Sensitive and selective analysis of polychlorinated dibenzo-p-dioxins/dibenzofurans and their precursors by supersonic jet/resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry.

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), some of which are extremely toxic, are present at low concentrations in incinerator flue gases. The on-line real-time measurement of these compounds is necessary, since these concentrations fluctuate drastically with the process conditions used. Supersonic jet/resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry (SSJ/REMPI/TOF-MS), which provides both high selectivity and sensitivity, appears suitable for application to the on-line real-time monitoring of PCDD/Fs. In this review, the resonant ionization wavelengths of PCDD/Fs and their precursors are given. Moreover, improvements in SSJ/REMPI/TOF-MS that lead to enhanced sensitivity and selectivity are presented. That is, novel ionization sources and advanced ionization schemes are reported for the sensitive measurement of PCDD/Fs and their precursors. Those techniques are advantageous for the trace analysis of these compounds.     

Gas chromatography/multiphoton ionization/time-of-flight mass spectrometry of polychlorinated biphenyls

A sample mixture of polychlorinated biphenyls (PCBs) was measured by gas chromatography/multiphoton ionization/time-of-flight mass spectrometry (GC/MPI/TOF-MS) using four types of laser sources. When a fourth harmonic emission (266 nm) of a picosecond Nd:YAG laser (1064 nm) was utilized, highly chlorinated PCBs larger than hepta-CBs were not observed. A fifth harmonic emission (213 nm) of the picosecond Nd:YAG laser allowed the measurement of PCBs from di-CBs to octa-CBs, and the limit of detection (LOD) was several pg for each component of PCBs. The LOD for the total amount of PCBs, which was calculated using the protocol provided by the Ministry of the Environment, Japan, was 1000 pg. The signal intensity of the congeners with chlorine atoms at the ortho positions (non-coplanar PCBs) was enhanced by using the fifth harmonic emission. When the fourth harmonic emission remaining after fifth harmonic generation was simultaneously used, the LOD for total PCBs was improved to 667 pg. The PCB sample was also measured using a third harmonic emission (267 nm) of a femtosecond Ti:sapphire laser (800 nm), providing an LOD of 677 pg. Thus, the two-color beam (266/213 nm) of a picosecond Nd:YAG laser had a comparable, or even slightly superior, performance to the more expensive femtosecond Ti:sapphire laser.     

Wavelength-dependent fragmentation in resonance-enhanced multiphoton ionization mass spectrometry

Wavelength-dependent effects in the resonance-enhanced multiphoton ionization/fragmentation mass spectra of p-chloroaniline and diphenyl ether are presented. For both molecules, the formation of low-energy fragments can be discriminated against in favor of higher-energy fragments by using ‘low’-energy radiation (290 nm region) for ionization/fragmentation. The same low-energy fragments become dominant when higher-energy radiation (266 nm) is used. This unique behavior is explained in terms of the narrow distribution of parent ion internal energies created through resonance-enhanced multiphoton ionization/fragmentation and the competing kinetic processes accessed by the parent ion as it absorbs each successive photon.     

Gas chromatography/multiphoton ionization/time-of-flight mass spectrometry using a femtosecond laser

A laser can be used for the selective excitation and subsequent ionization of a molecule with an absorption band at the laser wavelength. This technique of multiphoton ionization (MPI), when combined with time-of-flight mass spectrometry (TOF-MS), permits the efficient detection of induced ions in mass analysis. This combination of MPI/TOF-MS can be coupled with gas chromatography (GC) to achieve even more enhanced selectivity. Thus, GC/MPI/TOF-MS can be employed for trace analysis of samples containing numerous chemical species. A variety of laser sources have been used for this purpose. Since molecules that are classified as environmental pollutants frequently contain chlorine and bromine atoms, the lifetime of the excited state can be decreased by energy transfer from the singlet to triplet levels by spin–orbit interaction. A high-power femtosecond laser with a pulse width shorter than the lifetime of the analyte molecule provides femtogram or even subfemtogram detection limits, which have not yet been achieved using the most sensitive high-resolution double-focus sector-type mass spectrometers. Numerous environmental pollutants such as dioxins in soils and pesticides in foods have been successfully quantified using GC/MPI/TOF-MS, and this technique has proven itself to be a useful and practical method for trace analysis.

Analysis of thermal decomposition products arising from polyvinyl chloride analogs by supersonic jet/multiphoton ionization/mass spectrometry

Polyvinyl chloride (PVC) and chlorinated polyvinyl chloride (CPVC) were thermally decomposed at 200-500 degrees C, and the reaction products measured by supersonic jet/multiphoton ionization/mass spectrometry. No precursor molecules of dioxins, such as chlorobenzene, were observed from PVC, although benzene was produced as one of the major components. On the other hand, a large peak corresponding to chlorobenzene was observed, when CPVC was used as a sample. These results suggest that the release of hydrogen chloride and aromatic ring formation occur efficiently and produce chlorinated aromatic hydrocarbons only when excess chlorine atoms are present in the chain of PVC. This method, which has very high selectivity is preferred for trace analysis of specific compounds such as dioxin precursors in a complex mixture. Isomer-selective analysis, e.g. detection of o-, m-, and p-dichlorobenzenes, is also demonstrated in this study.     

Analysis of pesticides by gas chromatography/multiphoton ionization/mass spectrometry using a femtosecond laser

Gas chromatography/multiphoton ionization/time-of-flight mass spectrometry (GC/MPI/TOFMS) was utilized for analysis of a standard mixture sample containing 49 pesticides and 4 real samples using the third-harmonic emission (267 nm) of a femtosecond Ti:sapphire laser (100 fs) as the ionization source. A sample of a standard mixture of n-alkane was also measured for calibration of the retention time indices of the pesticides. Two photons are required for the excitation of n-alkane due to an absorption band located in the far ultraviolet region (140 nm). The n-alkane molecule in the excited state was subsequently ionized either directly or by absorbing another photon because of a high ionization potential. Due to a large excess of energy, the molecular ion was decomposed and formed many fragment ions. Compared to n-alkanes, most of the pesticides were softly ionized by the femtosecond laser; one photon was used for excitation and another was used for the subsequent ionization. The pesticides with no conjugated double bond had a lower ionization efficiency. The present analytical instrument was applied to several samples prepared from a variety of vegetables and a single fruit after pretreatment with solid-phase extraction. Three pesticides were found in these samples, although some of them were not detected by conventional GC/EI/MS–MS due to insufficient sensitivity and selectivity.     

Near-ultraviolet femtosecond laser ionization of dioxins in gas chromatography/time-of-flight mass spectrometry

Gas chromatography/multiphoton ionization/time-of-flight mass spectrometry (GC/MPI/TOF-MS) was applied to the trace analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). To determine the optimum wavelength for analysis of PCDD/Fs, the wavelength of the femtosecond laser utilized for multiphoton ionization was converted to near-ultraviolet status using stimulated Raman scattering. A femtosecond laser emitting at 300 nm completely eliminated the background signal arising from the bleeding compounds generated from a stationary phase of the capillary column in GC.     

Classical electron ionization mass spectra in gas chromatography/mass spectrometry with supersonic molecular beams

A major benefit of gas chromatography/mass spectrometry (GC/MS) with a supersonic molecular beam (SMB) interface and its fly-through ion source is the ability to obtain electron ionization of vibrationally cold molecules (cold EI), which show enhanced molecular ions. However, GC/MS with an SMB also has the flexibility to perform 'classical EI' mode of operation which provides mass spectra to mimic those in commercial 70 eV electron ionization MS libraries. Classical EI in SMB is obtained through simple reduction of the helium make-up gas flow rate, which reduces the SMB cooling efficiency; hence the vibrational temperatures of the molecules are similar to those in traditional EI ion sources. In classical EI-SMB mode, the relative abundance of the molecular ion can be tuned and, as a result, excellent identification probabilities and very good matching factors to the NIST MS library are obtained. Classical EI-SMB with the fly-through dual cage ion source has analyte sensitivity similar to that of the standard EI ion source of a basic GC/MS system. The fly-through EI ion source in combination with the SMB interface can serve for cold EI, classical EI-SMB, and cluster chemical ionization (CCI) modes of operation, all easily exchangeable through a simple and quick change (not involving hardware). Furthermore, the fly-through ion source eliminates sample scattering from the walls of the ion source, and thus it offers full sample inertness, tailing-free operation, and no ion-molecule reaction interferences. It is also robust and enables increased column flow rate capability without affecting the sensitivity.     

Analysis of triacetone triperoxide by gas chromatography/mass spectrometry and gas chromatography/tandem mass spectrometry by electron and chemical ionization

The explosive triacetone triperoxide (TATP) has been analyzed by gas chromatography/mass spectrometry (GC/MS) and sub-nanogram detection limits are reported by ammonia positive ion chemical ionization (PICI), electron ionization (EI) and methane negative ion chemical ionization (NICI). Analysis by methane PICI and ammonia NICI gave detection limits in the low nanogram range. Analyses were carried out on (linear) quadrupole and ion trap instruments. Analysis of TATP by PICI using ammonia reagent gas is the preferred analytical method, producing low limits of detection as well as an abundant (greater than 60% of base peak) diagnostic adduct ion at m/z 240 corresponding to [TATP + NH4]+. Isolation of the [TATP + NH4]+ ion with subsequent collision-induced dissociation (CID) produces extremely low abundance product ions at m/z values greater than 60, and the m/z 223 ion corresponding to [TATP + H]+ was not observed. Density functional theory (DFT) calculations at the B88LYP/DVZP level indicate that dissociation of the complex to form NH4+ and TATP occurs at energies lower than peroxide bond dissociation, while protonation of TATP leads to cleavage of the ring structure. These results provide a method for pico-gram detection levels of TATP using commercial instrumentation commonly available in forensic laboratories. As a point of comparison, a detection limit of 15 ng was obtained by flame ionization detection.     

Quantitative gas chromatography/time-of-flight mass spectrometry: a review

Time-of-flight (TOF) instruments have recently gained popularity in quantitative analyses. Normally, TOF mass spectrometers are used for accurate mass measurements for empirical formula verification. However, over the past decade, they have been used quantitatively as well. Because of the fast separations and narrow peaks that result from gas chromatography separations, scanning mass spectrometers are not ideal detectors. TOF mass spectrometers, however, have the ability to collect spectra at a faster rate. Two-dimensional gas chromatography has also been introduced to further resolve peaks from complex matrices. Two-dimensional gas chromatography results in a faster separation as well as narrower peaks. This paper reviews the methods currently in the literature for the quantitation of compounds using one- and two-dimensional gas chromatography and TOF mass spectrometry detection.     

Ganglioside analysis by thin-layer chromatography matrix-assisted laser desorption/ionization orthogonal time-of-flight mass spectrometry

Metastable decomposition of ions generated in matrix-assisted laser desorption/ionization (MALDI) mass spectrometers complicates analysis of biological samples that have labile bonds. Recently, several academic laboratories and manufacturers of commercial instruments have designed instruments that introduce a cooling gas into the ion source during the MALDI event and have shown that the resulting vibrational cooling stabilizes these labile bonds. In this study, we compared stabilization and detection of desorbed gangliosides on a commercial orthogonal time-of-flight (oTOF) instrument with results we reported previously that had been obtained on a home-built Fourier transform mass spectrometer. Decoupling of the desorption/ionization from the detection steps resulted in an opportunity for desorbing thin-layer chromatography (TLC)-separated gangliosides directly from a TLC plate without compromising mass spectral accuracy and resolution of the ganglioside analysis, thus coupling TLC and oTOF mass spectrometry. The application of a declustering potential allowed control of the matrix cluster and matrix adduct formation, and, thus, enhanced the detection of the gangliosides.     

Use of soft and hard ionization techniques for elucidation of unknown compounds by gas chromatography/time-of-flight mass spectrometry

Investigation of trace-level non-target compounds by gas chromatography/mass spectrometry (GC/MS) often is a challenging task that requires powerful software tools to detect the unknown components, to obtain the deconvoluted mass spectra, and to interpret the data if no acceptable library match is obtained. In this paper, the complementary use of electron ionization (EI) and chemical ionization (CI) is investigated in combination with GC/time-of-flight (TOF) MS for the elucidation of organic non-target (micro)contaminants in water samples. Based on accurate mass measurement of the molecular and fragment ions from the TOF MS, empirical formulae were calculated. Isotopic patterns, carbon number prediction filter and nitrogen rule were used to reduce the number of possible formulae. The candidate formulae were searched in databases to find possible chemical structures. Selection from possible structure candidates was achieved using information on substructures and observed neutral losses derived from the fragment ions. Four typical examples (bifenazate, boscalid, epoxiconazole, and fenhexamid) are used to illustrate the methodology applied and the various difficulties encountered in this process. Our results indicate that elucidation of unknowns cannot be achieved by following a standardized procedure, as both expertise and creativity are necessary in the process.     

Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry peak sorting algorithm

We report a novel peak sorting method for the two-dimensional gas chromatography/time-of-flight mass spectrometry (GC x GC/TOF-MS) system. The objective of peak sorting is to recognize peaks from the same metabolite occurring in different samples from thousands of peaks detected in the analytical procedure. The developed algorithm is based on the fact that the chromatographic peaks for a given analyte have similar retention times in all of the chromatograms. Raw instrument data are first processed by ChromaTOF (Leco) software to provide the peak tables. Our algorithm achieves peak sorting by utilizing the first- and second-dimension retention times in the peak tables and the mass spectra generated during the process of electron impact ionization. The algorithm searches the peak tables for the peaks generated by the same type of metabolite using several search criteria. Our software also includes options to eliminate non-target peaks from the sorting results, e.g., peaks of contaminants. The developed software package has been tested using a mixture of standard metabolites and another mixture of standard metabolites spiked into human serum. Manual validation demonstrates high accuracy of peak sorting with this algorithm.     

Characterization of silsesquioxanes by size-exclusion chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Liquid chromatography in combination with spectroscopic methods like matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) or nuclear magnetic resonance (NMR) spectroscopy is a powerful method to characterize silsesquioxanes and silsesquioxane mixtures. As new examples, the formation of silsesquioxyl-substituted silsesquioxanes [(n-octyl)(7)(SiO(1.5))(8)](2)O and [(n-octyl)(7)(SiO(1.5))(8)O](2)[(n-octyl)(6)(SiO(1.5))(8)] as well as the cage rearrangement of octa-[(n-heptyl)silsesquioxane] to larger structures [(n-heptyl)SiO(1.5))](n) up to n=28 are shown.     

Determination of anabolic steroids by gas chromatography/negative-ion chemical ionization mass spectrometry and gas chromatography/negative-ion chemical ionization tandem mass spectrometry with heptafluorobutyric anhydride derivatization

A gas chromatography/mass spectrometry (GC/MS) method is described which uses negative ion chemical ionization (NCI) and tandem mass spectrometry (MS/MS) for the determination of eight anabolic steroids in human urine. Eight anabolic steroids were derivatized by heptafluorobutyric anhydride (HFBA), and were determined using GC/NCI-MS and GC/NCI-MS/MS. The linear correlation coefficients for calibration in NCI-MS/MS were in the range 0.9880-0.9988. This method of derivatization with HFBA for use with GC/NCI was useful in determinations of 19-norandrosterone, boldenone, 19-noretiocholanolone, 2-methylandrosterone, nandrolone, 1-methyleneandrosterone, 1-methylandrosterone, 4-dihydroboldenone and mesterolone. The detection limits of this procedure were 5-20 ppb at a signal-to-noise (S/N) ratio of 3.     

Rapid determination of 5-hydroxymethylfurfural by DART ionization with time-of-flight mass spectrometry

DART (direct analysis in real time), a novel technique with wide potential for rapid screening analysis, coupled with high-resolution time-of-flight mass spectrometry (TOF-MS) has been used for quantitative analysis of 5-hydroxymethylfurfural (5-HMF), a typical temperature marker of food. The DART/TOF-MS method was optimised and validated. Quantification of 5-HMF was achieved by use of a stable isotope-labelled 5-HMF standard prepared from glucose. Formation of 5-HMF from saccharides, a potential source of overestimation of results, was evaluated. Forty-four real samples (honey and caramelised condensed sweetened milk) and 50 model samples of heated honey were analysed. The possibility of using DART for analysis of heated samples of honey was confirmed. HPLC and DART/TOF-MS methods for determination of 5-HMF were compared. The correlation equation between these methods was DART?=?1.0287HPLC?+?0.21340, R ²?=?0.9557. The DART/TOF-MS method has been proved to enable efficient and rapid determination of 5-HMF in a variety of food matrices, for example honey and caramel.     

Pulsed-valve chemical ionization for gas chromatography/fourier-transform mass spectrometry

The pressure requirements for chemical ionization g.c./F.t.m.s. which restrict mass resolution and accuracy are overcome through use of a pulsed valve that provides momentary reagent gas pressures. For alternate electron impact (EI)/chemical ionization (c.i.) g.c./F.t.m.s., similar resolution for both e.i. and c.i. data is demonstrated. The efficiency of chemical ionization with the pulsed valve is similar to static high pressure c.i. measurements of several model compounds. Results from the analysis of peppermint oil and a fuel additive illustrate the potential information available from a single g.c./F.t.m.s. experiment.     

Two-color multiphoton ionization of diazabicyclooctane in a supersonic free jet

Two-color multiphoton ionization (MPI) spectroscopy has been applied for diazabicyclooctane (DABCO) in a supersonic free jet. The MPI spectra due to transitions from the various vibronic levels of the S₁ (3s Rydberg) state which were excited by the first laser revealed the high Rydberg states above the adiabatic ionization potential. The ionization process and the vibrational potential of the ion are discussed.