Separation of metal ions by capillary electrophoresis--diversity, advantages, and drawbacks of detection methods.

Capillary electrophoresis (CE) has been applied to metal-ion analysis during the last 10 years. To improve sensitivity and selectivity different modes of detection have been adapted or developed. The selection of commercially available detection systems for metal-ion analysis is still primarily limited to UV-Vis detection, although other commercial systems, e.g. fluorescence, conductivity, or interfaces for coupling to mass spectrometry (MS) or inductively coupled plasma mass spectrometry (ICP-MS) are becoming available. High demands are made on any detector used in CE, because the analytical signal has to be extracted from less than 1 nL of sample, which corresponds to a total amount of < or = 10(-12) to 10(-15) mol analyte. This paper compares currently available and recently developed detection methods for CE as applied to the analysis of metal ions. Commercially available techniques, for example UV-Vis, fluorescence, or mass spectrometry, and other new detection methods including electrochemistry, radioactivity, and XRF, are discussed and future trends are anticipated.

Transient isotachophoretic-electrophoretic separations of lanthanides with indirect laser-induced fluorescence detection.

Indirect laser-induced fluorescence was used for the detection of several lanthanide species separated by capillary electrophoresis. Quinine sulfate was the fluorescent component of the background electrolyte, and α-hydroxyisobutyric acid was added as a complexing agent to enable the separation of analyte ions that have similar mobilities. The UV lines (333-364 nm) of an argon ion laser were used as the excitation source with a diode array detector for monitoring the fluorescent emission at 442 nm. Electrokinetic injections and transient isotachophoresis were implemented to stack the analyte ions into more concentrated zones. On-line preconcentration factors were determined to be ∼700 and resulted in limits of detection for La(3+), Ce(3+), Pr(3+), Nd(3+), Sm(3+), and Eu(3+) in the low-ppb range (6-11 nM).

Analysis of fission products using capillary electrophoresis with on-line radioactivity detection.

Capillary electrophoresis has been used to separate metal ions characteristically associated with nuclear fission. Indirect UV absorbance and on-line radioactivity detection were used simultaneously to monitor the analytes. The radioactivity detector consists of conical plastic scintillating material with the capillary passing through the center to provide a 4π detection geometry. The wide end of the cone is optically coupled to a photomultiplier tube. Transient isotachophoretic techniques were employed to stack large volumes of samples which had low specific activities. Radioactivity detection of (152)Eu and (137)Cs was achieved at the nanocurie level for 80-100 nL injections. The detector is approximately 80% efficient, enabling samples resident in the detector window for 0.1 min to be reliably assayed. The separation of (137)Cs and (137m)Ba isotopes, which are in secular equilibrium, was modeled to demonstrate the effects of the rapid decay of (137m)Ba.