Depth profiling of heterogeneously mixed aerosol particles using single-particle mass spectrometry

Infrared laser evaporation of single aerosol particles in a vacuum followed by vacuum ultraviolet (VUV) laser ionization and time-of-flight mass spectroscopy of the resulting vapor provides a depth profile of the particle's composition. Analyzing glycerol particles coated with 60-150-nm coatings of oleic acid using either a CO2 laser or a tunable optical parametric oscillator as an evaporation laser results in mass spectra that depend on the IR laser power. Low infrared laser powers incompletely vaporize particles and preferentially probe the composition of the surface layers of the particle, but high laser powers evaporate the entire particle and produce spectra representative of the particle's total composition. In the limit of low laser power, the fraction of oleic acid in the mass spectra is as much as 50 times greater than the fraction of oleic acid in the particle, providing a surface-layer-specific characterization. The OPO laser provides even more surface specificity, producing an [oleic acid]/[glycerol] ratio as much as four times larger (for a 60-nm coating) than that obtained using the CO2 laser. The infrared laser power required to sample the core of the particle increases with the thickness of the coating and is sensitive to changes in the coating thickness on the order of 10 nm. In contrast to these intuitively appealing results, high CO2 laser powers (approximately 90 mJ/pulse) produce mass spectra that, at short delays between the CO2 and VUV lasers, show enrichment of the core material rather than the coating. Likewise, tuning the OPO to frequencies that are resonant with the core material but transparent to the coating also results in selective detection of the core. The results suggest that a shattering mechanism dominates the vaporization dynamics in these situations.     

Analysis of Xanthate Derivatives by Vacuum Ultraviolet Laser-Time-of-Flight Mass Spectrometry

A series of liquid O,S-dialkyl dithiocarbonates (xanthate esters) have been synthesized, and time-of-flight (TOF) mass spectra were recorded for their vapors using both ultraviolet (UV) and vacuum ultraviolet (VUV) laser excitation. These compounds are chemical derivatives of low vapor pressure xanthate salts which have found important commercial application as collectors in mineral sulfide flotation circuits. Our experiments demonstrate that esters ionized by short-wavelength VUV light can be detected by parent mass with high efficiency and minimal fragmentation. In contrast, the mass spectra of the same compounds obtained by UV light excitation exhibit a large number of low molecular mass peaks. A preliminary quantitative analysis of the composition of a gas-phase mixture of xanthate esters has also been achieved, which indicates possible subfemtomole detection limits.     

Surface mass spectrometry of biotinylated self-assembled monolayers

Biotin and biotinylated self-assembled monolayers (SAMs) on gold have been investigated using time-of-flight secondary ion mass spectrometry, direct laser desorption, laser desorption with 193 nm photoionization of ion- and laser-desorbed species, and laser desorption with vacuum ultraviolet (VUV, 118 nm) photoionization. Our results indicate that direct laser desorption and laser desorption combined with 193 nm multiphoton ionization can detect a chromophoric molecule like biotin that is covalently bound to a SAM. However, secondary ion mass spectra were dominated by fragmentation, and ion desorption/193 nm photoionization detected no species related to biotin. The dominant features of the laser desorption/VUV mass spectra were neat and Au-complexed dimers of intact and fragmented biotinylated SAM molecules. Multiphoton and single-photon ionization of laser-desorbed neutrals from biotinylated SAMs both led to the production of ions useful for chemical analysis of the monolayer. Multiphoton ionization with ultraviolet radiation was experimentally less challenging but required a chromophore for ionization and resulted in significant fragmentation of the adsorbate. Single-photon ionization with VUV radiation was experimentally more challenging but did not require a chromophore and led to less fragmentation. X-ray photoelectron spectra indicated that the biotinylated SAM formed a disordered, 40-60 ? thick monolayer on Au. Additionally, projection photolithography with a Schwarzschild microscope was used to pattern the biotinylated SAM surface and laser desorption/photoionization was used to detect biotinylated adsorbates from the ～10 μm sized pattern.     

Application of laser-induced incandescence to the detection of carbon nanotubes and carbon nanofibers

Laser-induced incandescence applied to a heterogeneous, multielement reacting flow is characterized by temporally resolved emission spectra, time-resolved emission at selected detection wavelengths, and fluence dependence. Two-pulse laser measurements are used to further probe the effects of laser-induced changes on the optical signal. Laser fluences above 0.6 J/cm2 at 1064 nm initiate laser-induced vaporization, yielding a lower incandescence intensity, as found through fluence-dependence measurements. Spectrally derived temperatures show that values of excitation laser fluence greater than this value lead to superheated plasmas with temperatures well above the vaporization point of carbon. The temporal evolution of the emission signal at these fluences is consistent with plasma dissipation processes, not incandescence from solidlike structures. Two-pulse laser experiments reveal that other material changes are produced at fluences below the apparent vaporization threshold, leading to nanostructures with different optical and thermal properties.     

Assessment of the upper particle size limit for quantitative analysis of aerosols using laser-induced breakdown spectroscopy

The laser-induced plasma vaporization of individual silica microspheres in an aerosolized air stream was investigated. The upper size limit for complete particle vaporization corresponds to a silica particle diameter of 2.1 microm for a laser pulse energy of 320 mJ, as determined by the deviation from a linear mass response of the silicon atomic emission signal. Comparison of the measured silica particle sampling rates and those predicted based on Poisson sampling statistics and the overall laser-induced plasma volume suggests that the primary mechanism of particle vaporization is related to direct plasma-particle interactions as opposed to a laser beam-particle interaction. Finally, temporal and spatial plasma evolution is discussed in concert with factors that may influence the vaporization dynamics of individual aerosol particles, such as thermophoretic forces and vapor expulsion.     

On-line analysis of organic components in fine and ultrafine particles by photoionization aerosol mass spectrometry

A new method, photoionization aerosol mass spectrometry (PIAMS), is described for real-time analysis of organic components in airborne particles below approximately 300 nm in diameter. Particles are focused through an aerodynamic lens assembly into the mass spectrometer where they are collected on a probe in the source region. After a sufficient amount of sample has been collected, the probe is irradiated with a pulsed infrared laser beam to vaporize organic components, which are then softly ionized with coherent vacuum ultraviolet radiation at 118 nm (10.5 eV). Since the photon energy is close to the ionization energies of most organic compounds, fragmentation is minimized. Both aliphatic and aromatic compounds of atmospheric relevance are detected and quantified in the low- to midpicogram range. The photoionization signal intensity increases linearly with the amount of material sampled and is independent of particle size. The fragmentation induced by laser desorption is greater than that observed with thermal vaporization, suggesting that the internal energy imparted by the former is greater. Although some molecular fragmentation is observed, mass spectra from common sources of ambient organic aerosol are distinguishable and consistent with previous off-line measurements by gas chromatography/mass spectrometry. These results illustrate the potential of PIAMS for molecular characterization of organic aerosols in ambient and smog chamber measurements.     

Fragment-Free Mass Spectrometric Analysis with Jet Cooling/VUV Photoionization

We show that it is possible to obtain fragment-free mass spectra of large molecules by a combination of laser desorption, jet cooling, and VUV single-photon photoionization. The ability to obtain parent molecular masses is particularly important for the analysis of mixtures, such as combinations of fully saturated hydrocarbons. By varying the cooling conditions, we can also achieve partial fragmentation in order to obtain further structural information. The use of different wavelengths provides additional selectivity between aromatic and aliphatic compounds.     

Time-resolved laser-induced incandescence and laser elastic-scattering measurements in a propane diffusion flame

Laser-induced incandescence (LII) and laser elastic-scattering measurements have been obtained with subnanosecond time resolution from a propane diffusion flame. Results show that the peak and time-integrated values of the LII signal increase with increasing laser fluence to maxima at the time of the onset of significant vaporization, beyond which they both decrease rapidly with further increases in fluence. This latter behavior for the time-integrated value is known to be characteristic for a laser beam with a rectangular spatial profile and is attributed to soot mass loss from vaporization. However, there is no apparent explanation for the corresponding large decrease in the peak value. Analysis shows that the peak value occurs at the time in the laser pulse when the time-integrated fluence reaches approximately 0.2 J/cm(2) and that the magnitude of the peak value is strongly dependent on the rate of energy deposition. One possible explanation for this behavior is that, at high laser fluences, a cascade ionization phenomenon leads to the formation of an absorptive plasma that strongly perturbs the LII process.     

Vacuum ultraviolet postionization of aromatic groups covalently bound to peptides

Experiments demonstrate that peptides with ionization potentials (IPs) above 7.87 eV can be single-photon-ionized in the gas phase with a molecular fluorine laser following prior chemical derivatization with one of several aromatic tags acting as chromophores. 4-(Dimethylamino)benzoic acid, 1-naphthylacetic acid, and 9-anthracenecarboxylic acid (denoted Benz, Naph and Anth, respectively) behave as chromophores, allowing single-photon ionization for vacuum ultraviolet (VUV) laser light by lowering the IP of the tagged peptide. Anth-tagged peptides that are laser-desorbed from a substrate and subsequently postionized produce mass spectra dominated by the intact radical cation, although protonated ions and fragmented species are also observed. Electronic structure calculations on Anth-tagged peptides indicate that in addition to lowering the ionization potential, the presence of the aromatic tag increases charge localization on and delocalization across the ring structure, which presumably stabilizes the radical cation. Measurements on several tagged peptides confirm this calculation and show that the stabilizing effect of the tag increases with the size of the conjugated system in the order Benz < Naph < Anth. The tagged hexapeptide Anth-GAPKSC exhibits the parent ion, whereas the Benz- and Naph-tagged peptides do not. These results are supported by the experimental comparison of Anth-tagged vs untagged tryptophan, further suggesting that VUV postionization of tagged high-IP species is a promising method for expanding the capabilities of mass spectrometric analyses of molecular species.     

Thermodynamics of Refractory Nuclear Materials Studied by Mass Spectrometry of Laser-Produced Vapors

A new method of high-temperature mass spectrometry (MS) with laser-induced vaporization (LIV) has been developed. The initial problem of LIV MS, consisting of an inadequate correlation between the temperature of the surface and the MS signal, was successfully overcome.The method was developed on graphite, of which fast time-resolved MS measurements (ca. 20 ms) were performed over a large mass interval; the influence of geometrical parameters and of the laser pulse length on MS measurements was studied. Carbon sublimation relative partial pressures of C₁, C₂, C₃, and C₅ were measured up to 3810 K. This corresponds to a total pressure of about 0.8 bar estimated independently by the integral mass flux using the Hertz–Knudsen equation. The vaporization of UO₂ was studied at temperatures above ≈ 2500 K, where conventional Knudsen-cell mass spectrometry cannot be applied. The vaporization enthalpy obtained for the main species in UO₂ vapor was in good agreement with that of conventional mass spectrometry. Paper presented at the Seventh International Workshop on Subsecond Thermophysics, October 6–8, 2004, Orléans, France.     

Brominated tyrosine and polyelectrolyte multilayer analysis by laser desorption vacuum ultraviolet postionization and secondary ion mass spectrometry

The small molecular analyte 3,5-dibromotyrosine (Br(2)Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br(2)Y were analyzed by laser desorption postionization-mass spectrometry (LDPI-MS). LDPI-MS using a 7.87 eV laser and tunable 8-12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br(2)Y films allowed detection by ≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br(2)Y to be ~8.3 ± 0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at ≤8 eV photon energies. However, single photon ionization could only detect Br(2)Y adsorbed within PEMs when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi(3)(+) secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. However, the negative ion SIMS appeared strongly dependent on the high electron affinity of this specific analyte and the analyte's condensed phase environment.     

Resonant laser ablation of metals detected by atomic emission in a microwave plasma and by inductively coupled plasma mass spectrometry

It has been shown that an increase in sensitivity and selectivity of detection of an analyte can be achieved by tuning the ablation laser wavelength to match that of a resonant gas-phase transition of that analyte. This has been termed resonant laser ablation (RLA). For a pulsed tunable nanosecond laser, the data presented here illustrate the resonant enhancement effect in pure copper and aluminum samples, chromium oxide thin films, and for trace molybdenum in stainless steel samples, and indicate two main characteristics of the RLA phenomenon. The first is that there is an increase in the number of atoms ablated from the surface. The second is that the bandwidth of the wavelength dependence of the ablation is on the order of 1 nm. The effect was found to be virtually identical whether the atoms were detected by use of a microwave-induced plasma with atomic emission detection, by an inductively coupled plasma with mass spectrometric detection, or by observation of the number of laser pulses required to penetrate through thin films. The data indicate that a distinct ablation laser wavelength dependence exists, probably initiated via resonant radiation trapping, and accompanied by collisional broadening. Desorption contributions through radiation trapping are substantiated by changes in crater morphology as a function of wavelength and by the relatively broad linewidth of the ablation laser wavelength scans, compared to gas-phase excitation spectra. Also, other experiments with thin films demonstrate the existence of a distinct laser-material interaction and suggest that a combination of desorption induced by electronic transition (DIET) with resonant radiation trapping could assist in the enhancement of desorption yields. These results were obtained by a detailed inspection of the effect of the wavelength of the ablation laser over a narrow range of energy densities that lie between the threshold of laser-induced desorption of species and the usual analytical ablation regime. Normal ablation employs high-power lasers in an attempt to create a vapor plume without selective vaporization, and with a stoichiometry that accurately represents the stoichiometry of species in the solid sample. RLA, as a method of selective vaporization, appears to provide an opportunity to exploit selective vaporization in new ways.     

Performance characteristics of soot primary particle size measurements by time-resolved laser-induced incandescence

A detailed analysis of various factors that influence the accuracy of time-resolved laser-induced incandescence for the determination of primary soot particles is given. As the technique relies on the measurement of the signal ratio at two detection times of the enhanced thermal radiation after an intense laser pulse, guidelines are presented for a suitable choice of detection times to minimize statistical uncertainty. An error analysis is presented for the issues of laser energy absorption, vaporization, heat conduction, and signal detection. Results are shown for a laminar ethene diffusion flame that demonstrate that concurring results are obtained for various laser irradiances, detection characteristics, and times of observation.     

A mobile mass spectrometer for comprehensive on-line analysis of trace and bulk components of complex gas mixtures: parallel application of the laser-based ionization methods VUV single-photon ionization, resonant multiphoton ionization, and laser-induced electron impact ionization

A newly developed compact and mobile time-of-flight mass spectrometer (TOFMS) for on-line analysis and monitoring of complex gas mixtures is presented. The instrument is designed for a (quasi-)simultaneous application of three ionization techniques that exhibit different ionization selectivities. The highly selective resonance-enhanced multiphoton ionization (REMPI) technique, using 266-nm UV laser pulses, is applied for selective and fragmentationless ionization of aromatic compounds at trace levels (parts-per-billion volume range). Mass spectra obtained using this technique show the chemical signature solely of monocyclic (benzene, phenols, etc.) and polycyclic (naphthalene, phenathrene, indol, etc.) aromatic species. Furthermore, the less selective but still fragmentationless single photon ionization (SPI) technique with 118-nm VUV laser pulses allows the ionization of compounds with an ionization potential below 10.5 eV. Mass spectra obtained using this technique show the profile of most organic compounds (aliphatic and aromatic species, like nonane, acetaldehyde, or pyrrol) and some inorganic compounds (e.g., ammonia, nitrogen monoxide). Finally, the nonselective ionization technique laser-induced electron-impact ionization (LEI) is applied. However, the sensitivity of the LEI technique is adjusted to be fairly low. Thus, the LEI signal in the mass spectra gives information on the inorganic bulk constituents of the sample (i.e., compounds such as water, oxygen, nitrogen, and carbon dioxide). Because the three ionization methods (REMPI, SPI, LEI) exhibit largely different ionization selectivities, the isolated application of each method alone solely provides specific mass spectrometric information about the sample composition. Special techniques have been developed and applied which allow the quasi-parallel use of all three ionization techniques for on-line monitoring purposes. Thus, a comprehensive characterization of complex samples is feasible jointly using the characteristic advantages of the three ionization techniques. Laboratory applications show results on rapid overview characterization of mineral oil-based fuels and coffee headspace. The first reported field applications include timely resolved on-line monitoring results on automobile exhausts and of waste incineration flue gas.     

Porous silicon as a versatile platform for laser desorption/ionization mass spectrometry

Desorption/ionization on porous silicon mass spectrometry (DIOS-MS) is a novel method for generating and analyzing gas-phase ions that employs direct laser vaporization. The structure and physicochemical properties of the porous silicon surfaces are crucial to DIOS-MS performance and are controlled by the selection of silicon and the electrochemical etching conditions. Porous silicon generation and DIOS signals were examined as a function of silicon crystal orientation, resistivity, etching solution, etching current density, etching time, and irradiation. Pre-and postetching conditions were also examined for their effect on DIOS signal as were chemical modifications to examine stability with respect to surface oxidation. Pore size and other physical characteristics were examined by scanning electron microscopy and Fourier transform infrared spectroscopy, and correlated with DIOS-MS signal. Porous silicon surfaces optimized for DIOS response were examined for their applicability to quantitative analysis, organic reaction monitoring, post-source decay mass spectrometry, and chromatography.     

Assessment of soot particle vaporization effects during laser-induced incandescence with time-resolved light scattering

Although laser-induced incandescence (LII) has been successfully used for soot volume fraction and particle size measurements, uncertainties remain regarding issues of soot vaporization leading to mass loss and morphological changes occurring in soot due to intense heating. Prompt LII detection schemes are often based on the assumption that the associated time scale is shorter than the time scale of soot vaporization or sublimation. The validity of such assumptions is the focus of the current study. Time-resolved light-scattering measurements were made in combination with LII measurements to quantify soot particle vaporization effects resulting from the LII laser pulse. The light-scattering measurements revealed a sharp decrease in total soot particle mass during the time course of the 25 ns full-width LII laser pulse for fluences in the range of 0.5 J/cm2. Light-scattering theory was used to invert the scattering data, revealing approximately 80%-90% reductions in the soot particle volume for LII fluences of 0.47 and 0.61 J/cm2. In addition, the time-resolved scattering measurements show that the time scale of soot vaporization is completely confined to the LII laser pulse itself. Light scattering revealed no soot vaporization only for fluences of approximately 0.1 J/cm2, which is consistent with recent work on low-fluence LII. Possible mechanisms for soot vaporization are discussed, notably for near-threshold fluences.     

Characterization of phosphor materials for use in plasma display panel by time-resolved vacuum-ultraviolet laser spectrometry

Phosphor materials that were manufactured for use in a plasma display panel (PDP) were investigated by employing a newly designed time-resolved vacuum-ultraviolet (VUV) spectrometer, which consists of a pulsed VUV laser and a fast photodetector. The VUV spectrometer was used to collect quantum efficiency data as well as the rise and decay times for the PDP phosphor luminescence. Both the rise and decay times increased with decreasing excitation wavelength in the VUV region. This result can be explained by a change in the mechanisms of photoexcitation and luminescence, that is, from charge-transfer excitation to host-lattice excitation below 200 nm. The present instrument was also used for an evaluation of the phosphor materials (Ba(1 - x)MgAl10O17:Eu2+(x)) by changing the Eu2+ concentration. The obtained data suggest that the impurities and defects are located inside the host crystal. Thus, the VUV spectrometer constructed in this study has considerable potential for use in investigating the nature of PDP phosphor materials.     

Generation of highly charged peptide and protein ions by atmospheric pressure matrix-assisted infrared laser desorption/ionization ion trap mass spectrometry

We show that highly charged ions can be generated if a pulsed infrared laser and a glycerol matrix are employed for atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry with a quadrupole ion trap. Already for small peptides like bradykinin, doubly protonated ions form the most abundant analyte signal in the mass spectra. The center of the charge-state distribution increases with the size of the analyte. For example, insulin is detected with a most abundant ion signal corresponding to a charge state of four, whereas for cytochrome c, the 10 times protonated ion species produces the most intense signal. Myoglobin is observed with up to 13 charges. The high m/z ratios allow us to use the Paul trap for the detection of MALDI-generated protein ions that are, owing to their high molecular weight, not amenable in their singly protonated charge state. Formation of multiple charges critically depends on the addition of diluted acid to the analyte-matrix solution. Tandem mass spectra generated by collision-induced dissociation of doubly charged peptides are also presented. The findings allow speculations about the involvement of electrospray ionization processes in these MALDI experiments.     

VUV spectroscopy of a new fluoride system NaF–(Er, Y)F3

Emission and excitation spectra as well as luminescence decay kinetics of a new complex fluoride system Na_0.4(Y_1−xEr_x)_0.6F_2.2 (x=0.01, 0.1, 1) have been studied in the vacuum ultraviolet (VUV) spectral range. It has been shown that these crystals have intense VUV luminescence due to the interconfiguration 5d–4f transitions in Er³⁺ ion. The spin-allowed 5d–4f luminescence of Er³⁺ in this system is very weak, i.e., in these crystals there exists an efficient non-radiative relaxation from higher-lying 5d states of Er³⁺ to the lowest 5d level responsible for spin-forbidden luminescence. This makes the studied new fluoride system a promising active medium for the production of VUV solid state laser with optical pumping. Due to rather large bandwidth of Er³⁺ 5d–4f luminescence in this system there is a possibility for the construction of tuneable VUV laser.     

VUV and UV Florescence and Absorption Studies of Tb3+ and Tm3+ Trivalent Ions in LiYF4 Single Crystal Hosts

Abstract

The laser induced fluorescence spectra of LiYF₄:Tb³⁺ (YLF:Tb) and LiYF₄:Tm³⁺ (YLF:Tm) single crystals, pumped by an F₂ pulsed discharge molecular laser at 157 nm, were obtained in the vacuum ultraviolet (VUV) and ultraviolet (UV) regions of the spectrum, at room temperature. A number of new fluorescence peaks were observed for the first time. They were assigned to the dipole allowed transitions 4f⁷5d → 4f⁸ and 4f¹¹5d → 4f¹² of Tb³⁺ and Tm³⁺ ions respectively. The absorption spectra of the same crystal samples in the VUV and UV regions were taken as well. The edge (onset) and the energy of the states with 4f^{N ? 1}5d configuration were determined.