Thorsten Benter

The tropospheric degradation of isoprene : an updated module for the regional atmospheric chemistry mechanism

Abstract A highly condensed reaction scheme for the tropospheric oxidation of isoprene is presented. This mechanism was implemented into the regional atmospheric chemistry mechanism (RACM), which is an established chemical module for regional air quality modelling but contains an isoprene chemistry which is no longer state-of-the-art. The reaction scheme developed here is based on the recently published Mainz isoprene mechanism (MIM) that has been constructed for application in global chemistry transport models. The MIM code was reduced to a size suitable for use in regional atmospheric chemistry models. Redundant reactions were identified and removed from the reaction scheme by means of sensitivity analyses. The revised mechanism was successfully tested against the results of smog chamber experiments carried out in the European photoreactor EUPHORE. A model intercomparison between both the original and the updated RACM mechanism was performed for a number of well-defined scenarios employing conditions ranging from very clean to highly polluted air masses. The calculations revealed large deviations in the concentration–time profiles for key species of the isoprene degradation, particularly under “low-NOx” conditions. The new isoprene chemistry requires only a few additional reactants (7) and chemical reactions (7) and, therefore, offers the possibility for the successful application of the revised reaction scheme in chemistry-transport models (CTM) without an excessive increase in computational efforts.

Development of a multipurpose ion source for LC-MS and GC-API MS.

Over the past decade, multimode ion sources operating at atmospheric pressure (i.e., more than one ionization method is operative in the ion source enclosure) have received considerable interest. Simultaneous operation of different ionization methods targeting different compound classes within one analysis run has several advantages, including enhanced sample throughput and thus significant laboratory cost reductions. Potential drawbacks are enhanced ion suppression and other undesirable effects of the simultaneous operation of ionization methods. In this contribution we present an alternative approach—the development and characterization of a widely applicable, multipurpose ion source operating at atmospheric pressure. The optimized source geometry allows rapid changing from LC-API methods (ESI, APCI, APLI) to GC-API methods (APCI, APLI, DA-APLI) along with the appropriate coupling of chromatographic equipment required. In addition, true multimode operation of the source is demonstrated for LC-ESI/APLI and LC-APCI/APLI.

Atmospheric pressure laser ionization (APLI) coupled with Fourier transform ion cyclotron resonance mass spectrometry applied to petroleum samples analysis: comparison with electrospray ionization and atmospheric pressure photoionization methods

The analysis of crude oil samples remains a tough challenge due to the complexity of the matrix and the broad range of physical and chemical properties of the various individual compounds present. In this work, atmospheric pressure laser ionization (APLI) is utilized as a complementary tool to other ionization techniques for crude oil analysis. Mass spectra obtained with electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) are compared. APLI is primarily sensitive towards non-polar aromatic hydrocarbons, which are generally present in high amounts especially in heavy crude oil samples. The ionization mechanisms of APLI vs. APPI are further investigated. The results indicate the advantages of APLI over established methods like ESI and APPI. The application of APLI in combination with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is thus demonstrated to be a powerful tool for the analysis of aromatic species in complex crude oil fractions.

Combining chip-ESI with APLI (cESILI) as a multimode source for analysis of complex mixtures with ultrahigh-resolution mass spectrometry

Recently we have established atmospheric-pressure laser ionisation (APLI) as a method for coupling time-of-flight mass spectrometric detectors (TOF MS) with chromatographic systems (HPLC and GC) to allow two-photon ionisation of non-polar aromatic compounds. Here we demonstrate that APLI can be combined with chip-electrospray ionisation (cESI) coupled to Fourier-transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) for ultrahigh-resolution analysis of complex samples. With the laser turned off, the analytes are ionised only by ESI, whereas when the laser is switched on non-polar aromatic substances also are ionised. In combination with the extremely high mass resolution of an FT-ICR MS, simultaneous qualitative analysis of polar and non-polar analytes is possible in both positive and negative modes, as is exemplified with a crude oil sample. Nevertheless, ion suppression was observed (up to ca. 70% for D10-pyrene) and thus sample preparation with chromatographic or electrophoretic pre-separation is necessary for quantitative analysis of targets. In addition, for the first time, the dopant-assisted APLI method in combination with cESI (DA-cESILI) was used for determination of 1-nitrocoronene.

Generation of ion-bound solvent clusters as reactant ions in dopant-assisted APPI and APLI

We provide experimental and theoretical evidence that the primary ionization process in the dopant-assisted varieties of the atmospheric pressure ionization methods atmospheric pressure photoionization and atmospheric pressure laser ionization in typical liquid chromatography–mass spectrometry settings is—as suggested in the literature—dopant radical cation formation. However, instead of direct dopant radical cation–analyte interaction—the broadly accepted subsequent step in the reaction cascade leading to protonated analyte molecules—rapid thermal equilibration with ion source background water or liquid chromatography solvents through dopant ion–molecule cluster formation occurs. Fast intracluster chemistry then leads to almost instantaneous proton-bound water/solvent cluster generation. These clusters interact either directly with analytes by ligand switching or association reactions, respectively, or further downstream in the intermediate-pressure regions in the ion transfer stages of the mass spectrometer via electrical-field-driven collisional decomposition reactions finally leading to the predominantly observed bare protonated analyte molecules [M + H]+.

The distribution of ion acceptance in atmospheric pressure ion sources: Spatially resolved APLI measurements

It is demonstrated that spatially resolved mass selected analysis using atmospheric pressure laser ionization mass spectrometry (APLI MS) represents a new powerful tool for mechanistic studies of ion-molecule chemistry occurring within atmospheric pressure (AP) ion sources as well as for evaluation and optimization of ion source performance. A focused low-energy UV laser beam is positioned computer controlled orthogonally on a two-dimensional grid in the ion source enclosure. Resonance enhanced multiphoton ionization (REMPI) of selected analytes occurs only within the confined volume of the laser beam. Depending on the experimental conditions and the reactivity of the primary photo-generated ions, specific signal patterns become visible after data treatment, as visualized in, e.g., contour or pseudo-color plots. The resulting spatial dependence of sensitivity is defined in this context as the distribution of ion acceptance (DIA) of the source/analyzer combination. This approach provides a much more detailed analysis of the diverse processes occurring in AP ion sources compared with conventional bulk signal response measurements.

Investigations on the gas-phase photolysis and OH radical kinetics of methyl-2-nitrophenols

Methyl-2-nitrophenols can be emitted directly to the atmosphere or can be formed in situ via the oxidation of aromatic hydrocarbons. Nitrophenols possess phytotoxic properties and recent studies indicate their photooxidation is effective in producing secondary organic aerosols. Therefore, investigations on the major photooxidation pathways of these compounds with respect to assessing their environmental impacts and effects on human health are highly relevant. Presented here are determinations of the rate coefficients for the reactions of OH radicals with four methyl-2-nitrophenol isomers using a relative kinetic technique. The experiments were performed in a 1080 l photoreactor at (760 +/- 10) Torr total pressure of synthetic air at (296 +/- 3) K. The following rate coefficients (in units of cm(3) molecule(-1) s(-1)) have been obtained: 3-methyl-2-nitrophenol, (3.69 +/- 0.70) x 10(-12); 4-methyl-2-nitrophenol, (3.59 +/- 1.17) x 10(-12); 5-methyl-2-nitrophenol, (6.72 +/- 2.14) x 10(-12); 6-methyl-2-nitrophenol, (2.70 +/- 0.57) x 10(-12). Photolysis of the methyl-2-nitrophenols with the superactinic fluorescent lamps (320 < lambda < 480 nm, lambda(max) = 360 nm) used in the experiments was observed. Photolysis frequencies measured for the methyl-2-nitrophenols in the photoreactor have been determined and scaled to atmospheric conditions. The results suggest that photolysis rather than the reaction with OH radicals will be the dominant gas phase atmospheric loss process for methyl-2-nitrophenols.

Recent developments in atmospheric pressure photoionization‐mass spectrometry

Recent developments in atmospheric pressure photoionization (APPI), which is one of the three most important ionization techniques in liquid chromatography-mass spectrometry, are reviewed. The emphasis is on the practical aspects of APPI analysis, its combination with different separation techniques, novel instrumental developments - especially in gas chromatography and ambient mass spectrometry - and the applications that have appeared in 2009-2014.

Rate coefficients for the gas-phase reaction of OH radicals with dimethyl sulfide: temperature and O2 partial pressure dependence.

Rate coefficients for the gas-phase reaction of hydroxyl (OH) radicals with dimethyl sulfide (CH(3)SCH(3), DMS) have been determined using a relative rate technique. The experiments were performed under different conditions of temperature (250-299 K) and O(2) partial pressure (approximately 0 Torr O(2)-380 Torr O(2)), at a total pressure of 760 Torr bath gas (N(2) + O(2)), in a 336 l reaction chamber, using long path in situ Fourier transform (FTIR) absorption spectroscopy to monitor the disappearance rates of DMS and the reference compounds (ethene, propene and 2-methylpropene). OH was produced by the photolysis of H(2)O(2). The following Arrhenius expressions adequately describe the rate coefficients as a function of temperature (units are cm(3) molecule(-1) s(-1)): k = (1.56 +/- 0.20) x 10(-12) exp[(369 +/- 27)/T], for approximately 0 Torr O(2); (1.31 +/- 0.08) x 10(-14) exp[(1910 +/- 69)/T], for 155 Torr O(2); (5.18 +/- 0.71) x 10(-14) exp[(1587 +/- 24)/T], for 380 Torr O(2). The results are compared with previous investigations.

Evidence of neutral radical induced analyte ion transformations in APPI and Near-VUV APLI

We report on the reactions of neutral radical species [OH, Cl, O(3P), H], generated in a typical atmospheric pressure ionization (API) source upon irradiation of the sample gases with either 193 nm laser radiation or 124 nm VUV light, the latter commonly used in atmospheric pressure photoionization (APPI). The present investigations focus on the polycyclic aromatic hydrocarbon pyrene as representative of the aromatic compound class. Experimental results are supported by computational methods: simple kinetic models are used to estimate the temporal evolution of the concentrations of reactants, intermediates, and final products, whereas density functional theory (DFT) energy calculations are carried out to further elucidate the proposed reaction pathways. The neutral radicals are generated upon photolysis of background water and oxygen always present in appreciable mixing ratios in typical API sources. Substantial amounts of oxygenated analyte product ions are observed using both techniques. In contrast, upon atmospheric pressure laser ionization (APLI) with 248 nm radiation, oxygenated products are virtually absent. In addition, kinetic data evaluation yielded a bimolecular rate constant of k=(1.9±0.9)×10−9 cm3 molecule−1 s−1 for the reaction of the pyrene radical cation with OH radicals.