Pressure Laser Ionization Research Articles

Ion Source Complementarity for Characterization of Complex Organic Mixtures Using Fourier Transform Mass Spectrometry: A Review.

Complex organic mixtures are found in many areas of research, such as energy, environment, health, planetology, and cultural heritage, to name but a few. However, due to their complex chemical composition, which holds an extensive potential of information at the molecular level, their molecular characterization is challenging. In mass spectrometry, the ionization step is the key step, as it determines which species will be detected. This review presents an overview of the main ionization sources employed to characterize these kinds of samples in Fourier transform mass spectrometry (FT-MS), namely electrospray (ESI), atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI), atmospheric pressure laser ionization (APLI), and (matrix-assisted) laser desorption ionization ((MA)LDI), and their complementarity in the characterization of complex organic mixtures. First, the ionization techniques are examined in the common direct introduction (DI) usage. Second, these approaches are discussed in the context of coupling chromatographic techniques such as gas chromatography, liquid chromatography, and supercritical fluid chromatography.

Detailed Comparison of Xenon APPI (9.6/8.4 eV), Krypton APPI (10.6/10.0 eV), APCI, and APLI (266 nm) for Gas Chromatography High Resolution Mass Spectrometry of Standards and Complex Mixtures.

Photoionization schemes for mass spectrometry, either by laser or discharge lamps, have been widely examined and deployed. In this work, the ionization characteristics of a xenon discharge lamp (Xe-APPI, 9.6/8.4 eV) have been studied and compared to established ionization schemes, such as atmospheric pressure chemical ionization, atmospheric pressure photoionization with a krypton discharge lamp (Kr-APPI, 10.6/10 eV) and atmospheric pressure laser ionization (266 nm). Addressing the gas-phase ionization behavior has been realized by gas chromatography coupled to high-resolution mass spectrometry without the usage of a dopant. For standard substances, it has been found that Xe-APPI is able to ionize a broad range of polycyclic aromatic hydrocarbons as well as their heteroatom-containing and alkylated derivatives. However, thiol and ester compounds could not be detected. Moreover, Xe-APPI revealed a high tendency to generate oxygenated artifacts, most likely due to a VUV absorption band of oxygen at 148 nm. Beneficially, almost no chemical background, commonly caused by APCI or Kr-APPI due to column blood, plasticizers or impurities, is observed. This advantage is noteworthy for evolved gas analysis without preseparation or for chromatographic coelution. For the complex mixtures, Xe-APPI revealed the predominant generation of radical cations via direct photoionization with a high selectivity toward aromatic core structures with low alkylation. Interestingly, both Xe-APPI and Kr-APPI could sensitively detect sterane cycloalkanes, validated by gas chromatographic retention. The narrowly ionized chemical space could let Xe-APPI find niche applications, e.g., for strongly contaminated samples to reduce the background.

Characterization of Deasphalted Crude Oils Using Gas Chromatography–Atmospheric Pressure Laser Ionization–Trapped Ion Mobility Spectrometry–Time-of-Flight Mass Spectrometry

Characterization of Deasphalted Crude Oils Using Gas Chromatography–Atmospheric Pressure Laser Ionization–Trapped Ion Mobility Spectrometry–Time-of-Flight Mass Spectrometry

Comprehensive Screening of Polycyclic Aromatic Hydrocarbons and Similar Compounds Using GC-APLI-TIMS-TOFMS/GC-EI-MS.

In the present work, a novel workflow based on complementary gas-phase separations for the identification of isomeric PAHs from complex mixtures is described. This is the first report on the coupling of gas chromatography (GC), atmospheric pressure laser ionization (APLI), and trapped ion mobility spectrometry-mass spectrometry (TIMS-MS) for the characterization of polycyclic aromatic hydrocarbons. Over a hundred known unknowns are uniquely identified based on the molecular ion retention indices I (5%), mobility (RSD < 0.6% and R = 50-90 with Sr = 0.18 V/ms), mobility-based theoretical candidate assignment (<3%), accurate mass chemical formula assignment (<2 ppm), and electron impact fragmentation pattern and database search. The advantages of theoretical modeling of PAHs and similar compounds were evaluated using candidate structures ranked by retention indices and fragmentation pattern from GC-EI-MS data sets. Over 20 PAH isomeric and deuterated standards were utilized for the GC-APLI-TIMS-TOF MS workflow validation. Noteworthy is the analytical capability for untargeted screening of isomeric and isobaric compounds with additional characterization metrics not available in traditional GC-EI-MSn workflows.

Atmospheric Pressure Single Photon Laser Ionization (APSPLI) Mass Spectrometry Using a 157 nm Fluorine Excimer Laser for Sensitive and Selective Detection of Non- to Semipolar Hydrocarbons

Atmospheric pressure single photon ionization (APSPLI) mass spectrometry utilizing a fluorine excimer laser (157 nm, 7.9 eV) is presented for the first time. For evaluation and optimization, polycyclic aromatic hydrocarbon (PAH) standard mixtures were used. The presented technique allowed for the selective ionization of semi- to nonpolar compounds in a single photon ionization process using VUV photons. Molecular radical cations were found as a base peak, whereas protonated species were almost absent. Although the ionization chamber is flushed by pure nitrogen, remaining oxygen and water traces caused unwanted oxidized ionization artifacts. Installation of water and oxygen filter cartridges significantly reduced the abundance of artifacts. For evaluating complex mixture analysis, APSPLI was applied to characterize a light crude oil. In addition to aromatic hydrocarbons, APSPLI allowed for the sensitive ionization of sulfur-containing aromatic constituents (PASH). A comparison of APSPLI to atmospheric pressure laser ionization (266 nm, 4.7 eV) revealed the additional compositional space accessible by the single photon process. APLI, conducted with UV radiation, is mainly restricted to PAH analysis. APSPLI overcomes this limitation, and PAH and PASH, which often occur simultaneously in complex mixtures, can be detected. This novel ionization concept is envisioned to have a high analytical potential further explored in the future.

Identification of 7–9 ring polycyclic aromatic hydrocarbons in coals and petrol coke using High performance liquid chromatography – Diode array detection coupled to Atmospheric pressure laser ionization – Mass spectrometry (HPLC-DAD-APLI-MS)

Polycyclic aromatic hydrocarbons containing at least 24 carbon atoms (≥C24-PAH) are often associated with pyrogenic processes such as combustion of fuel, wood or coal, and occur in the environment in diesel particulate matter, black carbon and coal tar. Some of the ≥C24-PAH, particularly the group of dibenzopyrenes (five isomers, six aromatic rings) are known to show high mutagenic and carcinogenic activita.Gas chromatography – mass spectrometry is a well-established method for the analysis of lower molecular weight PAH but is not optimally suited for the analysis of ≥C24-PAH due to their low vapor pressures. Also, hundreds of ≥C24-PAH isomers are possible but only a few compounds are commercially available as reference standards. Therefore, in this study, a combination of multidimensional liquid chromatography, UV–Vis diode array detection, PAH selective and highly sensitive atmospheric pressure laser ionization – mass spectrometry is used to detect and unequivocally identify PAH. For identification of PAH in two bituminous coals and one petrol coke sample, unique and compound specific UV–Vis spectra were acquired. It was possible to identify ten compounds (naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[e,ghi]perylene, dibenzo[cd,lm]perylene, benzo[a]coronene, phenanthrol[5,4,3,2-abcde]perylene, benzo[ghi]naphtho[8,1,2-bcd]perylene, benzo[pqr]naphtho[8,1,2-bcd]perylene, naphtho[8,1,2-abc]coronene and tribenzo[e,ghi,k]perylene) by comparison of acquired spectra with spectra from literature. Additionally, it was possible to detect similar distribution patterns in different samples and signals related to alkylated naphthopyrenes, naphthofluoranthenes or dibenzopyrenes. Subsequent effect-directed analysis of a bituminous coal sample using the microEROD (ethoxyresorufin-O-deethylase) bioassay showed high suitability and revealed lower EROD induction for the ≥C24-PAH (TEQ range 0.67–10.07 ng/g) than for the allover < C24-PAH containing fraction (TEQ 84.00 ng/g). Nevertheless, the toxicity of ≥C24-PAH has a significant impact compared with <C24-PAH and must be considered for risk assessment. The LC-DAD-APLI-MS method, presented in this study, is a powerful tool for the unequivocal identification of these ≥ C24-PAH.

Systematic Ion Source Parameter Assessment by Automated Determination of the Distribution of Ion Acceptance (DIA) Using APLI.

The determination of the spatially resolved ion signal with atmospheric pressure laser ionization (APLI), which was introduced as distribution of ion acceptance (DIA), serves as a valuable tool for the understanding of complex and highly dynamical conditions in modern atmospheric pressure (AP) ion sources. DIA provides information about fluid dynamics, ion transport, and ion transformation processes in such sources and is an ideal basis for the validation of numerical models of the dynamics in the ion source enclosure.We present a fully automated setup for DIA measurements, which enabled us to acquire a comprehensive dataset of over 700 individual DIA measurements in a commercial AP ion source (Bruker Multi Purpose Ion Source, MPIS). Ion source parameters as voltages, gas heater temperatures and gas flows, were varied, and the effect of those parameters on the DIA of a chemically inert analyte, pyrene, was systematically investigated. It is shown that the response of the DIA is nonlinear and that gas dynamics largely dominates the ion transport in the ion source. Particularly, the position of the heated nebulizer, which is used to introduce one of two gas flows and the analyte into the ion source chamber, had a profound effect on the DIA. This suggests that the gas dynamics in the source switches between different states. The now available comprehensive DIA dataset reveals such critical effects and will guide further numerical modeling efforts to understand the details of the dynamics of ions in the source chamber. Graphical Abstract.

Analysis of 6- and 7-ring PAH and other non-EPA PAH by atmospheric pressure laser ionization – mass spectrometry (APLI-MS) in environmental certified reference materials NIST 1941b, NIST 1649b, BAM CC013a and IRMM BCR 535

Proceedings in environmental analytical chemistry of polycyclic aromatic hydrocarbons (PAH) in the past decades cover improvements in laboratory methods as well as new insights in the toxicology of single PAH compounds. A re-evaluation of the established list of 16 priority PAH published by the U. S. Environmental Protection Agency seems overdue. In this study we have applied PAH analysis by atmospheric pressure laser ionization – mass spectrometry (APLI-MS) to NIST 1941b, NIST 1649b, BAM CC013a and IRMM BCR 535 giving further references in addition to the certificates of analysis. Gas chromatography enables to distinguish between different alkylated PAH derivatives whereas liquid chromatography additionally allows detection of PAH tentatively with six or more aromatic rings on the level of chemical formula. For an optimal isomer-specific differentiation, LC-APLI-MS should be used in combination with fluorescence detection. Distribution patterns of 6 and 7-ring PAH are presented for urban dust, marine and harbor sediments and the soil sample. Additionally, a set of 14 nitrogen, sulfur and oxygen-containing polycyclic aromatic compounds were analyzed by APLI and quantified in all reference materials for the first time.

Eluent-assisted Nonresonant Multiphoton Ionization of Polycyclic Aromatic Hydrocarbons in a Liquid Chromatograph-mass Spectrometer

A sub-nanosecond visible laser coupled with a liquid chromatograph is utilized for atmospheric pressure laser ionization (APLI). We reveal that the range of applicable substances for nonresonant three-photon ionization is determined by the proton affinity and the ionization potential, the latter of which is lowered by solvation with eluents. APLI with a visible laser can be used for fragmentation- and background-free detection of analytes as well as to investigate the ionization threshold of solvated molecules.

Measuring the effects of Coulomb repulsion via signal decay in an atmospheric pressure laser ionization ion mobility spectrometer.

Using lasers in ion mobility spectrometry offers a lot of advantages compared to standard ionization sources. Especially, the ion yield can be drastically increased. It can, however, reach levels where the Coulomb repulsion leads to unwanted side effects. Here, we investigate how the Coulomb repulsion can be detected apart from the typical signal broadening by measuring effects created already in the reaction region and comparing them with corresponding finite element method simulations.

Direct Infusion Resonance-Enhanced Multiphoton Ionization Mass Spectrometry of Liquid Samples under Vacuum Conditions.

Direct infusion resonance-enhanced multiphoton ionization (DI-REMPI) was performed on liquid samples, which were introduced to the ion source via a direct liquid interface, to enable the investigation of dissolved aromatic compounds. Desolvation and nebulization of the samples were supported by a heated repeller using flow rates in the upper nL min-1 range. The obtained mass spectra of five pure polycyclic aromatic hydrocarbons as well as complex petroleum samples revealed predominantly molecular ions without evidence of solvent or dopant effects as observed in atmospheric pressure photoionization (APPI) and laser ionization (APLI) with limits of detection in the lower pmol range. Furthermore, it is demonstrated by the analysis of different complex oil samples that DI-REMPI covers a larger m/z range than external volatilization of the sample prior to introduction to the ion source by using thermogravimetry (TG) hyphenated to REMPI time-of-flight mass spectrometry (TOFMS). Analogous to reported setups with direct liquid interface and electron ionization, direct-REMPI may be an option for soft ionization in liquid chromatography.

Chemical Analysis of Water-accommodated Fractions of Crude Oil Spills Using TIMS-FT-ICR MS.

Multiple chemical processes control how crude oil is incorporated into seawater and also the chemical reactions that occur overtime. Studying this system requires the careful preparation of the sample in order to accurately replicate the natural formation of the water-accommodated fraction that occurs in nature. Low-energy water-accommodated fractions (LEWAF) are carefully prepared by mixing crude oil and water at a set ratio. Aspirator bottles are then irradiated, and at set time points, the water is sampled and extracted using standard techniques. A second challenge is the representative characterization of the sample, which must take into consideration the chemical changes that occur over time. A targeted analysis of the aromatic fraction of the LEWAF can be performed using an atmospheric-pressure laser ionization source coupled to a custom-built trapped ion mobility spectrometry-Fourier transform-ion cyclotron resonance mass spectrometer (TIMS-FT-ICR MS). The TIMS-FT-ICR MS analysis provides high-resolution ion mobility and ultrahigh-resolution MS analysis, which further allow the identification of isomeric components by their collision cross-sections (CCS) and chemical formula. Results show that as the oil-water mixture is exposed to light, there is significant photo-solubilization of the surface oil into the water. Over time, the chemical transformation of the solubilized molecules takes place, with a decrease in the number of identifications of nitrogen- and sulfur-bearing species in favor of those with a greater oxygen content than were typically observed in the base oil.

Liquid chromatography-atmospheric pressure laser ionization-mass spectrometry (LC-APLI-MS) analysis of polycyclic aromatic hydrocarbons with 6-8 rings in the environment.

A method has been developed for the sensitive and rapid analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples using liquid chromatography time-of-flight mass spectrometry as well as the selective atmospheric pressure laser ionization (APLI) process (LC-APLI-MS). Upon analyzing 34 PAHs, the limits of detection of this method were found to range from 0.008 to 1.824pg (0.024pg for benzo[a]pyrene). The method therefore provides 30-fold to 5,400-fold increased sensitivity compared with the established GC-MS technique. This LC-APLI-MS method was optimized for higher molecular weight PAHs (C24-C30 PAHs with 6-8 rings), which are difficult to detect or cannot be detected by GC-MS. Using the LC-APLI-MS method, various 6- to 8-ring PAHs were detected in environmental samples for the first time. After developing the method, it was successfully validated in ruggedness tests. The concentrations determined by the LC-APLI-MS method were in good accord with the certified concentrations in three certified reference materials (contaminated soils and sediments). Upon applying the method to environmental samples, it was found that (1) the presence of dibenzo[a,i]pyrene and dibenzo[a,h]pyrene in urban soil samples could only be detected using LC-APLI-MS (i.e., not GC-MS) due to its high sensitivity, (2) a bituminous coal sample yielded 211 tentative peaks from aromatic compounds in the C24-C30 range, and (3) eleven of those compounds occurred in different environmental samples in similar patterns. Hence, 6- to 8-ring PAHs occur in solid environmental samples in which other 6-ring PAHs such as indeno[1,2,3-cd]pyrene or benzo[ghi]perylene may also be present. Some of these numerous higher molecular weight PAH compounds could have very high carcinogenic potential, which will need to be elucidated to ensure the reliability of PAH risk assessments.

Signal deformation at high ion concentration in atmospheric pressure laser ionization ion mobility spectrometry (APLI-IMS)

When using laser radiation for ionization in ion mobility spectrometry, a large increase in the number of produced ions compared to e.g. standard radioactive sources can be achieved. This number can be so large that Coulomb broadening of the measured mobility signal can be observed. From a large enough charge density on, the Coulomb repulsion leads to effects on the motion of the ions that manifest themselves in deformations of the signal in addition to the broadening. Here we have investigated with help of finite elements method simulations the cause of this deformation and compared the calculated signals with measured ones. An important result is that the change of electric field strength when entering the drift region and its effect on the ion cloud distribution is a main factor responsible for the signal deformation.

Increasing Polyaromatic Hydrocarbon (PAH) Molecular Coverage during Fossil Oil Analysis by Combining Gas Chromatography and Atmospheric-Pressure Laser Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS).

Thousands of chemically distinct compounds are encountered in fossil oil samples that require rapid screening and accurate identification. In the present paper, we show for the first time, the advantages of gas chromatography (GC) separation in combination with atmospheric-pressure laser ionization (APLI) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for the screening of polyaromatic hydrocarbons (PAHs) in fossil oils. In particular, reference standards of organics in shale oil, petroleum crude oil, and heavy sweet crude oil were characterized by GC-APLI-FT-ICR MS and APLI-FT-ICR MS. Results showed that, while APLI increases the ionization efficiency of PAHs, when compared to other ionization sources, the complexity of the fossil oils reduces the probability of ionizing lower-concentration compounds during direct infusion. When gas chromatography precedes APLI-FT-ICR MS, an increase (more than 2-fold) in the ionization efficiency and an increase in the signal-to-noise ratio of lower-concentration fractions are observed, giving better molecular coverage in the m/z 100-450 range. That is, the use of GC prior to APLI-FT-ICR MS resulted in higher molecular coverage, higher sensitivity, and the ability to separate and characterize molecular isomers, while maintaining the ultrahigh resolution and mass accuracy of the FT-ICR MS separation.

SFC-APLI-(TOF)MS: Hyphenation of Supercritical Fluid Chromatography to Atmospheric Pressure Laser Ionization Mass Spectrometry.

Atmospheric-pressure laser ionization mass spectrometry (APLI-MS) is a powerful method for the analysis of polycyclic aromatic hydrocarbon (PAH) molecules, which are ionized in a selective and highly sensitive way via resonance-enhanced multiphoton ionization. APLI was presented in 2005 and has been hyphenated successfully to chromatographic separation techniques like high performance liquid chromatography (HPLC) and gas chromatography (GC). In order to expand the portfolio of chromatographic couplings to APLI, a new hyphenation setup of APLI and supercritical-fluid chromatography (SFC) was constructed and aim of this work. Here, we demonstrate the first hyphenation of SFC and APLI in a simple designed way with respect to different optimization steps to ensure a sensitive analysis. The new setup permits qualitative and quantitative determination of native and also more polar PAH molecules. As a result of the altered ambient characteristics within the source enclosure, the quantification of 1-hydroxypyrene (1-HP) in human urine is possible without prior derivatization. The limit of detection for 1-HP by SFC-APLI-TOF(MS) was found to be 0.5 μg L(-1), which is lower than the 1-HP concentrations found in exposed persons.

New derivatization strategies for the ultrasensitive analysis of non-aromatic analytes with APLI-TOF-MS

Atmospheric pressure laser ionization (APLI) (Constapel et al. in Rapid Commun Mass Spectrom 19:326-336, 2005; Schiewek et al. in Anal Chem 79:4135-4140, 2007; Schmitz and Benter (2007) J Chromatography Library 72:89-114) is an ultra-sensitive and selective ionization method for the determination of polycyclic aromatic compounds. The selectivity is an advantage but also a disadvantage. To overcome the limitation of APLI to aromatic compounds, we have already reported some derivatization strategies for common organic functional groups (Schiewek et al. in Angew Chem Int Ed 47:9989-9992, 2008). Here, we describe the synthesis of new APLI ionization labels and their use in new derivatization strategies. These new labels widen the range of APLI-(TOF)MS analysis to non-aromatic compounds with the most common functional groups such as amines, alcohols and carboxylic acids to gas chromatography (GC) and lower the limits of detection (LOD) down to concentrations as small as pmol/L and attomole on column.

Ionization of EPA contaminants in direct and dopant-assisted atmospheric pressure photoionization and atmospheric pressure laser ionization.

Seventy-seven EPA priority environmental pollutants were analyzed using gas chromatography-mass spectrometry (GC-MS) equipped with an optimized atmospheric pressure photoionization (APPI) and an atmospheric pressure laser ionization (APLI) interface with and without dopants. The analyzed compounds included e.g., polycyclic aromatic hydrocarbons (PAHs), nitro compounds, halogenated compounds, aromatic compounds with phenolic, acidic, alcohol, and amino groups, phthalate and adipatic esters, and aliphatic ethers. Toluene, anisole, chlorobenzene, and acetone were tested as dopants. The widest range of analytes was ionized using direct APPI (66/77 compounds). The introduction of dopants decreased the amount of compounds ionized in APPI (e.g., 54/77 with toluene), but in many cases the ionization efficiency increased. While in direct APPI the formation of molecular ions via photoionization was the main ionization reaction, dopant-assisted (DA) APPI promoted ionization reactions, such as charge exchange and proton transfer. Direct APLI ionized a much smaller amount of compounds than APPI (41/77 compounds), showing selectivity towards compounds with low ionization energies (IEs) and long-lived resonantly excited intermediate states. DA-APLI, however, was able to ionize a higher amount of compounds (e.g. 51/77 with toluene), as the ionization took place entirely through dopant-assisted ion/molecule reactions similar to those in DA-APPI. Best ionization efficiency in APPI and APLI (both direct and DA) was obtained for PAHs and aromatics with O- and N-functionalities, whereas nitro compounds and aliphatic ethers were the most difficult to ionize. Halogenated aromatics and esters were (mainly) ionized in APPI, but not in APLI.

Wood-Specific Polycyclic Aromatic Hydrocarbon (PAH) Patterns in Soot Using Gas Chromatography-Atmospheric Pressure Laser Ionization-Mass Spectrometry (GC-APLI-MS)

If organic matter is burnt, the combustion of wood produces the highest amounts of polycyclic aromatic hydrocarbons (PAHs) compared with other fossil energy sources such as oil, coal, or gas. Emissions from wood combustion are increasingly of special interest due to the rising use of wood as a renewable energy source in residential heating in Europe. To the authors' knowledge, reproducible wood-specific PAH patterns in soot were identified for the first time by use of a sampling interval of only 5 min in this study. The short sampling interval was enabled by the very sensitive analytical method of gas chromatography–atmospheric pressure laser ionization–mass spectrometry (GC-APLI-MS) applied. The analysis of 40 PAH of soot from wood logs of spruce, pine, larch (softwood) and beech, birch, oak (hardwood), and wood pellets, as well as wood briquettes, showed 13.46–250.62 mg/kg for ∑40 PAH and 10.75–177.94 mg/kg for the U.S. Environmental Protection Agency PAH standard (without acenaphthylene and anthracene). Highest concentrations occurred in the samples from birch with bark, beech, and wood briquettes. Indeno[1,2,3-cd]pyrene, naphthalene, and alkylated naphthalenes were also detected. Significant concentrations of the very toxic dibenzopyrenes (up to 11.30 mg/kg) are reported. Softwood soot contained highest amounts of 2–4-ring PAH, followed by hardwood which is in accordance with the presence of highest amounts of abietic acid in softwood, a known precursor of retene and phenanthrene. PAH in soot from five spruce samples from different locations show a mean ∑40 PAH concentration of 13.46 mg/kg (n = 5, minimum 8.03, maximum 23.32 mg/kg, SD = 5.65) and exhibited a typical pattern that differed from all other wood soot samples. The distributions of alkylated naphthalenes of the spruce samples show a bell-shape distribution in contrast to the alkylated phenanthrenes/anthracenes of all samples (except the wood pellets), showing a slope distribution. The data indicate that wood-specific PAH patterns exist and under the applied conditions, spruce logs produced the least toxic soot.

The ionization mechanisms in direct and dopant-assisted atmospheric pressure photoionization and atmospheric pressure laser ionization.

A novel, gas-tight API interface for gas chromatography-mass spectrometry was used to study the ionization mechanism in direct and dopant-assisted atmospheric pressure photoionization (APPI) and atmospheric pressure laser ionization (APLI). Eight analytes (ethylbenzene, bromobenzene, naphthalene, anthracene, benzaldehyde, pyridine, quinolone, and acridine) with varying ionization energies (IEs) and proton affinities (PAs), and four common APPI dopants (toluene, acetone, anisole, and chlorobenzene) were chosen. All the studied compounds were ionized by direct APPI, forming mainly molecular ions. Addition of dopants suppressed the signal of the analytes with IEs above the IE of the dopant. For compounds with suitable IEs or Pas, the dopants increased the ionization efficiency as the analytes could be ionized through dopant-mediated gas-phase reactions, such as charge exchange, proton transfer, and other rather unexpected reactions, such as formation of [M + 77](+) in the presence of chlorobenzene. Experiments with deuterated toluene as the dopant verified that in case of proton transfer, the proton originated from the dopant instead of proton-bound solvent clusters, as in conventional open or non-tight APPI sources. In direct APLI using a 266 nm laser, a narrower range of compounds was ionized than in direct APPI, because of exceedingly high IEs or unfavorable two-photon absorption cross-sections. Introduction of dopants in the APLI system changed the ionization mechanism to similar dopant-mediated gas-phase reactions with the dopant as in APPI, which produced mainly ions of the same form as in APPI, and ionized a wider range of analytes than direct APLI.