Gary M. Hieftje

Atmospheric Pressure Chemical Ionization Source. 1. Ionization of Compounds in the Gas Phase

A novel chemical ionization source for organic mass spectrometry is introduced. This new source uses a glow discharge in the flowing afterglow mode for the generation of excited species and ions. The direct-current gas discharge is operated in helium at atmospheric pressure; typical operating voltages and currents are around 500 V and 25 mA, respectively. The species generated by this atmospheric pressure glow discharge are mixed with ambient air to generate reagent ions (mostly ionized water clusters and NO+), which are then used for the ionization of gaseous organic compounds. A wide variety of substances, both polar and nonpolar, can be ionized. The resulting mass spectra generally show the parent molecular ion (M+ or MH+) with little or no fragmentation. Proton transfer from ionized water clusters has been identified as the main ionization pathway. However, the presence of radical molecular ions (M+) for some compounds indicates that other ionization mechanisms are also involved. The analytical capabilities of this source were evaluated with a time-of-flight mass spectrometer, and preliminary characterization shows very good stability, linearity, and sensitivity. Limits of detection in the single to tens of femtomole range are reported for selected compounds.

Microwave-Supported Discharges

A review is presented on the historical, fundamental, and practical aspects of microwave-induced plasmas (MIP) and their application to spectrochemical analysis. In particular, the mechanism of formation and stabilization of a microwave discharge is explored and possible excitation processes involving analyte atoms are described. Conditions under which a MIP can be operated are delineated and instrumentation necessary for MIP spectroscopy is described in detail. Methods for sample introduction into a MIP are reviewed and evaluated critically and the performance of MIP sources in real sample determinations is evaluated. Overall, the MIP appears to be a highly promising and under-utilized source in atomic spectrometry.

Atmospheric Pressure Chemical Ionization Source. 2. Desorption−Ionization for the Direct Analysis of Solid Compounds

The flowing afterglow-atmospheric pressure glow discharge (APGD) ionization source described in part 1 of this study (in this issue) is applied to the direct analysis of condensed-phase samples. When either liquids or solids are exposed to the ionizing beam of the APGD, strong signals for the molecular ions of substances present on their surfaces can be detected without compromising the integrity of the solid sample structure or sample substrate. As was observed for gas-phase compounds in part 1 of this study, both polar and nonpolar substances can be ionized and detected by mass spectrometry. The parent molecular ion (or its protonated counterpart) is usually the main spectral feature, with little or no fragmentation in evidence. Preliminary quantitative results show that this approach offers very good sensitivity (detection limits in the picogram regime are reported for several test compounds in part 1 of this study) and linear response to the analyte concentration. Examples of the application of this strategy to the analysis of real-world samples, such as the direct analysis of pharmaceutical compounds or foods is provided. The ability of this source to perform spatially resolved analysis is also demonstrated. Preliminary studies of the mechanisms of the reactions involved are described.

A microwave plasma torch assembly for atomic emission spectrometry

Abstract A new excitation source for atomic emission spectrometry, the microwave plasma torch (MPT) discharge, was developed and its analytical performance examined. The MPT works in a way that is significantly different from the ways in which the Beenakker cavity, surfatron or traditional capacitively coupled microwave plasma do. With the MPT, an argon discharge can be sustained at atmospheric pressure and at very low now rate (10 ml min ) and low forward power (40–500 W). Under slightly different conditions, a He or N2 microwave plasma (MP) can also be sustained. The plasma from the MPT is flame-like and has a central channel. Moreover, the sample aerosol can be introduced into the plasma with or without desolvation. Since the analyte is forced to pass through the central channel of the microwave discharge, it is efficiently vaporized, atomized, excited and ionized, and causes minimal perturbation to the plasma. The parameters that affect the plasma behavior have been studied in some detail. Background emission and the emission profiles of selected analytical lines were studied. The detection limits for most elements which have been studied are in the range of 1–50 ng ml , when an ultrasonic nebulizer with a simple desolvation system is employed. With the He MP, nonmetals including halogens are detectable even when samples are introduced in an aerosol form.

Use of a Solution Cathode Glow Discharge for Cold Vapor Generation of Mercury with Determination by ICP-Atomic Emission Spectrometry

A novel vapor-generation technique is described for mercury determination in aqueous solutions. Without need for a chemical reducing agent, dissolved mercury species are converted to volatile Hg vapor in a solution cathode glow discharge. The generated Hg vapor is then transported to an inductively coupled plasma for determination by atomic emission spectrometry. Mercury vapor is readily generated from a background electrolyte containing 0.1 M HNO 3. Vapor generation efficiency was found to be higher by a factor of 2-3 in the presence of low molecular weight organic acids (formic or acetic acids) or alcohols (ethanol). Optimal conditions for discharge-induced vapor generation and reduced interference from concomitant inorganic ions were also identified. However, the presence of chloride ion reduces the efficiency of Hg-vapor generation. In the continuous sample introduction mode, the detection limit was found to be 0.7 microg L (-1), and repeatability was 1.2% RSD ( n = 11) for a 20 microg L (-1) standard. In comparison with other vapor generation methods, it offers several advantages: First, it is applicable to both inorganic and organic Hg determination; organic mercury (thiomersal) can be directly transformed into volatile Hg species without the need for prior oxidation. Second, the vapor-generation efficiency is high; the efficiency (with formic acid as a promoter) is superior to that of conventional SnCl 2-HCl reduction. Third, the vapor generation is extremely rapid and therefore is easy to couple with flow injection. The method is sensitive and simple in operation, requires no auxiliary reagents, and serves as a useful alternative to conventional vapor generation for ultratrace Hg determination.

Plasma source mass spectrometry

Abstract Over the past decade, plasma-source mass spectrometry (PSMS) has become a viable alternative for multielemental analysis. The method offers (1) detection limits that are ordinarily two orders of magnitude below those offered by competitive emission techniques, (2) effective semiquantitative analysis, (3) isotope-analysis and isotope-ratio capability, (4) a broad linear dynamic range, and (5) virtually complete elemental coverage. However, even the most modern PSMS instruments remain plagued by a number of problems. High concentrations of sample material often pose difficulties, a number of spectral interferences (isobaric overlaps) can be devastating, instrumental drift is often troublesome, and new kinds of matrix interferences, not yet satisfactorily explained, are frequently encountered. In this paper, the current status of PSMS is first briefly reviewed, with an emphasis on current capabilities and shortcomings. A sampling of recent activities in the field is then documented. These activities understandably are aimed mostly at overcoming the remaining shortcomings of the method. Finally, recent instrumental developments are outlined. Included in these developments are modifications of conventional plasma ion sources, the introduction of new plasmas for PSMS, and the use of alternative mass spectrometers for elemental analysis.

Characterization of Direct-Current Atmospheric-Pressure Discharges Useful for Ambient Desorption/Ionization Mass Spectrometry

Two relatively new ambient ionization sources, direct analysis in real time (DART) and the flowing atmospheric-pressure afterglow (FAPA), use direct current, atmospheric-pressure discharges to produce reagent ions for the direct ionization of a sample. Although at a first glance these two sources appear similar, a fundamental study reveals otherwise. Specifically, DART was found to operate with a corona-to-glow transition (C-G) discharge whereas the FAPA was found to operate with a glow-to-arc transition (G-A) discharge. The characteristics of both discharges were evaluated on the basis of four factors: reagent-ion production, response to a model analyte (ferrocene), infrared (IR) thermography of the gas used for desorption and ionization, and spatial emission characteristics. The G-A discharge produced a greater abundance and a wider variety of reagent ions than the C-G discharge. In addition, the discharges yielded different adducts and signal strengths for ferrocene. It was also found that the gas exiting the discharge chamber reached a maximum of 235 °C and 55 °C for the G-A and C-G discharges, respectively. Finally, spatially resolved emission maps of both discharges showed clear differences for N2+ and O(I). These findings demonstrate that the discharges used by FAPA and DART are fundamentally different and should have different optimal applications for ambient desorption/ionization mass spectrometry (ADI-MS).

A New Background-correction Method for Atomic Absorption Spectrometry

A new method is described and tested for background correction in atomic absorption spectrometry. Applicable to flame or furnace atomizers, the method is capable of correcting backgrounds caused by molecular absorption, particulate scattering, and atomic-line overlap, even up to an absorbance value of 3. Like the Zeeman approach, the new method applies its correction very near the atomic line of interest, can employ single-beam optics, and requires no auxiliary source. However, no ancillary magnet or other costly peripherals are required and working curves are single-valued. The new technique is based on the broadening which occurs in a hollow-cathode spectral line when the lamp is operated at high currents. Under such conditions, the absorbance measured for a narrow (atomic) line is low, whereas the apparent absorbance caused by a broad-band background contributor remains as high as when the lamp is operated at conventional current levels. Background correction can therefore be effected by taking the difference in absorbances measured with the lamp operated at high and low currents. The new technique is evaluated in its ability to correct several different kinds of background interference and is critically compared with competitive methods.

Elucidation of Reaction Mechanisms Responsible for Afterglow and Reagent-Ion Formation in the Low-Temperature Plasma Probe Ambient Ionization Source

The development of ambient desorption/ionization mass spectrometry has shown promising applicability for the direct analysis of complex samples in the open, ambient atmosphere. Although numerous plasma-based ambient desorption/ionization sources have been described in the literature, little research has been presented on experimentally validating or determining the desorption and ionization mechanisms that are responsible for their performance. In the present study, established spectrochemical and plasma physics diagnostics in combination with spatially resolved optical emission profiles were applied to reveal a set of reaction mechanisms responsible for afterglow and reagent-ion formation of the Low-Temperature Plasma (LTP) probe, which is a plasma-based ionization source used in the field of ambient mass spectrometry. Within the dielectric-barrier discharge of the LTP probe, He(2)(+) is the dominant positive ion when helium is used as the plasma supporting gas. This helium dimer ion (He(2)(+)) has two important roles: First, it serves to carry energy from the discharge into the afterglow region in the open atmosphere. Second, charge transfer between He(2)(+) and atmospheric nitrogen appears to be the primary mechanism in the sampling region for the formation of N(2)(+), which is an important reagent ion as well as the key reaction intermediate for the formation of other reagent ions, such as protonated water clusters, in plasma-based ambient ionization sources. In the afterglow region of the LTP, where the sample is usually placed, a strong mismatch in the rotational temperatures of N(2)(+) (B (2)Σ(u)(+)) and OH (A (2)Σ(+)) was found; the OH rotational temperature was statistically identical to the ambient gas temperature (~300 K) whereas the N(2)(+) temperature was found to rise to 550 K toward the tail of the afterglow region. This much higher N(2)(+) temperature is due to a charge-transfer reaction between He(2)(+) and N(2), which is known to produce rotationally hot N(2)(+) (B (2)Σ(u)(+)) ions. Furthermore, it was found that one origin of excited atomic helium in the afterglow region of the LTP is from dielectronic recombination of vibrationally excited He(2)(+) ions.

Microplasma source based on a dielectric barrier discharge for the determination of mercury by atomic emission spectrometry.

A low-power, atmospheric-pressure microplasma source based on a dielectric barrier discharge (DBD) has been developed for use in atomic emission spectrometry. The small plasma (0.6 mm x 1 mm x 10 mm) is generated within a glass cell by using electrodes that do not contact the plasma. Powered by an inexpensive ozone generator, the discharge ignites spontaneously, can be easily sustained in Ar or He at gas flow rates ranging from 5 to 200 mL min(-1), and requires less than 1 W of power. The effect of operating parameters such as plasma gas identity, plasma gas flow rate, and residual water vapor on the DBD source performance has been investigated. The plasma can be operated without removal of residual water vapor, permitting it to be directly coupled with cold vapor generation sample introduction. The spectral background of the source is quite clean in the range from 200 to 260 nm with low continuum and structured components. The DBD source has been applied to the determination of Hg by continuous-flow, cold vapor generation and offers detection limits from 14 (He-DBD) to 43 pg mL(-1) (Ar-DBD) without removal of the residual moisture. The use of flow injection with the He-DBD permits measurement of Hg with a 7.2 pg limit of detection, and with repetitive injections having an RSD of <2% for a 10 ng mL(-1) standard.