Measured and modeled enhancement of transition metal emissions in the d.c. plasma jet

Enhancement of sensitive transition metal lines by a sodium matrix is measured in a 3-electrode d.c. plasma jet. Spiking with 0.43 M NaCI causes enhancement by factors of 1.85–2.92 in ionic lines and of 1.22–1.99 in atomic lines for eight of the structurally related analyte elements, but suppresses Zn I and Zn II emissions by about 25 %. Emission response to NaCI of lines within the same spectrum, or between different spectra of like ionization stage, can be simulated to 15 % and 20–25 %, respectively, by approximations linear in energy differences. For ionic lines these differences are the absolute value of the line excitation potential minus the energy of the ion state most readily pumped by Penning ionization by argon. For atomic lines it is the difference between emitting state excitation potential and the first ionization potential. Analyses of the experimental data strongly suggest that: (1) Na acts mainly to pertub radiative transfer rather than collisional redistribution processes; (2) population pumping of excited analyte states is largely driven by Penning ionization; (3) accelerated radiative cooling due to Na is manifested in a lowering of local kinetic temperature; (4) to a first-order of approximation, ambipolar diffusion, analyte-Na collisions of the second kind, and analyte ground state spin, do not influence emission line enhancement by easily ionized elements (EIE). Approximations are developed for predicting transition metal enhancements by arbitrary Na doping concentrations, and means are sketched for extending the method to other analyte group/EIE combinations. Practical implications of the work are noted.