for a study of the effectiveness of releasing fluoride from complexes with Al(III). Several ligands were examined as decomplexing agents such as EDTA, cyclohexane-1,2-diamine-N,N,N',N'-tetraacetic acid (DCTA), citrate and 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt (Tiron). In flow injection measurements, only Tiron was found suitable for decomposition of Al(III)-fluoride complexes. In stopped-flow measurements, using citrate or DCTA about a 10 min delay was required to release fluoride from Al(III) complexes. A flow injection system with resampling was also utilized for speciation of calcium ion-selective electrode in ligand solutions and in natural waters.

Abstract: A microchip-based capillary electrophoresis device supported by a microfluidic network made of poly(dimethylsiloxane), used for measuring target analytes from a continuous sample flow, is presented. The microsystem was fabricated by means of replica molding in combination with standard microfabrication technologies, resulting in microfluidic components and an electrochemical detector. A new hydrodynamic sample injection procedure is introduced, and the maximum number of consecutive measurements that can be made with a poly(dimethylsiloxane) capillary electrophoresis chip with amperometric detection is investigated with respect to reproducibility. The device features a high degree of functional integration, so the benefits associated with miniaturized analysis systems apply to it.