A new method using a micro-column packed with nanometer sized TiO2 as a sorbent has been developed for the on-line preconcentration of trace amounts of rare earth elements (La, Y, Yb, Eu and Dy) prior to their determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). The effects of pH, sample flow rate and volume, elution solution and interfering ions on the separation of analytes have been investigated. The adsorption capacity of nanometer TiO2 for La, Y, Yb, Eu and Dy was found to be 7.0, 6.1, 9.8, 8.3 and 8.8 mg g21, respectively. The method has been successfully applied for the determination of trace rare earth elements in some environmental samples.

A sensitive and simple method for low temperature electrothermal vaporization inductively coupled plasma optical emission spectrometry (ETV-ICP-OES) determination of V (Ⅳ) and V (Ⅴ) after separation/preconcentration by a micro-column packed with immobilized thenoyltrifluoroacetone (TTA) on microcrystalline naphthalene has been developed. Thenoyltrifluoroacetone was used as both a chelating agent for micro-column separation/preconcentration and a chemical modifier for ETV-ICP-OES determination of vanadium. Both vanadium species could be trapped by micro-column at pH 4.0, and the vanadate (VO2+) ion could be collected selectively at pH 2.4. Solid material loaded with analyte in the micro-column was dissolved with 100 AL of acetone containing 2.0 mmol L1 TTA and the vanadium was determined subsequently by ETV-ICP-OES. The concentration of vanadyl (VO2+) ion was calculated by subtracting the vanadate concentration from the total concentration of vanadium. Under the optimized experimental conditions, the detection limit (3r) for the preconcentration of 5mL of aqueous solution is 0.068 Ag L1 for both species and the relative standard deviations were 4.3% for vanadium (Ⅴ) and 4.8% for vanadium (Ⅵ) (c=10 Ag L1, n=7), respectively. The method was applied successfully to the determination of vanadium (Ⅳ) and vanadium (Ⅴ) in natural water samples.

A sensitive and rapid method for the determination of lanthanum, europium and ytterbium by inductively coupled plasma atomic emission spectrometry (ICP-AES) after solid-liquid extraction with microcrystalline naphthalene was developed. Analytes could be quantitatively adsorbed on tribromoarsenazo-cetylpyridinium bromide-naphthalene (TBA-CPB-naphthalene) packed in a column and determined by ICP-AES after desorption with 3mol l−1 HCl. The effect of various experimental parameters, such as pH, reagent amounts, naphthalene concentrations and diverse ions, on the determination of interesting elements were investigated in detail. Under the optimized experimental conditions, the detection limits of this method for La3+, Eu3+ and Yb3+ were 1.3-8.6ng ml−1, and the relative standard deviations obtained for nine replicate determinations at a concentration of 0.5gml−1 were 1.4-2.2%. The proposed method has been applied in the analysis of NIES CRM No.8 vehicle exhaust particulates and GBW 07602 GSV-1 bush branches and leaves for La, Eu and Yb, and La in NIST SRM 1752 citrus leaves samples; the analytical results were in good agreement with reference values.

A method was developed to determine refractory elements by inductively coupled plasma-atomic emission spectrometry (ICP-AES) with sample introduction by electrothermal vaporization (ETV). A slurry of polytetrafluoroethylene (PTFE) was used as fluorinating reagent to promote the vaporization of refractory elements from a graphite furnace and to avoid the formation of difficult volatile carbides. With this treatment the refractory elements can be efficiently vaporized, and subsequently introduced into the plasma. The detection limits of this method were in the picogram to sub-nanogram range and superior to those obtained with conventional nebulization systems, and were comparable with those obtained with similar ETV-ICP-AES techniques. The analyte vaporization and transport process was systematically explored, and the corresponding vaporization and transport mechanisms of refractory elements in this system have been proposed. The matrix effects and sample particle size effects in fluorination assisted ETV-ICP-AES were significantly reduced. Therefore, an effective method for lowering the matrix interferences has been proposed.

A method of glow discharge atomic emission spectroscopy (GD-AES) is described for the determination of rare earth elements (REEs) after separation and preconcentration by micro-column packed with immobilized 1-phenyl-3-methyl-4-benzoyl-5-pyrazone (PMBP) on icrocrystalline naphthalene. The graphite electrode with solution residue on its surface was used as a cathode. Various factors (the form of cathode, working condition) influencing the determination of the analytes were studied in detail. Under the experimental conditions selected, the detection limits for the determination of La, Nd, Eu, Dy and Y are 0.24, 0.32, 0.01, 0.07 and 0.06mg/mL, respectively, with relative standard deviations (RSDs) in the range of 5-10%. The method was applied to determine La, Nd, Eu, Dy and Y in geological samples, and the analytical results are in good agreement with the reference values.