Field-deployable, high-resolution, time-of-flight aerosol mass spectrometer

The development of a new high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is reported. The high-resolution capabilities of this instrument allow the direct separation of most ions from inorganic and organic species at the same nominal m/z, the quantification of several types of organic fragments (CxHy, CxHyOz, CxHyNp, CxHyOzNp), and the direct identification of organic nitrogen and organosulfur content. This real-time instrument is field-deployable, and its high time resolution (0.5 Hz has been demonstrated) makes it well-suited for studies in which time resolution is critical, such as aircraft studies. The instrument has two ion optical modes: a single-reflection configuration offers higher sensitivity and lower resolving power (up to approximately 2100 at m/z 200), and a two-reflectron configuration yields higher resolving power (up to approximately 4300 at m/z 200) with lower sensitivity. The instrument also allows the determination of the size distributions of all ions. One-minute detection limits for submicrometer aerosol are <0.04 microg m(-3) for all species in the high-sensitivity mode and <0.4 microg m(-3) in the high-resolution mode. Examples of ambient aerosol data are presented from the SOAR-1 study in Riverside, CA, in which the spectra of ambient organic species are dominated by CxHy and CxHyOz fragments, and different organic and inorganic fragments at the same nominal m/z show different size distributions. Data are also presented from the MIRAGE C-130 aircraft study near Mexico City, showing high correlation with independent measurements of surrogate aerosol mass concentration.     

Real-time measurement of oligomeric species in secondary organic aerosol with the aerosol time-of-flight mass spectrometer

Real-time detection of oligomers in secondary organic aerosols has been carried out with an aerosol time-of-flight mass spectrometer sampling particles generated in a smog chamber. The photooxidation products of 1,3,5-trimethylbenzene and NOx were studied over a range of initial 1,3,5-trimethylbenzene concentrations (137-1180 ppb), while keeping the 1,3,5-trimethylbenzene to NOx ratio nearly constant. The photooxidation products of a mixture of alpha-pinene (initial concentration 191 ppb), 1,3,5-trimethylbenzene (60 ppb), and NOx were also investigated. In both systems, ions were observed in the single-particle mass spectra up to 750 Da; the species observed differed in the two systems. These high-mass ions occur with characteristic spacing of 14 and 16 Da, indicative of oligomeric species. The results obtained agree well with off-line (matrix-assisted) laser desorption/ionization mass spectrometry results. The real-time capabilities of the aerosol time-of-flight mass spectrometer make it possible to investigate the temporal development of the oligomers with 5-min time resolution and also demonstrate that there are certain ions within the oligomer population that occur in nearly all of the particles and with relatively high signal intensity, suggesting that these ions have higher stability or that the species are formed preferentially.     

Ozonation of trifluralin particles: An experimental investigation with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer

The ozonation of trifluralin coated on azelaic acid particles is investigated with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer. The suspended trifluralin particles with the mean diameter of 270 nm react with 100 ppm ozone in an aerosol reaction chamber under ambient pressure and room temperature (1 atm, 298 K). The time-of-flight mass spectra of the trifluralin particles and the solid state ozonides are obtained. The assignments of the mass spectra reveal that the major primary ozonides of trifluralin particles are 2,6-dinitro-N-propyl-N-propanoyl-4-(trifluoromethyl) benzamine and 2,6-dinitro-N-(propan-2(and 3)-ol)-N-propyl-4-(trifluoromethyl) benzamine. The major secondary ozonides of trifluralin 2-ethyl-7-nitro-5-(trifluoromethyl) benzimidazole-3-oxide, 2,6-dinitro-N-propyl-4-(trifluoromethyl) benzenamine and 2,6-dinitro-N-(formyl)-N-propyl-4-(trifluoromethyl) benzamine are observed. The primary ozonides are directly resulted from the oxidation of N-propyl groups. The pathways of the primary ozonation are proposed in the paper.     

Pulsed oscillating mass spectrometer: a miniaturized type of time-of-flight mass spectrometer

We report the development, characterization, and performance of a new type of time-of-flight mass analyzer that employs an oscillatory ion flight path and uses secondary electrons to record the mass spectrum. The analyzer is simple in concept and design and inexpensive to build and has been made as small as 6-cm total length. The oscillating ions produce a periodic secondary electron signal whose frequency is mass dependent in mathematically the same way as a conventional time-of-flight analyzer. Because of the oscillating nature of the ions, we have called the analyzer the pulsed oscillating mass spectrometer.     

Estimating the precision of exact mass measurements on an orthogonal time-of-flight mass spectrometer

The combination of orthogonal TOF/ESI MS exact mass measurement and on-line chromatography represents a powerful analytical tool for identifying unknown components in complex mixtures and is being widely utilized. The precision of these mass data is often incorrectly estimated as the precision or mean deviation obtained for reference standards under standard conditions. But, the precision of a mass measurement is dependent on the number of ions sampled in the measurement and, thus, is likely to be different for every measurement. A simple procedure for correctly estimating the precision of a specific mass measurement is presented, the limits of the procedure are investigated, and the utility and validity of the procedure are demonstrated.     

TOFI: An isochronous time-of-flight mass spectrometer

A time-of-flight mass spectrometer was constructed to measure the masses of neutron-rich recoils produced in proton-induced fragmentation reactions. This system consists of four sector magnets designed such that the overall flight time is independent of the velocity of the recoil ions and thus depends only on their mass-to-charge ratios.     

Planar multipole ion trap/time-of-flight mass spectrometer

We present a novel, hybrid ion trap/time-of-flight mass spectrometer that is based on a planar multipole design. Compared with Paul trap/time-of-flight instruments, this design possesses the principal advantages of higher injection efficiency and more homogeneous extraction fields. We demonstrate the viability of the concept and describe the characterization of a first prototype. Ions can be injected into the trap with little mass discrimination and stored for several minutes. A resolution of over 1300 is achieved in reflectron mode, and the influence of the RF amplitude and pressure on the resolution is analyzed. We suggest several applications in which this new instrument could offer advantages over existing technology.     

C60 secondary ion mass spectrometry with a hybrid-quadrupole orthogonal time-of-flight mass spectrometer

A hybrid quadrupole orthogonal time-of-flight mass spectrometer optimized for matrix-assisted laser desorption ionization (MALDI) and electrospray ionization has been equipped with a C 60 cluster ion source. This configuration is shown to exhibit a number of characteristics that improve the performance of traditional time-of-flight secondary ion mass spectrometry (TOF-SIMS) experiments for the analysis of complex organic materials and, potentially, for chemical imaging. Specifically, the primary ion beam is operated as a continuous rather than a pulsed beam, resulting in up to 4 orders of magnitude greater ion fluence on the target. The secondary ions are extracted at very low voltage into 8 mTorr of N 2 gas introduced for collisional focusing and cooling purposes. This extraction configuration is shown to yield secondary ions that rapidly lose memory of the mechanism of their birth, yielding tandem mass spectra that are identical for SIMS and MALDI. With implementation of ion trapping, the extraction efficiency is shown to be equivalent to that found in traditional TOF-SIMS machines. Examples are given, for a variety of substrates that illustrate mass resolution of 12,000-15,600 with a mass range for inorganic compounds to m/ z 40,000. Preliminary chemical mapping experiments show that with added sensitivity, imaging in the MS/MS mode of operation is straightforward. In general, the combination of MALDI and SIMS is shown to add capabilities to each technique, providing a robust platform for TOF-SIMS experiments that already exists in a large number of laboratories.     

Multicomponent aerosol mass efficiency with various mixture types for polydispersed aerosol

Based on the filter-sampled chemical composition data the seasonal variation of the optical properties of polydispersed aerosols, extinction, scattering, and absorption coefficient, are estimated for various types of aerosol mixtures. The mixtures considered in this study are the internal mixture, elemental carbon (EC)/non-EC external mixture, and fully external mixture. This study also evaluated the sensitivity of the aerosol optical properties for different size distributions. The results show that the extinction coefficient can be mostly accounted for scattering and generally shows a good agreement with each mixture type in this case study. However, the absorption coefficient shows a different tendency for internal and external mixtures. This study also shows that the aerosol optical properties vary as a function of particle diameter at the same composition and mass concentration. This means that mass extinction, scattering, and absorption efficiencies, which were considered as constants in general, should be reassessed and more specifically described as a function of particle size.     

Interpretation of mass spectra from organic compounds in aerosol time-of-flight mass spectrometry

Organic compounds containing a variety of functional groups have been analyzed using aerosol time-of-flight mass spectrometry. Both positive and negative laser desorption/ionization mass spectra have been acquired for compounds of relevance to ambient air particulate matter, including polycyclic aromatic hydrocarbons, heterocyclic analogues, aromatic oxygenated compounds such as phenols and acids, aliphatic dicarboxylic acids, and reduced nitrogen species such as amines. In many cases, positive ion mass spectra are similar to those found in libraries for 70-eV electron impact mass spectrometry. However, formation of even-electron molecular ions due to adduct formation also plays a major role in ion formation. Negative ion mass spectra suggest that organic compounds largely disintegrate into carbon cluster fragments (C(n)- and C(n)H-). However, information about the heteroatoms present in organic molecules, especially nitrogen and oxygen, is carried dominantly by negative ion spectra, emphasizing the importance of simultaneous analysis of positive and negative ions in atmospheric samples.     

Simultaneous mass analysis of positive and negative ions using a dual-polarity time-of-flight mass spectrometer

Positive and negative ions produced from matrix-assisted laser desorption/ionization (MALDI) were simultaneously measured using a newly developed dual-polarity time-of-flight mass spectrometer. This instrument is effective not only for express and comprehensive mass analysis but also for studying the ionization mechanisms of biomolecules. It comprises two identical time-of-flight mass analyzers located symmetrically about a MALDI ion source. The ion optics are arranged to be able to extract positive and negative ions synchronously with equal efficiency to each corresponding mass analyzer. Mass spectra of various proteins with molecular weights as large as that of myoglobin monomer and dimer were obtained. The spectral patterns obtained in this work are approximately mirror images with opposite polarities.     

Direct chemical analysis of solids by laser ablation in an ion storage time-of-flight mass spectrometer

A laser ablation/ionization mass spectrometer system is described for the direct analysis of solids, particles, and fibers. The system uses a quadrupole ion trap operated in an ion storage mode, coupled with a reflectron time-of-flight mass spectrometer). The sample is inserted radially into the ring electrode, and an imaging system allows direct viewing and selected analysis of the sample. Measurements identified trace contaminants of Ag, Sn, and Sb in a Pb target with single laser shot experiments. Resolution (m/Delta m) of 1500 and detection limits of approximately 10 pg have been achieved with a single laser pulse. The system configuration and related operating principles for accurately measuring low concentrations of isotopes are described.     

Quantitative proteomic analysis using a MALDI quadrupole time-of-flight mass spectrometer

We describe an approach to the quantitative analysis of complex protein mixtures using a MALDI quadrupole time-of-flight (MALDI QqTOF) mass spectrometer and isotope coded affinity tag reagents (Gygi, S. P.; et al. Nat. Biotechnol. 1999, 17, 994-9.). Proteins in mixtures are first labeled on cysteinyl residues using an isotope coded affinity tag reagent, the proteins are enzymatically digested, and the labeled peptides are purified using a multidimensional separation procedure, with the last step being the elution of the labeled peptides from a microcapillary reversed-phase liquid chromatography column directly onto a MALDI sample target. After addition of matrix, the sample spots are analyzed using a MALDI QqTOF mass spectrometer, by first obtaining a mass spectrum of the peptides in each sample spot in order to quantify the ratio of abundance of pairs of isotopically tagged peptides, followed by tandem mass spectrometric analysis to ascertain the sequence of selected peptides for protein identification. The effectiveness of this approach is demonstrated in the quantification and identification of peptides from a control mixture of proteins of known relative concentrations and also in the comparative analysis of protein expression in Saccharomyces cerevisiae grown on two different carbon sources.     

On-line capillary electrophoresis/microelectrospray ionization-tandem mass spectrometry using an ion trap storage/time-of-flight mass spectrometer with SWIFT technology.

The development of a system capable of the speed required for on-line capillary electrophoresis-tandem mass spectrometry (CE-MS/MS) of tryptic digests is described. The ion trap storage/reflectron time-of-flight (IT/reTOF) mass spectrometer is used as a nonscanning detector for rapid CE separation, where the peptides are ionized on-line using electrospray ionization (ESI). The ESI produced ions are stored in the ion trap and dc pulse injected into the reTOF-MS at a rate sufficient to maintain the separation achieved by CE. Using methodology generated by software and hardware developed in our lab, we can produce SWIFT (Stored Waveform Inverse Fourier Transform) ion isolation and TICKLE activation/fragmentation voltage waveforms to generate MS/MS at a rate as high as 10 Hz so that the MS/MS spectra can be optimized on even a 1-2 s eluting peak. In CE separations performed on tryptic digests of dogfish myelin basic protein (MBP) where eluting peaks 4-8 s wide are observed, it is demonstrated that an acquisition rate of 4 Hz provides > 20 spectra/peak and is more than sufficient to provide optimized MS/MS spectra of each of the eluting peaks in the electropherogram. The detailed structural analysis of dogfish MBP including several posttranslational modifications using CE-MS and CE-MS/MS is demonstrated using this method with < 10 fmol of material consumed.     

Synchrotron radiation based aerosol time-of-flight mass spectrometry for organic constituents

A synchrotron radiation based aerosol time-of-flight mass spectrometer using tunable vacuum-ultraviolet (VUV) light is described for real-time analysis of organic compounds in ultrafine and large aerosol particles. Particles are sampled from atmospheric pressure and are focused through an aerodynamic lens assembly into the mass spectrometer. As the particles enter the source region, they impinge on a cartridge heater and are vaporized. The particle vapor expands back into the source region and is softly ionized with tunable, quasicontinuous VUV light generated with synchrotron radiation. The radiation can be tuned to an energy close to the ionization energy of the sample molecules, thus minimizing the complications resulting from ion fragmentation. Photoionization efficiency scans (photon scans) can be readily collected, which permit measurement of the molecule's ionization energy and fragmentation onsets. Four high molecular weight, low vapor pressure organic compounds of importance in atmospheric aerosols are analyzed and their ionization energies measured with uncertainties of +/-60 meV. These are oleic acid (8.68 eV), linoleic acid (8.52 eV), linolenic acid (8.49 eV), and cholesterol (8.69 eV).     

Possibility of analyzing deuterium-tritium gas mixtures using a time-of-flight mass spectrometer

The use of a time-of-flight mass spectrometer, whose ion source and detector operate in a synchronous regime, is proposed for the chemical and isotope analysis of gas mixtures containing radioactive tritium. The experiments performed confirm that the detector background current caused by tritium β electrons scarcely influences the signal-to-noise ratio and does not diminish the accuracy of analyses. Pis’ma Zh. Tekh. Fiz. 23, 83–87 (October 26, 1997)     

Detection of chemical warfare-related species on complex aerosol particles deposited on surfaces using an ion trap-based aerosol mass spectrometer

A new type of aerosol mass spectrometer was developed by minimal modification of an existing commercial ion trap to analyze the semivolatile components of aerosols in real time. An aerodynamic lens-based inlet system created a well-collimated particle beam that impacted into the heated ionization volume of the commercial ion trap mass spectrometer. The semivolatile components of the aerosols were thermally vaporized and ionized by electron impact or chemical ionization in the source. The nascent ions were extracted and injected into the ion trap for mass analysis. The utility of this instrument was demonstrated by identifying semivolatile analytes in complex aerosols. This study is part of an ongoing effort to develop methods for identifying chemical species related to CW agent exposure. Our efforts focused on detection of CW-related species doped on omnipresent aerosols such as house dust particles vacuumed from various surfaces found in any office building. The doped aerosols were sampled directly into the inlet of our mass spectrometer from the vacuumed particle stream. The semivolatile analytes were deposited on house dust and identified by positive ion chemical ionization mass spectrometry up to 2.5 h after deposition. Our results suggest that the observed semivolatile species may have been chemisorbed on some of the particle surfaces in submonolayer concentrations and may remain hours after deposition. This research suggests that identification of trace CW agent-related species should be feasible by this technique.     

Ion isolation in a continuous zero angle reflecting time-of-flight mass spectrometer

A continuous zero angle reflecting time-of-flight mass spectrometer capable of tandem mass spectrometry measurements with high resolution and high sensitivity has been developed. The instrument design features two pulsed-ion mirrors in a coaxial geometry. Ions can be reflected back and forth with the mirrors, which increases the net flight length and permits kinetic energy focusing for enhanced resolution. The instrument also contains an electrostatic particle guide which increases ion transmission efficiency and can be used in a bipolar pulsed mode to isolate ions of interest for structural study.     

Identification of in-gel digested proteins by complementary peptide mass fingerprinting and tandem mass spectrometry data obtained on an electrospray ionization quadrupole time-of-flight mass spectrometer

The present study reports a procedure developed for the identification of SDS-polyacrylamide gel electrophoretically separated proteins using an electrospray ionization quadrupole time-of-flight mass spectrometer (Q-TOF MS) equipped with pressurized sample introduction. It is based on in-gel digestion of the proteins without previous reduction/alkylation and on the capability of the Q-TOF MS to provide data suitable for peptide mass fingerprinting database searches and for tandem mass spectrometry (MS/MS) database searches (sequence tags). Omitting the reduction/alkylation step reduces sample contamination and sample loss, resulting in increased sensitivity. Omitting this step can leave disulfide-connected peptides in the analyte that can lead to misleading or ambiguous results from the peptide mass fingerprinting database search. This uncertainty, however, is overcome by MS/MS analysis of the peptides. Furthermore, the two complementary MS approaches increase the accuracy of the assignment of the unknown protein. This procedure is thus, highly sensitive, accurate, and rapid. In combination with pressurized nanospray sample introduction, it is suitable for automated sample handling. Here, we apply this approach to identify protein contaminants observed during the purification of the yeast DNA mismatch repair protein Mlh 1.