Excitation of analytes and enhancement of emission intensities in a d.c. plasma jet: a critical review leading to proposed mechanistic models

Experimental data and theoretical criteria are used to critically review existing models for analyte emission enhancement in the 3-electrode d.c. plasma (DCP). The analytical zone is characterized as a non-optically thin recombining plasma in partial thermodynamic equilibrium (PTE). Spectrochemical excitation the authors ascribe largely to: (1) argon resonance line radiative transport; (2) inversion of optically pumped argon states; (3) inversion of analyte populations by Franck-Condon collisions with argon; (4) energy cascading in analytes via a multitude of channels. Adding an easily ionized element (EIE): (1) induces additional resonance line radiative transfer; (2) raises electron densities in cooler, analyte-rich plasma margins; (3) locally increases argon optical absorption cross sections via Stark broadening; (4) redistributes ohmic heating. Coupling between the proposed mechanisms is non-linear. Relationships between radiative transfer and collisional redistribution and (1) background suppression by EIE and (2) analyte emission enhancement by helium are also examined. Similarities between DCP and inductively coupled plasma (ICP) excitation mechanisms are noted and practical implications are addressed.