Detection and Monitoring of PAH and Oxy-PAHs by High Resolution Mass Spectrometry: Comparison of ESI, APCI and APPI Source Detection

Ghislain, Thierry; Faure, Pierre; Michels, Raymond

doi:10.1007/s13361-011-0304-8

Cited by 59 publications

(47 citation statements)

References 28 publications

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“…Ghislain et al described a similar phenomenon in APPI. [30] They observed quite strong protonated signal next to radical cation using hexane as solvent. They also compared ESI, APCI and APPI ionization sources in the analysis of polycyclic aromatic hydrocarbons and pointed out specific behavior of hexane in APPI conditions, showing also, that in some cases it is preferable to use in the analysis only hexane without a dopant.…”

Section: Resultsmentioning

confidence: 99%

Comparison of the sensitivity of mass spectrometry atmospheric pressure ionization techniques in the analysis of porphyrinoids

et al. 2013

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The porphyrinoids chemistry is greatly dependent on the data obtained in mass spectrometry. For this reason, it is essential to determine the range of applicability of mass spectrometry ionization methods. In this study, the sensitivity of three different atmospheric pressure ionization techniques, electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization, was tested for several porphyrinods and their metallocomplexes. Electrospray ionization method was shown to be the best ionization technique because of its high sensitivity for derivatives of cyanocobalamin, free-base corroles and porphyrins. In the case of metallocorroles and metalloporphyrins, atmospheric pressure photoionization with dopant proved to be the most sensitive ionization method. It was also shown that for relatively acidic compounds, particularly for corroles, the negative ion mode provides better sensitivity than the positive ion mode. The results supply a lot of relevant information on the methodology of porphyrinoids analysis carried out by mass spectrometry. The information can be useful in designing future MS or liquid chromatography-MS experiments.

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Section: Resultsmentioning

confidence: 99%

Comparison of the sensitivity of mass spectrometry atmospheric pressure ionization techniques in the analysis of porphyrinoids

et al. 2013

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“…There is significant value in the rapid, quantitative prescreening of samples prior to speciated measurements with standard methods such as solid phase microextraction followed by GC-MS [17], allowing the targeted analysis of contaminated samples and exclusion of prescreen non-detects, saving time and reducing overall cost. As future alternatives for speciated and unbiased direct PAH measurements in complex, real-world samples, high resolution mass spectrometry may be used to mitigate nominal mass isobaric interferences for other matrix components [34], chemical ionization (CI) approaches could affect PAH isomer differentiation [35], and MS/MS used to differentiate alkylated PAHs [24].…”

Section: Resultsmentioning

confidence: 99%

Condensed Phase Membrane Introduction Mass Spectrometry with Direct Electron Ionization: On-line Measurement of PAHs in Complex Aqueous Samples

Termopoli

Famiglini

Palma

et al. 2015

J. Am. Soc. Mass Spectrom.

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Abstract. Polycyclic aromatic hydrocarbons (PAHs) are USEPA regulated priority pollutants. Their low aqueous solubility requires very sensitive analytical methods for their detection, typically involving preconcentration steps. Presented is the first demonstrated 'proof of concept' use of condensed phase membrane introduction mass spectrometry (CP-MIMS) coupled with direct liquid electron ionization (DEI) for the direct, on-line measurement of PAHs in aqueous samples. DEI is very well suited for the ionization of PAHs and other nonpolar compounds, and is not significantly influenced by the co-elution of matrix components. Linear calibration data for low ppb levels of aqueous naphthalene, anthracene, and pyrene is demonstrated, with measured detection limits of 4 ppb. Analytical response times (t 10%-90% signal rise) ranged from 2.8 min for naphthalene to 4.7 min for pyrene. Both intra-and interday reproducibility has been assessed (<3% and 5% RSD, respectively). Direct measurements of ppb level PAHs spiked in a variety of real, complex environmental sample matrices is examined, including natural waters, sea waters, and a hydrocarbon extraction production waste water sample. For these spiked, complex samples, direct PAH measurement by CP-MIMS-DEI yielded minimal signal suppression from sample matrix effects (81%-104%). We demonstrate the use of this analytical approach to directly monitor real-time changes in aqueous PAH concentrations with potential applications for continuous on-line monitoring strategies and binding/adsorption studies in heterogeneous samples.

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“…They are typically used for small (<1000 u) molecules that are not sufficiently polar for efficient ionization by electrospray ionization (ESI). However, APPI is generally perceived to be more efficient for low polarity compounds than APCI, as has been shown for polycyclic aromatic hydrocarbons (PAHs) [5], triterpenes [6], certain steroids [7], and pharmaceuticals [8].…”

Section: Introductionmentioning

confidence: 99%

Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

Vaikkinen

Kauppila

Kostiainen

2016

J. Am. Soc. Mass Spectrom.

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Abstract. The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M +. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques.

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Detection and Monitoring of PAH and Oxy-PAHs by High Resolution Mass Spectrometry: Comparison of ESI, APCI and APPI Source Detection

Cited by 59 publications

References 28 publications

Comparison of the sensitivity of mass spectrometry atmospheric pressure ionization techniques in the analysis of porphyrinoids

Comparison of the sensitivity of mass spectrometry atmospheric pressure ionization techniques in the analysis of porphyrinoids

Condensed Phase Membrane Introduction Mass Spectrometry with Direct Electron Ionization: On-line Measurement of PAHs in Complex Aqueous Samples

Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

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