Use of a spectrally segmented photodiode-array spectrometer for inductively coupled plasma atomic-emission spectroscopy Examination of procedures for the evaluation of detection limits.

The utility of a spectrally segmented photodiode array spectrometer was examined by using inductively coupled plasma atomic-emission spectrometry (ICP-AES). The spectrometer used in this study is capable of high resolution (reciprocal linear dispersion of approximately 0.08 nm/mm at 300 nm) over a wide spectral range (190-415 nm). The effect of using spectral peak areas instead of peak heights as a signal definition was examined by using the emission signals from 10 molybdenum lines obtained with various photodiode-array integration periods. In addition, a procedure to determine the detection limits obtainable with such a spectrometer is proposed. It was found that a signal definition involving a summation over a range of 5 pixels offered the best signal-to-noise ratio when the noise was defined as the standard deviation of the residual values from the line fitted to the sideband background level. A detection limit of 6 ng/ml was determined in this way for molybdenum. The multichannel capability of the spectrometer was found to permit continuous background correction, thereby reducing errors caused by low-frequency noise or plasma drift. The linearity of response was found to extend over three orders of magnitude with use of a single integration period. However, by use of different integration periods, the linear range of the detector could be extended to at least four orders of magnitude. The precision (RSD) of the spectrometer for a molybdenum concentration of 0.5 mug/ml was found to be about 3-4% for molybdenum peaks where the background emission was relatively low.