Pressure Interface Research Articles

Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products: from methylcyclohexenes toward understanding α-pinene.

Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4-methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO3(-)) based ionization scheme. The experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO2) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. These conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D2O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with our previous work on cyclohexene, whereas in α-pinene ozonolysis different mechanistic steps are needed to explain the products observed.

Transversal modulation ion mobility spectrometry (IMS) coupled with mass spectrometry (MS): exploring the IMS-IMS-MS possibilities of the instrument.

A prototype is introduced based on the transversal modulation ion mobility spectrometry (TMIMS) technique, which provides a continuous output of mobility-selected ions, greatly easing the synchronization between different analyzing stages. In the new architecture, two stages of filtration are used to drastically reduce the background produced by one stage alone. Two-stages TMIMS was coupled with two different atmospheric pressure interface mass spectrometers (MS). The new system enables IMS-IMS-MS analysis and other modes of operation: IMS prefiltration, IMS-IMS, and full transmission mode. It provides a resolving power R > 60 in IMS mode, and R > 40 in each stage of IMS-IMS mode. 2-Propanol vapors were introduced in one of the stages to enhance the mobility variations, and their effect was studied on a set of tetraalkylammonium ions. We found that concentrations as low as 1% (in partial pressure) produce mobility variations as high as 20%, which suggest that IMS-IMS separation using dried N2 (in one stage) and a dopant (in the other stage), could be a very powerful way to enhance the separation capacity of the IMS-IMS prefiltration approach.

On the composition of ammonia–sulfuric-acid ion clusters during aerosol particle formation

Abstract. The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3–H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from < 2 to 1400 pptv, [H2SO4] from 3.3 × 106 to 1.4 × 109 cm−3 (0.1 to 56 pptv), and a temperature range from −25 to +20 °C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer, as they initially formed from gas-phase NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH3–H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O–H2SO4 clusters (observed as clusters of only H2SO4) only form at [NH3] / [H2SO4] < 0.1 to 1. For larger values of [NH3] / [H2SO4], the composition of NH3–H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Δm/Δ n), where n is in the range 4–18 (negatively charged clusters) or 1–17 (positively charged clusters). For negatively charged clusters, Δ m/Δn saturated between 1 and 1.4 for [NH3] / [H2SO4] > 10. Positively charged clusters grew on average by Δm/Δn = 1.05 and were only observed at sufficiently high [NH3] / [H2SO4]. The H2SO4 molecules of these clusters are partially neutralized by NH3, in close resemblance to the acid–base bindings of ammonium bisulfate. Supported by model simulations, we substantiate previous evidence for acid–base reactions being the essential mechanism behind the formation of these clusters under atmospheric conditions and up to sizes of at least 2 nm. Our results also suggest that electrically neutral NH3–H2SO4 clusters, unobservable in this study, have generally the same composition as ionic clusters for [NH3] / [H2SO4] > 10. We expect that NH3–H2SO4 clusters form and grow also mostly by Δm/Δn > 1 in the atmosphere's boundary layer, as [NH3] / [H2SO4] is mostly larger than 10. We compared our results from CLOUD with APi-TOF measurements of NH3–H2SO4 anion clusters during new-particle formation in the Finnish boreal forest. However, the exact role of NH3–H2SO4 clusters in boundary layer particle formation remains to be resolved.

Development of a miniature mass spectrometer with continuous atmospheric pressure interface.

The demand for on-the-spot analysis is met by a miniature mass spectrometer which is preferred to be robust, stable, as small as possible and capable of analyzing different samples by coupling with various ionization methods. However, largely constrained by the atmospheric pressure interface (API), these aspects are difficult to be realized in one system. Herein, we describe the development of a new miniature mass spectrometer with balanced performance. The miniature mass spectrometer is small in size (30 × 30 × 18 cm) but has a continuous API, which was achieved by high-pressure ion trap operation and maximized ion transfer efficiency with the utilization of a differential pumping system. The miniature mass spectrometer was characterized and optimized in terms of stability, sensitivity, mass range, mass resolution and scan speed. Rapid analysis of mixtures was demonstrated by coupling the miniature mass spectrometer with the ambient ionization technique of paper spray. This is the smallest miniature mass spectrometer to date, which has a continuous API.

Exploring the peptide fragmentation mechanisms under atmospheric pressure photoionization using tunable VUV synchrotron radiation

Intensive fragmentations into b/y- and c-sequence ions have been reported for Substance P ionized under dopant-assisted atmospheric pressure photoionization (APPI) conditions. It was postulated that the fragmentation comes from the reaction of the doubly charged peptide with photoelectrons, released upon photoionization of the dopant, through an electron capture or transfer dissociation-type mechanism. In order to investigate further the origin of each fragment ion type, a tunable VUV synchrotron radiation source coupled to a modified APPI source has been used. Using this set-up, the photon energy can be scanned continuously below and above the photoionization threshold of the dopant, i.e. toluene, probing the ionization/fragmentation processes occurring on Substance P peptide at the atmospheric pressure interface of the mass spectrometer.

Design of portable mass spectrometers with handheld probes: aspects of the sampling and miniature pumping systems.

Miniature mass spectrometry analytical systems of backpack configuration fitted with sampling probes could potentially be of significant interest for in-field, real-time chemical analysis. In this study, various configurations were explored in which a long narrow tube was used to connect the turbo and backing pumps used to create and maintain vacuum. Also, for the first time we introduced two new types of pumps for miniature mass spectrometers, the Creare 130 g drag pump and Creare 350 g scroll backing pump. These pumps, along with another Creare 550 turbo pump and the commercially available Pfeiffer HiPace 10 turbo and KnF diaphragm backing pumps, were tested with the backpack configurations. The system performance, especially the scan time, was characterized when used with a discontinuous atmospheric pressure interface (DAPI) for ion introduction. The pumping performance in the pressure region above 1 mtorr is critical for DAPI operation. The 550 g turbo pump was shown to have a relatively higher pumping speed above 1 mtorr and gave a scan time of 300 ms, almost half the value obtained with the larger, heavier HiPace 10 often used with miniature mass spectrometers. The 350 g scroll pump was also found to be an improvement over the diaphragm pumps generally used as backing pumps. With a coaxial low temperature plasma ion source, direct analysis of low volatility compounds glass slides was demonstrated, including 1 ng DNP (2,4-Dinitrophenol) and 10 ng TNT (2,4,6-trinitrotoluene) with Creare 550 g turbo pump as well as 10 ng cocaine and 20 ng DNP with Creare 130 g drag pump.

The formation of highly oxidized multifunctional products in the ozonolysis of cyclohexene.

The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3(-))-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1 in monomers and O/C > 0.55 in dimers) from cyclohexene ozonolysis was determined as (4.5 ± 3.8)%. Fully deuterated cyclohexene and cis-6-nonenal ozonolysis, as well as the influence of water addition to the system (either H2O or D2O), were also investigated in order to strengthen the arguments on the proposed mechanism. Deuterated cyclohexene ozonolysis resulted in a less oxidized product distribution with a lower yield of highly oxygenated products and cis-6-nonenal ozonolysis generated the same monomer product distribution, consistent with the proposed mechanism and in agreement with quantum chemical modeling.

High-Resolution Mobility and Mass Spectrometry of Negative Ions Produced in a 241Am Aerosol Charger

This work concentrates on the simultaneous mobility and mass measurement of negative ions generated by the ionizing radiation in a 241Am aerosol charger in N2 (5.0), a 1:1-mixture of N2 and synthetic air, pure synthetic air (5.0), and filtered laboratory air at ∼30% relative humidity. Therefore, a high-resolution mobility analyzer (UDMA) and an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) were operated in series. Experiments with N2 as carrier gas showed a dominating signal at an electrical mobility of 2.09 cm2/Vs with 90% of the ions being nitrate based. The ion composition was altered after a baking-out to a spectrum with three strong mobility-peaks at Z1 = 2.34 cm2/Vs, Z2 = 1.42 cm2/Vs, Z3 = 1.08 cm2/Vs and a higher diversity of ions in the corresponding mass spectra. The carrier gas was gradually changed from N2 (5.0) to a 1:1-mixture of N2 with synthetic air and pure synthetic air (5.0), having only a minor effect on the overall pattern of the ion spectrum. Using room air...

Changes in concentration of nitrogen-containing compounds in 10 nm particles of boreal forest atmosphere at snowmelt

Measurements to clarify the chemical composition and especially the nitrogen compounds in 10nm ultrafine aerosol particles were carried out at the boreal forest site at the SMEAR II station, Hyytiälä, Finland, during spring–summer–autumn of 2010 and in spring 2011. In 2011, laser aerosol mass spectrometer (laser AMS) provided in-situ chemical composition data for 10nm particles. Laser AMS results, for samples collected in 2011, were clarified through comparison with findings for partly published 30nm and all-sized particles from filter samples analyzed by chromatographic techniques, re-analysis of the selected 30nm filter samples for quinoline identification by LC–MS and modified results from previously published atmospheric pressure interface time-of-flight mass spectrometer (APi-TOFMS) data. The chemistry of the atmosphere was found to change markedly in mid April 2011, just after snow melt: the concentrations of 35% of the laser AMS ions and compounds determined in 30nm particles from filter samples clearly increased or decreased at this time. Notably, the amount of nitrogen compounds increased and the amount of aldehydes decreased. The laser AMS results for 10nm aerosol samples demonstrated the tendency for nitrogen-containing compounds and oxygenated and non-oxygenated hydrocarbons to increase in concentration after snow melt. More detailed analysis confirmed that the two most interesting, frequently observed, and abundant laser AMS ions, m/z 143 and 185, originated from 1-(X-methylquinolin-X-yl) ethanone. According to laser AMS and APi-TOFMS data, when the quinoline concentrations in the 10nm particulate phase increased, the concentrations in the molecular clusters decreased, indicating changes in the partitioning between particle and gas phases.

Characterization of a DAPI-RIT-DAPI System for Gas-Phase Ion/Molecule and Ion/Ion Reactions

The discontinuous atmospheric pressure interface (DAPI) has been developed as a facile means for efficiently introducing ions generated at atmospheric pressure to an ion trap in vacuum [e.g., a rectilinear ion trap (RIT)] for mass analysis. Introduction of multiple beams of ions or neutral species through two DAPIs into a single RIT has been previously demonstrated. In this study, a home-built instrument with a DAPI-RIT-DAPI configuration has been characterized for the study of gas-phase ion/molecule and ion/ion reactions. The reaction species, including ions or neutrals, can be introduced from both ends of the RIT through the two DAPIs without complicated ion optics or differential pumping stages. The primary reactant ions were isolated prior to reaction and the product ions were mass analyzed after controlled reaction time period. Ion/molecule reactions involving peptide radical ions and proton-transfer ion/ion reactions have been carried out using this instrument. The gas dynamic effect due to the DAPI operation on internal energy deposition and the reactivity of peptide radical ions has been characterized. The DAPI-RIT-DAPI system also has a unique feature for allowing the ion reactions to be carried out at significantly elevated pressures (in 10(-1) Torr range), which has been found to be helpful to speed up the reactions. The viability and flexibility of the DAPI-RIT-DAPI system for the study of gas-phase ion reactions have been demonstrated.

Simulation of Rarefied Gas Flows in Atmospheric Pressure Interfaces for Mass Spectrometry Systems

The understanding of the gas dynamics of the atmospheric pressure interface is very important for the development of mass spectrometry systems with high sensitivity. While the gas flows at high pressure (>1Torr) and low pressure (<10(-3)Torr) stages are relatively well understood and could be modeled using continuum and molecular flows, respectively, the theoretical modeling or numeric simulation of gas flow through the transition pressure stage (1 to 10(-3)Torr) remains challenging. In this study, we used the direct simulation Monte Carlo (DMSC) method to develop the gas dynamic simulations for the continuous and discontinuous atmospheric pressure interfaces (API), with different focuses on the ion transfer by gas flows through a skimmer or directly from the atmospheric pressure to a vacuum stage, respectively. The impacts by the skimmer location in the continuous API and the temporal evolvement of the gas flow with a discontinuous API were characterized, which provide a solid base for the instrument design and performance improvement.

Evolution of particle composition in CLOUD nucleation experiments

Abstract. Sulphuric acid, ammonia, amines, and oxidised organics play a crucial role in nanoparticle formation in the atmosphere. In this study, we investigate the composition of nucleated nanoparticles formed from these compounds in the CLOUD (Cosmics Leaving Outdoor Droplets) chamber experiments at CERN (Centre européen pour la recherche nucléaire). The investigation was carried out via analysis of the particle hygroscopicity, ethanol affinity, oxidation state, and ion composition. Hygroscopicity was studied by a hygroscopic tandem differential mobility analyser and a cloud condensation nuclei counter, ethanol affinity by an organic differential mobility analyser and particle oxidation level by a high-resolution time-of-flight aerosol mass spectrometer. The ion composition was studied by an atmospheric pressure interface time-of-flight mass spectrometer. The volume fraction of the organics in the particles during their growth from sizes of a few nanometers to tens of nanometers was derived from measured hygroscopicity assuming the Zdanovskii–Stokes–Robinson relationship, and compared to values gained from the spectrometers. The ZSR-relationship was also applied to obtain the measured ethanol affinities during the particle growth, which were used to derive the volume fractions of sulphuric acid and the other inorganics (e.g. ammonium salts). In the presence of sulphuric acid and ammonia, particles with a mobility diameter of 150 nm were chemically neutralised to ammonium sulphate. In the presence of oxidation products of pinanediol, the organic volume fraction of freshly nucleated particles increased from 0.4 to ~0.9, with an increase in diameter from 2 to 63 nm. Conversely, the sulphuric acid volume fraction decreased from 0.6 to 0.1 when the particle diameter increased from 2 to 50 nm. The results provide information on the composition of nucleated aerosol particles during their growth in the presence of various combinations of sulphuric acid, ammonia, dimethylamine and organic oxidation products.

Ambient Aerodynamic Desorption/Ionization Method for Microparticle Mass Measurement

An ambient desorption/ionization method, named aerodynamic desorption (AD), was proposed for the in situ rapid mass measurement of microparticles. The AD method exploited the discontinuous atmospheric pressure interface (DAPI) to generate a pulsed airflow, which was used to desorb the microparticles under atmospheric pressure. Various microparticles, e.g., bacteria, cell, polystyrene, synthetic diamond, and silica particles, with different size and surface component were successfully desorbed. Similar to that in the conventional laser-induced acoustic desorption (LIAD) method, these microparticles were desorbed as precharged ions in the AD process and the charge number was largely relevant to the particle size. However, compared with LIAD, the sensitivity of the AD method was higher. A lower concentration of particles was required for the analysis. In addition, the construction and sampling process of AD source were much simpler. All types of liquid, solid, or/and gaseous samples can be directly sampled under ambient condition. As a demonstration of this AD method, the in situ mass analysis of red blood cells (RBCs) and E. coli bacteria were carried out using a homemade ambient AD mass spectrometer consisting of AD source, QIT mass analyzer, and charge detector. Their mass and mass distributions were obtained successfully.

Soft Ionization of Saturated Hydrocarbons, Alcohols and Nonpolar Compounds by Negative-Ion Direct Analysis in Real-Time Mass Spectrometry

Large polarizable n-alkanes (approximately C18 and larger), alcohols, and other nonpolar compounds can be detected as negative ions when sample solutions are injected directly into the sampling orifice of the atmospheric pressure interface of the time-of-flight mass spectrometer with the direct analysis in real time (DART) ion source operating in negative-ion mode. The mass spectra are dominated by peaks corresponding to [M + O2]‾(•). No fragmentation is observed, making this a very soft ionization technique for samples that are otherwise difficult to analyze by DART. Detection limits for cholesterol were determined to be in the low nanogram range.

Synchronized Discharge Ionization for Analysis of Volatile Organic Compounds Using a Hand-Held Ion Trap Mass Spectrometer

The sensitivity of mass analysis is highly dependent on the efficiencies of the sample introduction, analyte ionization, and subsequent ion transfer to the mass analyzer. For miniature mass spectrometry (MS) systems, it is highly desirable to maximize the amount of the samples that can be introduced at the pumping capability highly compromised and to have the MS analysis performed with simple electronics and robust in-vacuum components. In this study, a discharge ionization source synchronized with the sample introduction has been developed for hand-held mass spectrometers with discontinuous atmospheric pressure interfaces (DAPI). The flow rate of the sample introduced with a DAPI can be much higher than that allowed with a conventional continuous atmospheric pressure interface. The pressure variation associated with the DAPI operation was used to turn on and off the synchronized discharge ionization (SDI). For analysis of volatile organic compounds (VOCs) in air samples, the SDI has been shown to be soft and molecular ions of the VOCs have been observed as the major species. Since the ions could be transferred directly to the ion trap mass analyzer without a barrier for maintaining pressure differences, high sensitivity in chemical analysis was also achieved, with limits of detection (LODs) better than 1 ppbv obtained for PAHs (polycyclic aromatic hydrocarbons) in air.

Comparing simulated and experimental molecular cluster distributions

Formation of secondary atmospheric aerosol particles starts with gas phase molecules forming small molecular clusters. High-resolution mass spectrometry enables the detection and chemical characterization of electrically charged clusters from the molecular scale upward, whereas the experimental detection of electrically neutral clusters, especially as a chemical composition measurement, down to 1 nm in diameter and beyond still remains challenging. In this work we simulated a set of both electrically neutral and charged small molecular clusters, consisting of sulfuric acid and ammonia molecules, with a dynamic collision and evaporation model. Collision frequencies between the clusters were calculated according to classical kinetics, and evaporation rates were derived from first principles quantum chemical calculations with no fitting parameters. We found a good agreement between the modeled steady-state concentrations of negative cluster ions and experimental results measured with the state-of-the-art Atmospheric Pressure interface Time-Of-Flight mass spectrometer (APi-TOF) in the CLOUD chamber experiments at CERN. The model can be used to interpret experimental results and give information on neutral clusters that cannot be directly measured.

CO2 laser ionization of acoustically levitated droplets

For many analytical purposes, direct laser ionization of liquids is desirable. Several studies on supported droplets, free liquid jets, and ballistically dispensed microdroplets have been conducted, yet detailed knowledge of the underlying mechanistics in ion formation is still missing. This contribution introduces a simple combination of IR-MALDI mass spectrometry and an acoustical levitation device for contactless confinement of the liquid sample. The homebuilt ultrasonic levitator supports droplets of several millimeters in diameter. These droplets are vaporized by a carbon dioxide laser in the vicinity of the atmospheric pressure interface of a time of flight mass spectrometer. The evaporation process is studied by high repetition rate shadowgraphy experiments elucidating the ballistic evaporation of the sample and revealing strong confinement of the vapor by the ultrasonic field of the trap. Finally, typical mass spectra for pure glycerol/water matrix and lysine as an analyte are presented with and without the addition of trifluoracetic acid, and the ionization mechanism is briefly discussed. The technique is a promising candidate for a reproducible mass spectrometric detection scheme for the field of microfluidics.

Development and Characterization of a Field-Deployable Ion-Trap Mass Spectrometer with an Atmospheric Pressure Interface

A field-deployable quadrupole ion-trap mass spectrometer with an atmospheric pressure interface is designed, built, and characterized. The instrument enclosure (48 cm × 43 cm × 42 cm) includes a roughing pump and a helium lecture bottle; the total weight of the instrument is 68 kg. Peak power consumption during the instrument operation is ∼500 W. The instrument has a mass range of m/z 30-2500, across which it provides better than unit mass resolution. The typical peak width at half height is 0.3 Th for a scan speed of 4000 Th/s. Operation of the instrument with electrospray and atmospheric-pressure matrix-assisted laser desorption ionization (AP-MALDI) ion sources is demonstrated. AP-MALDI analysis of low femtomole amounts of peptides reveals that the sensitivity of the instrument is on par with modern commercially available quadrupole ion-trap mass spectrometers. Tandem mass spectrometry capabilities of the instrument include simultaneous isolation and fragmentation of several different compounds. Two ways to reduce the size, weight, and power consumption of the portable instrument were explored, and results of these initial studies are presented. One of the ways includes utilization of hydrogen as a buffer gas for operation of the ion-trap mass analyzer in combination with a metal hydride method for storage of hydrogen in a compact rechargeable cartridge. Furthermore, careful selection of the inlet capillary dimensions allowed to eliminate the first "1 Torr" stage of the differential pumping without any significant loss of the instrument sensitivity. The elimination of this first pumping stage removed two turbo drag pumps, which substantially decreased the instrument's maximum power consumption (to ∼300 W in peak use, and ∼150 W during standby), as well as its size (to 30 cm × 43 cm × 50 cm) and weight (to 35 kg).

Gas-Phase Ozonolysis of Selected Olefins: The Yield of Stabilized Criegee Intermediate and the Reactivity toward SO2

The gas-phase reaction of ozone with olefins represents an important path for the conversion of unsaturated hydrocarbons in the atmosphere. The current interest is focused on the formation of stabilized Criegee intermediates (sCI) and possible further reactions of sCI. We report results from the ozonolysis of 2,3-dimethyl-2-butene (TME), trans-2-butene and 1-methyl-cyclohexene (MCH) carried out in an atmospheric pressure flow tube at 293 ± 0.5 K and RH = 50% using chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry to detect H2SO4 produced from SO2 oxidation by sCI. The yields of sCI were found to be in good agreement with recently observed data: 0.62 ± 0.28 (TME), 0.53 ± 0.24 (trans-2-butene) and 0.16 ± 0.07 (MCH). The rate coefficients for sCI + SO2 from our experiment, (0.9–7.7) × 10–13 cm3 molecule–1 s–1, are within the range of recommendations from indirect determinations as given so far in the literature. Our study helps to assess the importance of sCI in atmospheric chemistry, especially for the oxidation of SO2 to H2SO4.

Transversal Modulation Ion Mobility Spectrometry (TM-IMS), A New Mobility Filter Overcoming Turbulence Related Limitations

The analysis of ions according to their mobility is a technique that is attracting increasing interest. The new technology presented here, which we have termed Transversal Modulation Ion Mobility Spectrometry (TM-IMS), utilizes only electric fields, operates at atmospheric pressure, produces a continuous output of mobility selected ions (according to their true mobility and not to nonlinear effects), and has a very accessible inlet and outlet. These features would make it an ideal choice for tandem IMS-MS analysis in combination with most commercial Atmospheric Pressure Interface MS (API-MS) systems. We modeled and evaluated two different TM-IMS configurations (TM-IMS, and multistage TM-IMS), and we concluded that the most promising configuration would be a two-stage TM-IMS. We developed and tested a TM-IMS, and the measured resolving power is R = 55. The TM-IMS behaves similarly to the planar Differential Mobility Analyzer, but the TM-IMS utilizes only electric fields, and no fragile flow with high Reynolds numbers is required. We tested the robustness of the TM-IMS, which proves to be a very robust and reliable analyzer: the required voltage accuracy is 5 V in 10 kV, and the mechanical precision is 1 mm in 5 cm.