IntroductionRecently, capillary electrophoresis (CE) has proved to be efficient for the separation and detection of transition-metal cations. For the CE determination of such non-UV absorbing metal ions, indirect UV detection is widely used. [1][2][3][4] To improve the detection sensitivities, a direct UV detection method is proposed using pre-and in-capillary complexation with various organic and inorganic ligands.
5-26The development in CE determination of inorganic cations as their complexes is reviewed. [27][28][29][30][31][32][33][34][35] Based on precolumn complexation with a lacunary 7-anion, we propose a new approach to the simultaneous determination of metal ions belonging to the same group in a periodic table, such as Sb(III) and Bi(III), 36 Sc(III) and Y(III), 37 or Zr(IV) and Hf(IV). 38 The determination of toxic metal ions is often required for environmental monitoring. However, the application of such complexation methods to seawater analysis is difficult, owing to high concentrations of matrix ions. 39 The CE determination of toxic metal ions in seawater is a challenging area in environmental chemistry.The present study focused on the development of a simple and sensitive CE method for the determination of Cd(II) in environmental samples. We found that trace amounts of Cd(II) reacted spontaneously with [PW11O39] 7-to form the Keggin-type [P(CdW11)O39] 5-anion. Because the ternary Keggin anion possesses high molar absorptivities in the UV region, the use of [PW11O39] 7-as a complexing reagent allows direct UV detection with a satisfactory detection limit. In this study, we developed a new in-capillary complexation method for the determination of Cd(II) in river-water and seawater samples. To our knowledge, this is the first report on the sensitive CE determination of Cd(II) in seawater.
Experimental
InstrumentationA P/ACE MDQ system (Beckman Instruments) equipped with a built-in UV diode-array detector was used for CE measurements. A fused-silica capillary (GL Sciences, Tokyo, Japan) with 75 μm i.d. and 70 cm total length was used as a separation and reaction capillary. The 31 P (202.46 MHz) NMR spectra were recorded on a Bruker Model AVANCE 500 spectrometer in a 5 mm diameter NMR tube with a concentric capillary containing D2O for an instrumental lock. Chemical shifts were expressed in parts per million with respect to 85% (v/v) H3PO4. The 31 P NMR measurements were made at 25 ± 0.1˚C. UV-visible spectra were recorded with a Hitachi Model U-3000 spectrophotometer.
CE procedureFor in-capillary complexation, the capillary was filled with a running electrolyte consisting of 0.20 mM [PW11O39] 7-and 0.10 M malonate buffer (pH 3.0). Samples were injected at the cathodic end of the capillary by applying a pressure of 3.4 × 10 3 Pa for 10 -20 s. Throughout the work, direct UV detection was made at 250 nm, and the capillary temperature was held at 30˚C.
ChemicalsAll chemicals were of analytical reagent grade and used as received. , which possesses high molar absorbtivities in the UV region, is formed in...