Laser-enhanced Ionization Research Articles

Modern methods for identification of atoms, molecules, and aerosols in various objects

The study is aimed at developing highly sensitive methods of laser analytical spectroscopy. The physical mechanisms of forming useful signals (selective ionization signal and cavity ring-down signal) were identified that provided registration of parameters of atomic and aerosol systems in the intensive pulsed laser field. High-sensitive laser methods of laser resonance ionization spectroscopy in vacuum, laser-enhanced ionization spectrometry in flame, and cavity ringdown laser absorption spectroscopy (CRLAS) are used for the determination of ultra-small concentrations of atoms in different phase states of the substance. Samples of aqueous standard solutions and solid metals of s (Li, K, Na, Ca, Cs), p (Al, In), d (Cr, Mn, Fe, Co, Ni, Cu, Ag, Au, Pt, Zn, Hg), f (Yb) elements, aluminum alloys, especially pure solvents, crystals (NH4F, NaF), semi-conductor materials (GaAs, Si) and various aerosols of salts (NaCl, CsCl, NaI, NaF, KCl AgNO3), chemicals, organic dyes, alloys, soils and rocks were studied. The new mechanisms of getting free particles are revealed and new methods increasing the efficiency of atomization, selective ionization and excitation of atoms in systems «flame», «rod – flame», in atomizer «graphite – furnace» are proposed. The particle size distribution of aerosols formed under the impact of high-power laser radiation on the surface of a solid sample has been studied. The dependence of the absolute concentration of aerosol particles on their size has been determined. Aerosol extinction coefficients and extinction efficiency have been measured using intracavity laser spectroscopy. For the first time new parameters of aerosols are revealed by physical and chemical properties of aerosol plumes from solid surfaces and aerosols of salt of metals and organic aerosols. Methods of additives and calibration curve were used to examine the effects of the matrix on the analytical signal of the studied atoms.

Determination of lithium in lithium-ionic conductors by laser-enhanced ionization spectrometry with laser ablation

Laser-enhanced ionisation (LEI) with laser ablation (LA) into a methane–air flame was used for lithium determination in ferrites. Since there is a lack of certified reference materials matrix-matched to ferrites powders, a set of spinel samples were synthesised by means of aerosol spray pyrolysis (ASP) or by annealing the mixture of Li and Fe(III) nitrates. Characterisation by X-ray diffraction showed that the annealed ceramics contained two phases, such as either α-LiFe5O8 and Fe2O3 or α-LiFeO2 and Fe2O3, while ASP ferrites consisted mainly of α-LiFe5O8. Total lithium content in samples was certified by conventional flame photometry after dissolution. We explained the strong matrix effects on the LA-LEI signal by the discrepancy of surface microstructure (and hardness) due to the difference in the conditions of sample preparation. The optoacoustic signal and emission line of Fe I at 382 nm were recorded simultaneously with the LA-LEI signal in order to compensate for matrix effects. We suggest that the microstructure (ceramics or pellets from spherical microparticles) influences both mass removal (proportional to OA signal) and plasma temperature (proportional to AE signal). Correlation plots between OA and AE signals deviated strongly from sample to sample, which was the basis for the application of a multivariate correction procedure to reduce strong matrix effects. 3D correlation plots (LEI vs. OA + AE) for each sample were built to obtain a new analytical signal, which represented the slope of the correlation line to the plane of the OA + AE signals. This normalised signal was free from matrix effects within a concentration range of 0.6–7.5 Li%. The proposed approach allows the use of ferrites synthesised by the various techniques as reference materials in order to build a unified calibration curve.

Nonlinear normalization for laser-enhanced ionization spectrometry with laser sampling into a flame

The conditions for the appearance of a significant linear correlation between laser-enhanced ionization and reference signals are found. The parameters of this correlation (polynomial coefficients) are suggested to be used as a normalized analytical signal. The use of nonlinear correlation makes it possible to extend the range of ablation laser energies.

Lasers as Light Sources for Analytical Atomic Spectrometry

Lasers have advantages compared to conventional light sources, which include high power, a monochromatic emission profile, stability, and rapid tuning across an atomic line. These advantages have resulted in superior analytical figures of merit and methods of background correction compared to conventional light sources. The most widely used lasers for atomic spectrometry include dye laser systems, optical parametric oscillator systems, and diode lasers. Three principal techniques employ lasers as light sources. Laser‐excited atomic fluorescence spectrometry (LEAFS) involves the use of laser light to excite atoms that emit fluorescence and serves as the analytical signal. Laser‐enhanced ionization (LEI) involves laser excitation of atoms to an excited state energy level at which collisional ionization occurs at a higher rate than from the ground state. Diode laser atomic absorption spectrometry (DLAAS) employs a DL as a source to excite atoms in an atom cell from the ground state to an excited state. The analytical signal is involves the ratio of the incident and transmitted beams. Recent applications of these techniques are discussed, including practical applications, hyphenated techniques employing laser‐induced plasmas, and work to characterize fundamental spectroscopic parameters.

Multivariate correction in laser-enhanced ionization with laser sampling

The opportunity of normalizing laser-enhanced ionization (LEI) signals by several reference signals (RS) measured simultaneously has been examined in view of correcting variations of laser parameters and matrix interferences. Opto-acoustic, atomic emission and non-selective ionization signals and their paired combination were used as RS for Li determination in aluminum alloys (0–6% Mg, 0–5% Cu, 0–1% Sc, 0–1% Ag). The specific normalization procedure in case of RS essential multicollinearity has been proposed. LEI and RS for each definite ablation pulse energy were plotted in Cartesian co-ordinates ( x and y axes — the RS values, z axis — LEI signal). It was found that in the three-dimensional space the slope of the correlation line to the plane of RS depends on the analyte content in the solid sample. The use of this slope has therefore been proposed as a multivariate corrected analytical signal. Multivariate correlative normalization provides analytical signal free of matrix interferences for Al–Mg–Cu–Li alloys. The application of this novel approach to the determination of Li allows plotting unified calibration curves for Al-alloys of different matrix composition.

Reduction of the matrix influence on analytical signal in laser-enhanced ionization spectrometry with laser sampling

The novel approach using a slope of correlation line (laser-enhanced ionization of lithium versus laser-induced plasma emission of aluminum) as analytical signal was proposed for reduction of matrix interferences in laser-enhanced ionization spectrometric determination of Li with laser sampling.

Analytical signal normalization in laser-enhanced ionization spectrometry with laser ablation of solid samples into a flame

The characteristics of analytical and reference signals (RS) were studied in laser-enhanced ionization (LEI) spectrometry combined with laser ablation of solid samples into a flame. Optoacoustic (OA) and atomic emission (AE) signals have been considered as possible RS. An algorithm of RS selection has been developed. Correlations between LEI signals and RS, which carry information on sample evaporation processes, have been explored. OA (the 1st minimum) and AE (AlI, λ = 396.1 nm) signals were found to be useful as RS (the correlation coefficients were 0.992 and 0.993, respectively). Both RS did not depend on the analyte (Li) content in the sample. It has been shown that the slope of the correlation plots (LEI vs. RS) depends on the Li content in the solid sample. This slope may be used as a novel type of normalized analytical signal, which does not depend on the ablation pulse energy. The influence of both ablating laser radiation characteristics and sample matrix composition on the analytical signal is eliminated (or at least diminished) when using this normalization.

Advances in Laser‐Excited Atomic Fluorescence and Ionization

Laser‐excited atomic fluorescence spectrometry (LEAFS) and laser‐enhanced ionization (LEI) are very sensitive methods for elemental analysis. LEAFS involves excitation of atoms by laser radiation followed by detection of the resulting fluorescence, while LEI involves laser excitation, which serves to enhance ionization, producing electrons and ions that can be collected in an electric field. In this article, the spectroscopic transitions involved in LEAFS and LEI are discussed, followed by a review of the instrumentation employed. Several recent developmens in LEAFS and LEI are reviewed, including the use of tungsten coil atomizers for LEAFS; the determination of mercury, aluminum, lead, thulium, and chromium using various graphite electrothermal atomizers; the use of LEAFS and LEI as detectors for gas chromatography for the determination of volatile tin compounds; and the determination of a variety of elements by LEI with a flame atom cell. LEAFS and LEI will continue in the future to be high‐sensitivity alternatives to conventional methods of elemental analysis.

Use of Sol−Gels as Solid Matrixes for Trace Analysis by UV Laser Ablation and Laser-Enhanced Ionization Detection

Zirconium and silicon sol-gels were investigated as solid materials for trace elemental analysis of pelletized solid samples by laser ablation and laser-enhanced ionization. The highly homogeneous dispersion of an internal standard spiked in the solid material obtained with the sol-gel formation process leads to a significant improvement in signal repeatability and to an increase in the precision of measurements through better correction of variations in the laser ablation rate. Signal repeatability values of 5-8% RSD were obtained for Pb in NIST 1632c Bituminous Coal sample pellets prepared using both sol-gels, as compared to 9-21% for graphite-based sample pellets. Furthermore, the zirconium sol-gel was shown to offer better resilience to signal bias due to preferential ablation and a more accurate correction of ablation rate using the internal standardization method.

Investigation of hydroxyl-mediated spectral interference from easily ionized elements in laser-enhanced ionization spectrometry in the 281–285 nm range

The spectral background from 281 to 285 nm in the laser-enhanced ionization (LEI) spectrum of aqueous samples containing easily ionized elements (EIE) at concentrations similar to those found in blood was investigated. A complex, structured spectral background was observed, which appears in the presence of Na or K, but does not match the spectral signature of either element. The same behavior was also observed for Li. It was established that this background originates from an energy transfer between laser-excited hydroxyl (OH) molecules and ground-state EIEs. The intensity of this spectral feature was found to increase with EIE concentration and applied electrode voltage. This unexpected source of spectral interference may complicate the determination of trace metals by LEI in the presence of EIEs, since it can not be prevented by simply avoiding interference from atomic lines.

Multielemental Laser-Enhanced Ionization Spectrometry for the Determination of Lead at the Trace Level in Pelletized Coal Using Laser Ablation and Internal Standard Signal Normalization

Laser ablation laser-enhanced ionization (LA-LEI) was used for the simultaneous measurement of lead and indium in pelletized graphite and coal samples. UV Laser ablation of the solid samples was performed in an ablation cell and the ablated material was carried by a flow of gas to a miniature LEI flame where lead was detected. The influence of parameters such as binder content of the solid pellets and dispersion of the analytes spiked in the sample material, as well as the number of ablation pulses per crater on signal repeatability and on the size and shape of ejected particles was examined. Measurement repeatability values of 2 to 5% of relative standard deviation were obtained using indium as an internal standard to correct for variations in the ablation rate. A limit of detection of 120 nanograms per gram was calculated for the determination of Pb in high-purity graphite. The Pb concentration in the NIST 1632c Bituminous Coal certified reference material was determined to within 1% of its certified value, using graphite as the matrix-matching material and In as the internal standard in pelletized solid samples.

Laser-enhanced ionization with avalanche amplification: detection of cesium at fg/mL levels.

The avalanche amplification of the laser-enhanced ionization signal of Cs atoms in a flame has been studied. Ionization of Cs atoms, enhanced by two-step excitation, was detected in hydrogen and propane flames. By employing the effect of avalanche amplification of electrons, high signal-to-noise ratio (approximately 10(4)) was obtained for a 100 ppt Cs solution. The extrapolated limit of detection was 30 fg/mL (ppq).

Trace level determination of lead in solid samples by UV laser ablation and laser-enhanced ionization detection.

Laser-enhanced ionization was investigated as a detection technique for trace elemental analysis of solid samples by laser ablation. Laser ablation of aluminum samples was performed in an ablation cell, and the ablated material was carried by a flow of gas to a miniature LEI flame where Pb was detected. This decoupling of ablation cell and detector allowed the independent optimization of vaporization and detection processes. We have investigated the different excitation schemes for Pb and uncovered five new LEI-active transitions in the visible range. We have demonstrated that the use of an argon-oxygen/acetylene flame sheathed with argon resulted in the elimination of background interference from the two-photon ionization of nitric oxide. We have shown that the use of helium as a carrier gas results in a higher ablation yield and lower pulse-to-pulse variations in LEI signal and in better analytical figures of merit. We have characterized the performance of the technique in terms of detection limits and dynamic range, and we have obtained a detection limit of 60 ng/g for the determination of Pb in high purity aluminum.

Electron kinetics and selective ionization of recoil atoms in an ion guide ion source plasma

An electrodeless plasma produced in an ion guide ion source by a high-energy heavy ion beam propagating through a noble gas has been studied. The plasma parameters in Ar and He buffer gases have been calculated and analysed for projectile beam intensities from 10. The plasma is characterized by very low electron and gas temperatures, but with an appreciable number of electrons with energy sufficient to ionize atoms of most chemical elements. The ion guide ion source plasma, combined with laser-enhanced ionization of the studied element, is used to improve the detection limit by enhancing the signal-to-noise ratio.

Development of ultratrace laser spectrometry techniques for measurements of arsenic

Several techniques based on laser induced fluorescence (LIF) spectrometry and laser enhanced ionization (LEI) spectrometry have been investigated for ultratrace measurements of arsenic. Studies by our group in this area that have been published previously are reviewed here, and are presented along with the results of recent studies that have not yet been published. The techniques presented include LIF detection in the inductively coupled plasma atomizer, the electrothermal atomizer, the tungsten coil atomizer, the flame atomizer and LEI detection in the flame atomizer, and include approaches that utilize hydride generation or laser ablation sample introduction. Recent efforts have been directed towards developing speciation approaches for arsenic that utilize LIF spectrometric detection. The capabilities of each technique are summarized including the sensitivity and limits of detection, which range from sub-pg ml −1 to ng ml −1 levels. Selected applications of the techniques are presented to demonstrate their utility for environmental and biological samples, and areas for future investigation and further development are discussed.

Signal Formation in Laser-Enhanced Atomic Ionization Spectrometry with Laser Sampling into the Flame

The results of the observation of ionization signals in the laser-ablation sampling of solid samples into the flame were reported. The signals exhibited two maxima. The first, nonselective, maximum, which appeared immediately after the pulse of the volatilization laser, is due to thermions formed in the laser plasma. The second, selective (analytical), signal appeared after the pulse of the optical excitation laser. The nonselective signal may interfere with the detection of the analytical signal. The dependence of both signals on parameters such as the height of the cathode and the height of signal observation above the burner and the time delay between the laser pulses was studied. The optimal conditions for the detection of signals in laser-enhanced atomic ionization spectrometry were found.

Interferences and Methods for Their Elimination in the Determination of Lanthanum as LaO by Laser-Enhanced Molecular Flame Ionization Spectrometry

Interfering effects of some elements on the determination of lanthanum as LaO in a natural gas–air flame by laser-enhanced molecular ionization spectrometry were studied. It was demonstrated that easily ionized elements (Li, K, Na, Mg) exert an ionization effect; in addition, sodium introduces spectral interference. Techniques were proposed for the elimination of these interfering effects.

Application of Laser‐Enhanced Ionization Spectroscopy: Effect of Dissociation Constant on the Atomization Efficiency Determination in an Acetylene‐Air Flame

AbstractBy using laser‐enhanced ionization (LEI) technique, we have studied atomization efficiencies of the alkalihalides in an acetylene/air flame. As an aqueous solution of the metal salt was nebulized into the burner head, a flame with a high temperature of about 2500 K may cause dissociation of the ionic bond to release the free metal atoms. The ratio of the number density of free metal atoms present in the flame to the total number density of the same metal element nebulized determines the atomization efficiency. In this work, binary salt solutions including LiX, NaX, and KX (X=Cl, Br, and I) were used; each was prepared at 5 ppm (μg/mL) metal concentration. The atomization efficiency of the metal element was measured, as the accompanied halogen species was varied. We found that the ratios of atomization efficiencies of the akalielement in different halide compounds were almost equal to one. Atomization efficiency determination is dominated by the metal atom, but weakly influenced by the binding halogen species. The observation may be interpreted satisfactorily by using the Sugden‐Bulewicz model. Based on this model, the metal atomization efficiency for different halide compounds depends on the number densities of the halogen atoms and the related dissociation constants. For the binary salt with a small concentration and a large dissociation constant, the atomization efficiency determination tends to be dominated by the metal atom alone.

Laser-enhanced ionization and laser-induced atomic fluorescence as element-specific detection methods for gas chromatography: Application to organotin analysis

We have demonstrated that flame laser-enhanced ionization (LEI) and flame laser-induced atomic fluorescence (LIAF) techniques can be used as, alternative sensitive detectors for gas chromatographic (GC) analysis of organotin compounds. These two element-specific detection methods are free from interferences from the organic solvent. Two types of LEI schemes for Sn detection are employed. For the two-step LEI scheme (TLEI), the tin atoms in the flame were stepwise excited and then ionized collisionally. In contrast, in detection with the single-step LEI scheme (SLEI), only one dye laser is used. For the analysis of tetramethyltin and tetraethyltin, the GC–TLEI, GC–SLEI, and GC–LIAF systems yield linear dynamic ranges of 0.015–400, 0.39–600 and 0.5–600 ng, respectively. The corresponding detection limits reach 0.15, 3.9 and 5.0 mg/l, with absolute quantities corresponding to 15, 390 and 500 pg, respectively, for an injection volume of 0.1 μl. These detection methods prove to be more sensitive and selective than the conventional flame ionization detection, which achieves absolute detection limits of 800 and 1667 pg for tetraethyltin and tetramethyltin, respectively, under identical GC conditions.

Laser-enhanced ionization: recent developments

Initially developed for the analysis of simple aqueous solutions, laser-enhanced ionization (LEI) is a very sensitive trace analysis technique which is based on the spectrally selective laser excitation of analyte atoms followed by their collisional ionization and detection in a suitable atom reservoir. Its unique versatility, granted by a rich choice of excitation wavelengths, and its high efficiency of charge creation and collection make LEI one of the most sensitive techniques for elemental analysis. Despite these attractive features, LEI has not been widely used for the chemical analysis of liquid and solid samples having more complex matrices. This article describes the current limitations of LEI and recent achievements in the ongoing development of this promising technique.