Spatially resolved measurements to improve analytical performance of solution-cathode glow discharge optical-emission spectrometry

Past studies of the solution-cathode glow discharge (SCGD) revealed that elemental and molecular emission are not spatially homogenous throughout the source, but rather conform to specific zones within the discharge. Exploiting this inhomogeneity can lead to improved analytical performance if emission is collected only from regions of the discharge where analyte species emit strongly and background emission (from continuum, elemental and/or molecular sources) is lower. Effects of this form of spatial discrimination on the analytical performance of SCGD optical emission spectrometry (OES) have been investigated with an imaging spectrograph for fourteen atomic lines, with emphasis on detection limits and precision. Vertical profiles of the emission intensity, signal-to-background ratio, and signal-to-noise ratio were collected and used to determine the optimal region to view the SCGD on a per-element basis. With optimized spatial filtering, detection limits ranged from 0.09–360 ppb, a 1.4–13.6 fold improvement over those obtained when emission is collected from the full vertical profile (1.1–840 ppb), with a 4.2-fold average improvement. Precision was found to be unaffected by spatial filtering, ranging from 0.5–2.6% relative standard deviation (RSD) for all elements investigated, closely comparable to the 0.4–2.4% RSD observed when no spatial filtering is used. Spatial profiles also appear useful for identifying optimal line pairs for internal standardization and for flagging the presence of matrix interferences in SCGD-OES. - Highlights: • Spatial discrimination was used to enhance detection limits in SCGD-OES. • Optimized spatial filtering yields detection limits improved by a factor of 1.4–13.6. • Spatial emission profiles are useful for identification of line pairs for internal standardization. • Matrix interferences can be flagged through use of spatial profiles.