A novel
interrupted gas flow (IF) technique has been proposed for
highly sensitive determination of ultratrace levels of arsenic and
antimony in water samples by atmospheric pressure glow discharge (APGD)
excitation source coupled with HCl-KBH4 hydride generation
(HG). It is demonstrated that the gas flow interruption technique
provides a dramatic and reproducible enhancement of emission signals
of 1–2 orders of magnitude for As and Sb over conventional
continuous gas flow (CF) in APGD. The enhanced analyte emission sensitivities
in IF-APGD were investigated from the viewpoint of changes in plasma
excitation temperature and analyte density. With eight As lines as
the thermometric probe, no measurable change in excitation temperature
was found, suggesting that the enhancement is caused by an increase
in analyte number density in the plasma immediately following the
gas flow interruption. Furthermore, the enhancement factor was found
to increase with the time interval in between the gas interruption,
supporting an analyte adsorption (or trap)-release mechanism hypothesis.
Under optimized conditions, the detection limits (DLs) of IF-APGD
mode for As and Sb were calculated to be 0.02 and 0.003 μg L–1, which are, respectively, about 27- and 120-fold
improved compared to CF-APGD mode. The linearity of calibration for
both As and Sb reached R
2 > 0.999 in
the
0.1–5 μg L–1 range. The accuracy of
the proposed method was validated by the determination of certified
reference materials (CRMs), and the results agreed well with the certified
values.