Steven J. Ray

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.

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.

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.

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).

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.

Laser Ablation Coupled to a Flowing Atmospheric Pressure Afterglow for Ambient Mass Spectral Imaging

A plasma-based ambient desorption/ionization mass spectrometry (ADI-MS) source was used to perform molecular mass spectral imaging. A small amount of sample material was ablated by focusing 266 nm laser light onto a spot. The resulting aerosol was transferred by a nitrogen stream to the flowing afterglow of a helium atmospheric pressure glow discharge ionization source; the ionized sample material was analyzed by a Leco Unique time-of-flight mass spectrometer. Two-dimensional mass spectral images were generated by scanning the laser beam across a sample surface. The total analysis time for a 6 mm (2) surface, which is limited by the washout of the ablation chamber, was less than 30 min. With this technique, a spatial resolution of approximately 20 microm has been achieved. Additionally, the laser ablation configuration was used to obtain depth information of over 2 mm with a resolution of approximately 40 microm. The combination of laser ablation with the flowing atmospheric pressure afterglow source was used to analyze several sample surfaces for a wide variety of analytes and with high sensitivity (LOD of 5 fmol for caffeine).

Hadamard Transform Ion Mobility Spectrometry

A detection scheme that makes use of the Hadamard transform has been employed with an atmospheric-pressure ion mobility spectrometer fitted with an electrospray ionization source. The Hadamard transform was implemented through the use of a linear-feedback shift register to produce a pseudorandom sequence of 1023 points. This pseudorandom sequence was applied to the ion gate of the spectrometer, and deconvolution of the ion signal was accomplished by the Hadamard transform to reconstruct the mobility spectrum. Ion mobility spectra were collected in both a conventional and Hadamard mode, with comparisons made between the two approaches. Initial results exhibited low spectral definition, so an oversampling technique was applied to increase the number of data points across each analyte spectral peak. The use of the Hadamard transform increases the duty cycle of the instrument to 50% and results in a roughly 5-fold enhancement of the signal-to-noise ratio with a negligible loss of instrument resolution. It is also shown that any potential multiplex disadvantage, which limits the attractiveness of some high-throughput techniques, is not a limiting factor in this new implementation.

A new, versatile, direct-current helium atmospheric-pressure glow discharge

A novel direct current glow discharge sustained in helium at atmospheric pressure has been developed. Current–voltage behavior and spectroscopic characteristics strongly suggest that the system operates in the glow regime, in spite of the high pressure. The diffuse and extremely stable discharge is typically operated within a voltage range of 300–900 volts (in the current-controlled mode) and at currents ranging over tens to hundreds of milliamps. Spatially resolved spectroscopic measurements of some selected species are presented. Rotational temperature profiles were calculated using the OH emission spectrum, yielding values in the positive column ranging from 1300 to 1600 K.

Time-of-Flight Mass Spectrometry for Elemental Analysis

Inductively coupled plasma mass spectrometry (ICPMS),1 ® rst introduced by Houk et al. in 1980,2 has become the method of choice for routine elemental analysis in a wide range of applications. ICPMS offers nearly complete elemental and isotopic analysis for most samples over a broad range of element concentrations. Although ICPMS has matured into a powerful technique, several limitations remain; a list of its strengths and weaknesses can be found in Table I. To overcome the shortcomings of ICPMS, a number of researchers have investigated other types of mass analyzers as alternatives to the commonly used quadrupole mass ® lter and sector-® eld analyzer. The advantages of each type of mass analyzer have been reviewed previously,3 and only a short description of recent advances in ICPMS with each type of mass analyzer is given below. A detailed overview of the development and performance of an ICP± time-of̄ ight (TOF) instrument, ® rst described by Myers and Hieftje,4 is then given wherein the

Development of a direct current gas sampling glow discharge ionization source for the time-of-flight mass spectrometer

A direct current, reduced-pressure, gas sampling glow discharge (GSGD) ionization source has been developed and interfaced to an orthogonally extracted time-of-flight mass spectrometer for the purpose of generating both atomic and molecular fragmentation mass spectra. The discharge is contained within the first vacuum stage of the differentially pumped interface of the mass spectrometer. The source is mechanically and logistically simple to construct, operate, and maintain. Switching between the atomic and molecular modes of operation is achieved by altering the discharge gas composition, the operating pressure, and the current. Helium was used to generate atomic mass spectra, whereas molecular spectra were produced by use of argon. Gas flow rates were less than 1 l min –1 for each mode of ionization. This report focuses primarily upon the atomic (elemental) analytical capabilities of the GSGD interface. Atomic detection limits are in the range of 20-90 pg s –1 (as the halogen) for analytes introduced into the system with an exponential dilution device, and with boxcar averagers employed for data collection. Precision is better than 0.4% relative standard deviation (RSD) for measurement of the 79 Br + / 81 Br + isotope ratio (presented to the source as bromoform vapor) over a period of 2.5 h. A variety of chlorinated hydrocarbons were introduced into the discharge via a flow cell, and it was possible to differentiate (i.e., speciate) the compounds based upon their 35 Cl + / 12 C + elemental ratios with a correlation coefficient (R) of 0.996.