Laser-induced fluorescence of As, Se and Sb in the inductively coupled plasma

Abstract Stimulated Raman shifting (SRS) has been used to generate tunable UV radiation at 193.7 nm, 197.2 nm and 196.0 nm for the excitation of laser-induced fluorescence (LIF) of As and Se, respectively, in the ICP. An excited-state, stepwise LIF approach has also been explored for Se using laser excitation at 206.279 nm. LIF of Sb has been accomplished using laser excitation at 206.833 nm and 212.739 nm. Power dependence studies of the LIF signals for As, Se and Sb have been performed. Saturation behavior has been observed for each element and saturation spectral energy densities are reported at 193.696 nm and 197.197 nm for As, at 196.026 nm for Se and at 212.739 nm for Sb. Evaluation of the saturation spectral energy density provides insight into the relative magnitude of the fluorescence quantum efficiency of Se at 196.026 nm in the ICP. Limits of detection of the ICP LIF approaches are 4 ng ml −1 , 2 ng ml −1 and 15 ng ml −1 for As, Se and Sb, respectively, and compare favorably with those reported previously by ICP emission and ICP atomic fluorescence spectroscopy approaches. Also reported are the first observations of high-lying excited-state transitions of Se in a flame by a LIF technique.

[1]  H. Zacharias,et al.  Continuously tunable VUV radiation (129–210 nm) by anti-Stokes Raman scattering in cooled H2 , 1988 .

[2]  William R. Cullen,et al.  Arsenic speciation in the environment , 1989 .

[3]  G. Schoknecht,et al.  High-sensitivity detection of selenium and arsenic by laser-excited atomic fluorescence spectrometry using electrothermal atomization , 1994 .

[4]  G. Tölg,et al.  A Survey of selenium in the environment and a critical review of its determination at trace levels , 1983 .

[5]  C. Corliss,et al.  Experimental transition probabilities for spectral lines of seventy elements , 1962 .

[6]  R. Wallenstein,et al.  Tunable UV radiation at short wavelengths (188–240 nm) generated by sum-frequency mixing in lithium borate , 1991 .

[7]  J. Winefordner,et al.  Some considerations on the saturation parameter for 2- and 3-level systems in laser excited fluorescence , 1982 .

[8]  W. Schmidt,et al.  Tunable coherent radiation source covering a spectral range from 185 to 880 nm , 1979 .

[9]  A. P. D'Silva,et al.  Evaluation of stimulated Raman scattering of tunable dye laser radiation as a primary excitation source for exciting atomic fluorescence in an inductively coupled plasma , 1986 .

[10]  J. Ruedy,et al.  The Arc Spectrum of Selenium , 1934 .

[11]  H. Haraguchi,et al.  Steady-state atomic fluorescence radiance expressions for continuum excitation. , 1978, Applied optics.

[12]  M. L. Parsons,et al.  Handbook of Flame Spectroscopy , 1975 .

[13]  D. Grégoire,et al.  Background spectral features in electrothermal vaporization inductively coupled plasma mass spectrometry: molecular ions resulting from the use of chemical modifiers , 1993 .

[14]  J. Winefordner,et al.  Fluorescence dip spectroscopy of sodium atoms in an inductively coupled plasma , 1988 .

[15]  C. Alkemade Anomalous saturation curves in laser-induced fluorescence , 1985 .

[16]  S. Svanberg,et al.  Oscillator strengths for resonance transitions in neutral selenium and tellurium derived from time-resolved laser spectroscopy , 1992 .

[17]  D. Hueber,et al.  Argon Fluoride Laser-Excited Atomic Fluorescence of Arsenic in a H2/Air Flame and in an Ar ICP , 1994 .

[18]  O. Axner,et al.  Direct detection of antimony in environmental and biological samples at trace concentrations by laser-induced fluorescence in graphite furnace with an intensified charge coupled device , 1995 .

[19]  J. Winefordner,et al.  A Comprehensive Table of Atomic Fluorescence Detection Limits and Experimental Conditions , 1989 .

[20]  R. Michel,et al.  Determination of tellurium and antimony in nickel alloys by laser excited atomic fluorescence spectrometry in a graphite furnace , 1993 .