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.     

Interference from easily ionizable element matrices in inductively coupled plasma emission spectrometry—a spatial study

Utilizing a photodiode array based spatial profiling spectrometer an extensive spatial characterization of the effect of an excess of an easily ionizabie element (EIE) on analyte emission in the inductively coupled plasma has been carried out. Significant spatial shifts, enhancements and depressions are induced on analyte emission by the presence of an EIE and it is shown that limited fixed height measurements may be seriously misleading with respect to interpretation of the effects of ElEs. In general, the addition of excess EIE enhances emission in the lower regions of the analyte channel for both atom and ion lines and in the upper regions of the analyte channel, emission intensity is depressed for both atom and ion species. Radial emission maps (for CaI and CaII) reveal that the enhancements low in the discharge occur along the off axis boundary of the analyte channel and the plasma discharge. Higher in the discharge CaI emission is generally depressed but CaII emission undergoes a central axis depression coupled with an off axis enhancement. Overall the data suggests that low in the discharge enhancement appears to be the result of increased collisional excitation and that higher in the discharge ambipolar diffusion may exert an influence on the spatial distribution of analyte species.     

Wavelength-dependent enhancement of DCP metal lines by saline matrices

Sodium-induced emission enhancement of transition metal resonance lines are measured in a d.c. plasma (DCP) for wavelengths from 210 to 395 nm. Systematic differences in enhancement are observed within individual spectra (Fe I, Ni I, Sc II), and the enhancement and the excitation potential of a line are found to be linearly related. Electron density and apparent temperature data lead to an interpretation of thiis energy dependence within the context of a recombining plasma in partial thermodynamic equilibrium.     

A possible steady state kinetic model for the atomization and excitation processes during inductively coupled plasma atomic emission spectrometry: Application to interference effects of lithium on calcium

A possible steady state kinetic model is presented for the atomization and excitation processes during inductively coupled plasma atomic emission spectrometry. The model takes into account the relative rates of (a) thermal dissociation of analyte salt, (b) recombination of counter atom and analyte atoms, (c) charge transfer between analyte and interferent species, (d) charge transfer between analyte and argon species, and (e) ion/electron collisional de-ionization. Number density ratio data, n_u′/n_u, where n_u denotes the excited state and the prime denotes the presence of an interferent element, are presented showing that the predictions of the model are consistent with the signal enhancement observed at low analyte concentrations when Ca is determined by ICP in the presence of excess Li.     

Some spatial effects observed in the axially viewed filament argon microwave induced plasma with solution nebulization

Spatial profiles of analyte emission in an axially viewed argon filament microwave induced plasma sustained in the TE₁₀₁ rectangular cavity have been measured along a discharge tube cross-section for neutral atoms as well as ion lines of several elements. The filament diameter was approximately 1 mm. The analyte solution was introduced by means of an ultrasonic nebulizer without desolvation. The radial emission distribution depends on the operating parameters and is different for each of the analytes examined. Spatial distributions of excitation temperature (4000–6000 K) measured with Ar I lines by the Boltzmann plot method as well as electron temperature (6000–8000 K) by line to continuum emission ratio measurements at Ar I 430 nm and electron number density (1–1.5×10¹⁵ cm⁻³) by the Stark broadening method of the H_β line were determined to support the evidence of plasma processes. In the presence of excess sodium the enhancement of emission intensity and its shift to the plasma center appears to be the result of increased analyte penetration to the plasma. Changes in spatial emission profiles for Ca atoms and ions suggest that for this element ambipolar diffusion may be important as an additional interference mechanism. A possibility of minimizing spectral interferences from argon emission lines by choosing an off-axis plasma region for emission intensity measurements is indicated.     

Mechanism of Spectrum Excitation in a Solid Aerosol-Laden Plasma Jet of a Two-Jet Argon Arc Plasmatron

A possible reason for the high intensity of the ion emission in the spectrum excitation in a plasma jet generated by a two-jet argon arc plasmatron was considered. The injection of a test substance as an air–solid suspension between the plasma jets (i.e., mixing of a hot plasma with a cold directional carrier-gas flow) created a radial temperature gradient and induced an intense argon influx from the dense plasma jets to the cold axial plasma zone used for analytical purposes. Favorable conditions were thus created for the analyte Penning impact ionization with argon ions. This was confirmed by the existence of a correlation between an increase in the intensity of ion lines with the carrier-gas flow rate (cooling rate) and the total energy of ionization and excitation of an element. It was shown that charge transfer from the argon ion to the analyte occurred only in the case when the total energy of the element was lower than 16 eV, i.e., lower than the ionization energy of argon plus its kinetic energy.     

A possible steady state kinetic model for the atomization and excitation processes during inductively coupled plasma atomic emission spectrometry: application to interference effects of lithium on calcium

A possible steady state kinetic model is presented for the atomization and excitation processes during inductively coupled plasma atomic emission spectrometry. The model takes into account the relative rates of (a) thermal dissociation of analyte salt, (b) recombination of counter atom and analyte atoms, (c) charge transfer between analyte and interferent species, (d) charge transfer between analyte and argon species, and (e) ion/electron collisional de-ionization. Number density ratio data, n(u)'/n(u), where n(u) denotes the excited state and the prime denotes the presence of an interferent element, are presented showing that the predictions of the model are consistent with the signal enhancement observed at low analyte concentrations when Ca is determined by ICP in the presence of excess Li.     

A detailed consideration of resonance radiation trapping in the argon inductively coupled plasma

The extent and duration of trapping of argon resonance radiation (106.7 and 104.8 nm) in the ICP was calculated using a model incorporating line shape contributions from both Doppler and pressure broadening. The trap was found to be at the pressure-broadened limit, giving an escape factor of 7.9 × 10^?4 when excitation of the 4s states in the plasma annulus is assumed. Theoretical apparent radiative lifetimes τ_app for argon ³P₁ and ¹P₁ resonance states are calculated to be 8 and 1.9μs respectively. The quartet of 4s states, rapidly mixed by electron collisions, are presumed to share an overall apparent radiative lifetime τ_app = 1.6μs for the purpose of plasma modeling. Effects of this radiation trapping on the argon 4s atom density and on electron-ion recombination are discussed.     

Appreciation of a collisional-radiative model for the description of an inductively coupled argon plasma

The collisional-radiative model has been applied to the argon ICP discharge in order to elucidate the excitation mechanism in the plasma. The population density distributions of 25 argon energy levels were calculated under a steady-state approximation by using the literature values of electron number density, 5 × 10 ¹⁴cm^?3 and electron temperature, 9000 K. In the case of an optically thin plasma, in which the induced absorption can be neglected, the calculated population densities showed an overpopulation for low lying states, and were very close to LTE values for the upper levels. These results suggest the following excitation mechanisms in the argon ICP; corona model for lower levels and ladder-like excitation and ionization by electron impact for upper levels. According to the present calculation, the non-overpopulation of argon metastable can be interpreted by the interconversion between metastable and radiative states. It has been found that the induced absorption of resonance lines in an optically thick plasma and the motion of species in an inhomogeneous plasma have significant effects on the population densities. The non-linear processes by collision between heavy particles were not predominant compared to electron impact processes.     

Comparison of dielectric barrier discharge, atmospheric pressure radiofrequency-driven glow discharge and direct analysis in real time sources for ambient mass spectrometry of acetaminophen

Three plasma-based ambient pressure ion sources were investigated; laboratory constructed dielectric barrier and rf glow discharges, as well as a commercial corona discharge (DART source). All were used to desorb and ionize a model analyte, providing sampling techniques for ambient mass spectrometry (MS). Experimental parameters were optimized to achive highest signal for acetaminophen as the analyte. Insight into the mechanisms of analyte desorption and ionization was obtained by means of emission spectrometry and ion current measurements. Desorption and ionization mechanisms for this analyte appear to be identical for all three plasma sources. Emission spectra differ only in the intensities of various lines and bands. Desorption of solid analyte requires transfer of thermal energy from the plasma source to sample surface, in the absence of which complete loss of MS response occurs. For acetaminophen, helium was the best plasma gas, providing 100- to 1000-fold higher analyte response than with argon or nitrogen. The same trend was also evident with background ions (protonated water clusters). MS analyte signal intensity correlates with the ion density (expressed as ion current) in the plasma plume and with emission intensity from excited state species in the plasma. These observations support an ionization process which occurs via proton transfer from protonated water clusters to analyte molecules.     

Effect of excess sodium on the excitation of potassium in an air-acetylene flame: a steady state kinetic model which takes into account collisional excitation

Summary The effects of excess Na on the ionization and excitation of K in an air-acetylene flame were studied using absorbance signal and emission signal ratios, A/A and E/E respectively, as probes, where A and E are the line absorbance and line emission readings in the presence of excess Na interferent, and unprimed quantities represent readings in the absence of the interferent. An emission signal enhancement which increases exponentially as the ratio of interferent to analyte increases (up to about 2000), was observed irrespective of whether measurements were made from the primary or secondary reaction zones of the flame, while a similar line absorbance signal enhancement was observed only when measurements were made from the primary reaction zone. For both line emission and line absorbance, the maximum enhancements observed are in excess of those predicted on the basis of complete suppression of ionization of analyte atoms as a result of the increased partial pressure of electrons. A steady state kinetic model is presented, which takes into account radiative recombination collisional excitation of K⁺ ions and collisional charge transfer between the heavy particles, and whose predictions are consistent with the observed interference effects.     

Excitation processes in an r.f.-boosted,pulsed hollow cathode lamp

Time and space resolved emission spectroscopy was used to examine the excitation processes in an r.f.-boosted, pulsed hollow cathode lamp. Sealed commercial hollow cathode lamps with copper cathodes and neon or argon buffer gases were driven with temporally spaced unidirectional current pulses and radio frequency bursts. The neon filled lamp was studied most extensively; the argon lamp was used for comparison.Three excitation periods were considered: the current pulse, the r.f. burst, and the afterglow. Each of these periods was marked by a unique set of emission characteristics that suggested different combinations of excitation processes. Excitation during the current pulse appears to be a combination electron impact and charge exchange. Charge exchange excites the 3d⁹5s levels of Cull while electron impact excites the other ion levels and the neutral levels. Charge exchange continues to excite the ion spectrum during the afterglow. Afterglow emission from the neutral spectrum apparently results from two types of recombination processes. The exact recombination mechanisms could not be unambiguously assigned. Emission results from the r.f. burst suggest that electron impact is the dominant excitation process. Excitation of the neutral and ion spectra are from their respective ground states. There appears to be little ionization by electron impact.To evaluate the lamp's suitability as a line source for analytical atomic spectroscopy the profile of the 324.8 nm neutral resonance line was examined during the current pulse and the r.f. burst. The profile during the current pulse is strongly dependent on radial position in the cathode bore. Near the edges of the cathode the line is severely self-reversed. The profile during the r.f. burst is uniform across the cathode bore and is affected only slightly by self-absorption.     

Some fundamental measurements of the atmospheric-pressure,microwave-induced discharge

Measurements of several fundamental parameters in a microwave-induced atmospheric-pressure flowing plasma are presented. Optical and electrical measurements were performed on argon and argon/nitrogen plasmas in the region 1–7 cm outside the cavity, as the applied microwave power, and plasma composition were varied.The stability of the plasma, atomic emission from the argon support gas, and emission from the analyte species, are proportional to the electron density. The observed electron density was varied when the power was changed,-when an electrophilic species was added, and as the observation zone was moved relative to the microwave field. In all cases, the change in the emission signal followed the change in electron density.The electron temperature, as measured by the double-probe method, is related to the kinetic energy of the fastest-moving electrons in the plasma. It is unchanged by variations in power, plasma gas composition, flow rate, and is independent of the location of the probes relative to the cavity. The spectroscopic and electrical data are consistent with excitation by ion—electron radiative recombination.     

Spectral, spatial and temporal characteristics of a millisecond pulsed glow discharge: metastable argon atom production

Time resolved atomic emission, atomic absorbance, and laser-induced atomic fluorescence measurements of a millisecond pulsed glow discharge, made perpendicular to the insertion probe, provide temporal profiles of 1s₅ (³P₂) and 1s₃ (³P₀) metastable argon atom populations. Acquisition of these profiles at different spatial positions in the plasma provides data from which two-dimensional spatial plots of relative populations are constructed. Each map, the result of 368 individual pulse profiles, provides insight into the production of metastable argon atoms as a function of time and position within the plasma. During power application, intensities plateau after 3 ms as the plasma reaches a steady state condition. Metastable argon atoms are most abundant 1–2 mm above the cathode surface during this time. Excitation mechanisms such as electron excitation and fast atom/ion impact appear to dominate in this temporal regime. In contrast, argon ion–electron recombination dominates metastable formation after pulse termination. The relative population maximum for metastable argon atoms in the afterpeak shifts to 5–9 mm above the cathode surface. This shift should impact signals for analyte species generated by Penning processes in the plasma. Absorption and fluorescence measurements of the ³P₂ (11.55 eV) and the ³P₀ (11.72 eV) metastable argon atom states indicate possible differences in the populations of these two states between the plateau and afterpeak time regimes.     

Applications of d.c. argon plasma emission spectroscopy to saline waters: a study of enhancement effects

A commercially available d.c. argon plasma emission spectrometer was used to determine transition metals (3d and 4d) and also Be in salt and brackish water. The effects of salinity on the enhancement of emission intensities of the analyte lines were studied using an empirical approach combined with statistical analysis. One set of experiments deals with the effects of trace metal concentration and salinity on the relative emission intensities of 14 elements using a completely randomized experimental design, i.e. the sequence in which the 48 treatment combinations (12 levels of salinity and 4 levels of metal concentration) were measured was determined by randomization, with the results evaluated by an analysis of variance program. The second set deals with the effect of relative enhancement to salinity on selected ion and atom emission line pairs for various elements at 100 and 50% salinity relative to fresh water (0% salinity). These results are analyzed by a stepwise linear multiple regression analysis program using selected parameters of theoretical interest. It was discovered that the differences in relative enhancement for ion—atom emission line pairs for 100% salinity could be predicted basically with two variables. A coefficient of determination of 95% was achieved by employing the energy of transition for the atomic line and the number of unpaired d-electrons in the lower atomic state.     

Comparative studies on excitation of nickel ionic lines between argon and krypton glow discharge plasmas

The emission characteristics of nickel ionic lines in a glow discharge plasma are investigated when argon or krypton was employed as the plasma gas. Large difference in the relative intensities of nickel ionic lines which are assigned to the 3d⁸4p–3d⁸4s transition is observed between the krypton plasma and the argon plasma. Different intense Ni II lines appear in the krypton spectrum and in the argon spectrum, such as the Ni II 231.601 nm for Kr and the Ni II 230.009 nm for Ar. The excitation energy of these Ni II emission lines can give a key in considering their excitation mechanisms. The explanation for these experimental results is that charge-transfer collisions between nickel atom and the plasma gas ion play a major role in exciting the 3d⁸4p excited levels of nickel ion. The conditions for energy resonance in the charge-transfer collision determine particular energy levels having much larger population; for example, the 3d⁸4p ⁴D_7/2 level (6.39 eV) for Kr and the 3d⁸4p ⁴P_5/2 level (8.25 eV) for Ar.     

Furnace atomization plasma emission spectrometry with He/Ar mixed gas plasmas

The influence of plasma gas composition on the operating and analytical characteristics of a furnace atomization plasma emission source (FAPES) is presented. He I and Ar I excitation temperatures increase 30% in the mixed gas plasmas whereas argon ion excitation temperatures decrease from 33 000 K to 26 000 K in the presence of He. Collisional exchange of internal energy between excited states of Ar and He accounts for these changes. Average analyte ionization temperatures (for Cr, Mn, Mg, Co, Fe, Cd and Zn), derived from the relative emission intensities of their ionic and atomic lines in a 40-MHz 50-W plasma, increase from 5270 K to 6740 K with the addition of Ar to He. Ionic line intensities increase from 10-fold (Mn) to 40-fold (Cd, Zn) with addition of Ar to the plasma while atomic line intensities increase only twofold. Limits of detection remain substantially unaltered for atomic transitions due to increased noise but are improved twofold (Cd) to 24-fold (Mn) for ionic transitions. The analytical advantages and disadvantages of mixed gas plasmas are discussed. The Ne I excitation temperature at 40 MHz and 50 W was determined to be 4330±80 K.     

Emission characteristics of nickel ionic lines excited by reduced-pressure laser-induced plasmas using argon, krypton, nitrogen, and air as the plasma gas

The emission characteristics of nickel ionic lines in low-pressure laser-induced plasmas are investigated when argon, krypton, nitrogen, or air gas was employed as the plasma gas. The spectrum patterns and the relative intensities of the ionic lines are measured with and without a blind cylinder surrounding the sample surface to separate the detected emission area into two portions roughly: an initial breakdown zone and an expansion zone of the plasma. Their emission intensities are strongly dependent on both the kind and the pressure of the plasma gas. Different major ionic lines are observed in the argon and the krypton plasmas: for example, the Ni II 230.010-nm line (8.25 eV) for argon and the Ni II 231.604-nm line (6.39 eV) for krypton. The excitation mechanism of these ionic lines is considered to be a resonance charge-transfer collision with argon or krypton ion due to good energy matching to the corresponding energy levels of nickel ion. These ionic lines measured with the blind cylinder at reduced pressures of around 1300 Pa give the largest signal-to-background ratios; therefore, the analytical application under such optimum plasma conditions is recommended.     

Spatially resolved spectroscopic diagnostics of an argon MIP produced by surface wave propagation (Surfatron)

Spatially resolved spectroscopic diagnostics of an argon MIP have been obtained after Abel inversion. The plasma is sustained by surface wave propagation and is working at atmospheric pressure. The inner diameter of the discharge tube has been selected to obtain one stable discharge filament. Electronic excitation temperatures with argon and rotational temperatures of some molecular species (OH and N₂⁺), electron number and metastable densities and absolute values of the continuum emission coefficient have been determined. In contrast to ICPs and DCPs, the origin of the continuum in the visible part of the spectrum cannot be attributed only to radiative recombination.     

The influence of molecular gases and analytes on excitation mechanisms in atmospheric microwave sustained argon plasmas

The effect of introducing molecular compounds into argon plasmas has been studied using an expanding microwave induced plasma at atmospheric pressure. Besides the use of optical emission spectroscopy (OES), also the time dependent behavior of line intensities during power interruptions has been studied. From the measurements it is found that even an injection of small amounts of molecular compounds (> 0.5%) leads to important changes in excitation mechanisms in the plasma. It is also found that in the recombination zone downstream in the plasma an excitation mechanism which is independent of the electron density, e.g. excitation transfer from metastables or Penning ionization, must be responsible for the excitation of analytes. Received: 12 February 1998 / Revised: 14 April 1998 / Accepted: 17 April 1998