Abstract: Organic carbocyanine dye coatings have been analyzed by time-of-flight static secondary ion mass spectrometry (TOF-S-SIMS) using three types of primary ions: Ga+ operating at 25 keV, and Xe+ and SF5+ both operating at 9 keV. Secondary ion yields obtained with these three primary ions have been compared for coatings with different layer thickness, varying from (sub)-monolayer to multilayers, on different substrates (Si, Ag and AgBr cubic microcrystals). For (sub)-monolayers deposited on Ag, Xe+ and SF5+ primary ions generate similar precursor ion intensities, but with Ga+ slightly lower precursor ion intensities were obtained. Thick coatings on Ag as well as mono- and multilayers on Si produce the highest precursor and fragment ion intensities with the polyatomic primary ion. The yield difference between SF5+ and Xe+ can reach a factor of 6. In comparison with Ga+, yield enhancements by up to a factor of 180 are observed with SF5+. For the mass spectrometric analysis of dye layers on AgBr microcrystals, SF5+ again proves to be the primary ion of choice. Copyright (C) 2004 John Wiley Sons, Ltd.

Abstract: Time-of-flight static secondary ion mass spectrometry (TOF-S-SIMS) was used to characterize thin layers of oxy- and thiocarbocyanine dyes on Ag and Si. Apart from adduct ions a variety of structural fragment ions were detected for which a fragmentation pattern is proposed. Peak assignments were confirmed by comparing spectra of dyes with very similar structures. All secondary ions were assigned with a mass accuracy better than 50 ppm. The intensity of molecular ions as well as fragment ions has been studied as a function of the type of organic dye, the substrate, the layer thickness and the type of primary ion. A large yield difference of two orders of magnitude was observed between the precursor ions of cationic carbocyanine dyes and the protonated molecules of the anionic dyes. Fragment ions, on the other hand, yielded similar intensities for both types of dye. As the dye layers deposited on an Ag substrate yielded higher secondary ion intensities than those deposited on a Si substrate, the Ag metal clearly acts as a promoting agent for secondary ion formation. The effect was more pronounced for precursor signals than for fragment ions. The promoting effect decreased as the deposited layer thickness of the organic dye layer was increased. Copyright (C) 2003 John Wiley Sons, Ltd.

Abstract: The daily and seasonal atmospheric concentrations, deposition fluxes and emission sources of a few C3C9 gaseous alkyl nitrates (ANs) at the Belgian coast (De Haan) on the Southern North Sea were determined. An adapted sampler design for low- and high-volume air-sampling, optimized sample extraction and clean-up, as well as identification and quantification of ANs in air samples by means of gas chromatography mass spectrometry, are reported. The total concentrations of ANs ranged from 0.03 to 85 pptv and consisted primarily of the nitro-butane and nitro-pentane isomers. Air mass backward trajectories were calculated by the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to determine the influence of main air masses on AN levels in the air. The shorter chain ANs have been the most abundant in the Atlantic/Channel/UK air masses, while longer chain ANs prevailed in continental air. The overall mean N fluxes of the ANs were slightly higher for summer than those for winter-spring, although their contributions to the total nitrogen flux were low. High correlations between AN and HNO2 levels were observed during winter/spring. During summer, the shorter chain ANs correlated well with precipitation. Source apportionment by means of principal component analysis indicated that most of the gas phase ANs could be attributed to traffic/combustion, secondary photochemical formation and biomass burning, although marine sources may also have been present and a contributing factor.