Browsing by Subject "CHEMICAL-IONIZATION"

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  • Berndt, Torsten; Mender, Bernhard; Scholz, Wiebke; Fischer, Lukas; Herrmann, Hartmut; Kulmala, Markku; Hansel, Armin (2018)
    alpha-Pinene (C10H16) represents one of the most important biogenic emissions in the atmosphere. Its oxidation products can significantly contribute to the secondary organic aerosol (SOA) formation. Here, we report on the formation mechanism of C-19 and C-20 accretion products from alpha-pinene oxidation, which are believed to be efficient SOA precursors. Measurements have been performed in a free-jet flow system. Detection of RO2 radicals and accretion products was carried out by recent mass spectrometric techniques using different ionization schemes. Observed C-10-RO2 radicals from alpha-pinene ozonolysis were O,O-C10H15(O-2)(x)O-2 with x = 0, 1, 2, 3 and from the OH radical reaction HO-C10H16(O-2)(alpha)O-2 with alpha = 0, 1, 2. All detected C 20 accretion products can be explained via the accretion reaction RO2 + R'O-2 -> ROOR' + O-2 starting from the measured C-10-RO2 radicals. We speculate that C-19 accretion products are formed in an analogous way assuming CH2O elimination. Addition of isoprene (C5H8), producing C-5-RO2 radicals, leads to C-15 accretion products formed via cross-reactions with C-10-RO2 radicals. This process is competing with the formation of C-19/C-20 products from the pure alpha-pinene oxidation. A similar behavior has been observed for ethylene additives that form C-12 accretion products. In the atmosphere, a complex accretion product spectrum from self- and cross-reactions of available RO2 radicals can be expected. Modeling atmospheric conditions revealed that C-19/C-20 product formation is only reduced by a factor of 1.2 or 3.6 in isoprene-dominated environments assuming a 2- or 15-fold isoprene concentration over alpha-pinene, respectively, as present in different forested areas.
  • Kauppila, T. J.; Flink, A.; Pukkila, J.; Ketola, R. A. (2016)
    RATIONALE: Fast methods that allow the in situ analysis of explosives from a variety of surfaces are needed in crime scene investigations and home-land security. Here, the feasibility of the ambient mass spectrometry technique desorption atmospheric pressure photoionization (DAPPI) in the analysis of the most common nitrogen-based explosives is studied. METHODS: DAPPI and desorption electrospray ionization (DESI) were compared in the direct analysis of trinitrotoluene (TNT), trinitrophenol (picric acid), octogen (HMX), cyclonite (RDX), pentaerythritol tetranitrate (PETN), and nitroglycerin (NG). The effect of different additives in DAPPI dopant and in DESI spray solvent on the ionization efficiency was tested, as well as the suitability of DAPPI to detect explosives from a variety of surfaces. RESULTS: The analytes showed ions only in negative ion mode. With negative DAPPI, TNT and picric acid formed deprotonated molecules with all dopant systems, while RDX, HMX, PETN and NG were ionized by adduct formation. The formation of adducts was enhanced by addition of chloroform, formic acid, acetic acid or nitric acid to the DAPPI dopant. DAPPI was more sensitive than DESI for TNT, while DESI was more sensitive for HMX and picric acid. CONCLUSIONS: DAPPI could become an important method for the direct analysis of nitroaromatics from a variety of surfaces. For compounds that are thermally labile, or that have very low vapor pressure, however, DESI is better suited. Copyright (C) 2016 John Wiley & Sons, Ltd.
  • Pöhö, Paivi; Scholz, Karen; Kärkkäinen, Niina; Haapala, Markus; Räikkönen, Heikki; Kostiainen, Risto; Vaikkinen, Anu (2019)
    A new heated capillary photoionization (CPI) ion source design was developed to photoionize analytes inside a transfer capillary between a gas chromatograph (GC) and a mass spectrometer (MS). The CPI setup included a wide, oval-shaped vacuum-ultraviolet (VUV) transparent magnesium fluoride (MgF2) window to maximize photoionization efficiency and thus sensitivity. The source contained a nitrogen housing around the ionization chamber inlet to avoid undesirable hydrolysis and oxidation reactions with ambient air and to maximize the proportion of formed molecular radical cations of analytes. The feasibility of the ion source was studied by analyzing 18 endogenous steroids in urine as their trimethylsilyl (TMS) derivatives with gas chromatography-tandem mass spectrometry (GC-MS/MS). The method was validated and applied to human urine samples. To our best knowledge, this is the first time that a capillary photoionization ion source has been applied for quantitative analysis of biological samples. The GC-CPI-MS/MS method showed good chromatographic resolution (peak half-widths between 3.1 to 5.3 s), acceptable linearity (coefficient of determination between 0.981 to 0.996), and repeatability (relative standard deviation (RSD%) between 5 to 18%). Limits of detection (LOD) were between 2 to 100 pg mL(-1) and limits of quantitation (LOQ) were between 0.05 to 2 ng mL(-1). In total, 15 steroids were quantified either as a free steroid or glucuronide conjugate from the urine of volunteers. The new CPI source design showed excellent sensitivity for analysis of steroids in complex biological samples. (C) 2019 Elsevier B.V. All rights reserved.
  • Iyer, Siddharth; Reiman, Heidi; Moller, Kristian H.; Rissanen, Matti P.; Kjaergaard, Henrik G.; Kurten, Theo (2018)
    The oxidation of biogenically emitted volatile organic compounds (BVOC) plays an important role in the formation of secondary organic aerosols (SOA) in the atmosphere. Peroxy radicals (RO2) are central intermediates in the BVOC oxidation process. Under clean (low-NOx) conditions, the main bimolecular sink reactions for RO2 are with the hydroperoxy radical (HO2) and with other RO2 radicals. Especially for small RO2, the RO2 + HO2 reaction mainly leads to closed-shell hydroperoxide products. However, there exist other known RO2 + HO2 and RO2 + RO2 reaction channels that can recycle radicals and oxidants in the atmosphere, potentially leading to lower-volatility products and enhancing SOA formation. In this work, we present a thermodynamic overview of two such reactions: (a) RO2 + HO2 -> RO + OH + O-2 and (b) R'O-2 + RO2 -> R'O + RO + O-2 for selected monoterpene + oxidant derived peroxy radicals. The monoterpenes considered are alpha-pinene, beta-pinene, limonene, trans-beta-ocimene, and Delta(3)-carene. The oxidants considered are the hydroxyl radical (OH), the nitrate radical (NO3), and ozone (O-3). The reaction Gibbs energies were calculated at the DLPNO-CCSD(T)/def2-QZVPP//omega B97X-D/aug-cc-pVTZ level of theory. All reactions studied here were found to be exergonic in terms of Gibbs energy. On the basis of a comparison with previous mechanistic studies, we predict that reaction a and reaction b are likely to be most important for first-generation peroxy radicals from O-3 oxidation (especially for beta-pinene), while being less so for most first-generation peroxy radicals from OH and NO3 oxidation. This is because both reactions are comparatively more exergonic for the O-3 oxidized systems than their OH and NO3 oxidized counterparts. Our results indicate that bimolecular reactions of certain complex RO, may contribute to an increase in radical and oxidant recycling under high HO2 conditions in the atmosphere, which can potentially enhance SOA formation.
  • Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John; Kolb, Charles; Davidovits, Paul; Worsnop, Douglas; Brune, William (2017)
    Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O-3) is photolyzed at 254 nm to produce O(D-1) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O-3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(D-1) + N2O -> 2NO, followed by the reaction NO + O-3 -> NO2 + O-2. Laboratory measurements coupled with photochemical model simulations suggest that O(D-1) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3-) reagent ion to detect gas-phase oxidation products of isoprene and alpha-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.
  • Draper, Danielle C.; Myllys, Nanna; Hyttinen, Noora; Moller, Kristian H.; Kjaergaard, Henrik G.; Fry, Juliane L.; Smith, James N.; Kurten, Theo (2019)
    NO3 radical oxidation of most monoterpenes is a significant source of secondary organic aerosol (SOA) in many regions influenced by both biogenic and anthropogenic emissions, but there are very few published mechanistic studies of NO3 chemistry beyond simple first generation products. Here, we present a computationally derived mechanism detailing the unimolecular pathways available to the second generation of peroxy radicals following NO3 oxidation of Delta-3-carene, defining generations based on the sequence of peroxy radicals formed rather than number of oxidant attacks. We assess five different types of unimolecular reactions, including peroxy and alkoxy radical (RO2 and RO) hydrogen shifts, RO2 and RO ring closing (e.g., endoperoxide formation), and RO decomposition. Rate constants calculated using quantum chemical methods indicate that this chemical system has significant contribution from both bimolecular and unimolecular pathways. The dominant unimolecular reactions are endoperoxide formation, RO H-shifts, and RO decomposition. However, the complexity of the overall reaction is tempered as only 1 or 2 radical propagation pathways dominate the fate of each radical intermediate. Chemical ionization mass spectrometry (CIMS) measurements using the NO3- reagent ion during Delta-3-carene + NO3 chamber experiments show products consistent with each of the three types of unimolecular reactions predicted to be important from the computational mechanism. Moreover, the SIMPOL group contribution method for predicting vapor pressures suggests that a majority of the closed-shell products inferred from these unimolecular reactions are likely to have low enough vapor pressure to be able to contribute to SOA formation.
  • Molteni, Ugo; Bianchi, Federico; Klein, Felix; El Haddad, Imad; Frege, Carla; Rossi, Michel J.; Dommen, Josef; Baltensperger, Urs (2018)
    Anthropogenic volatile organic compounds (AV-OCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O:C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AV-OCs may contribute substantially to new particle formation events that have been detected in urban areas.
  • Li, Haiyan; Almeida, Thomas Golin; Luo, Yuanyuan; Zhao, Jian; Palm, Brett B.; Daub, Christopher D.; Huang, Wei; Mohr, Claudia; Krechmer, Jordan E.; Kurten, Theo; Ehn, Mikael (2022)
    Proton transfer reaction (PTR) is a commonly applied ionization technique for mass spectrometers, in which hydronium ions (H3O+) transfer a proton to analytes with higher proton affinities than the water molecule. This method has most commonly been used to quantify volatile hydrocarbons, but later-generation PTR instruments have been designed for better throughput of less volatile species, allowing detection of more functionalized molecules as well. For example, the recently developed Vocus PTR time-of-flight mass spectrometer (PTR-TOF) has been shown to agree well with an iodide-adduct-based chemical ionization mass spectrometer (CIMS) for products with 3-5 O atoms from oxidation of monoterpenes (C10H16). However, while several different types of CIMS instruments (including those using iodide) detect abundant signals also at "dimeric" species, believed to be primarily ROOR peroxides, no such signals have been observed in the Vocus PTR even though these compounds fulfil the condition of having higher proton affinity than water. More traditional PTR instruments have been limited to volatile molecules as the inlets have not been designed for transmission of easily condensable species. Some newer instruments, like the Vocus PTR, have overcome this limitation but are still not able to detect the full range of functionalized products, suggesting that other limitations need to be considered. One such limitation, well-documented in PTR literature, is the tendency of protonation to lead to fragmentation of some analytes. In this work, we evaluate the potential for PTR to detect dimers and the most oxygenated compounds as these have been shown to be crucial for forming atmospheric aerosol particles. We studied the detection of dimers using a Vocus PTR-TOF in laboratory experiments, as well as through quantum chemical calculations. Only noisy signals of potential dimers were observed during experiments on the ozonolysis of the monoterpene alpha-pinene, while a few small signals of dimeric compounds were detected during the ozonolysis of cyclohexene. During the latter experiments, we also tested varying the pressures and electric fields in the ionization region of the Vocus PTR-TOF, finding that only small improvements were possible in the relative dimer contributions. Calculations for model ROOR and ROOH systems showed that most of these peroxides should fragment partially following protonation. With the inclusion of additional energy from the ion-molecule collisions driven by the electric fields in the ionization source, computational results suggest substantial or nearly complete fragmentation of dimers. Our study thus suggests that while the improved versions of PTR-based mass spectrometers are very powerful tools for measuring hydrocarbons and their moderately oxidized products, other types of CIMS are likely more suitable for the detection of ROOR and ROOH species.
  • Anttalainen, Osmo; Lattouf, Elie; Kotiaho, Tapio; Eiceman, Gary (2021)
    The abundance of ions is an essential parameter for ion mobility and mass spectrometry instrument design and for the control or optimization of chemical reactions with reactant ions. This information also advances the study of atmospheric pressure ion kinetics under continuous ionization, which has a role in developing trace level chemical analyzers. In this study, an ionization chamber is described to measure the abundance of ions produced by a 4.9 keV, model L12535, soft x-ray source from Hamamatsu Corporation. Ions of positive and negative polarity were measured independently in an 8 x 30 mm(2) cross section at distances of 12-136 mm at ambient air from an uncollimated beam. Ions were collected using electric fields and 16 sets of plates. The ion current decreased exponentially with distance from the source, and the calculated ion concentration varied between 1.0 x 10(8) and 3.8 x 10(5) ions cm(-3) on plates. A 2D-COMSOL model including losses by recombination and diffusion was favorably matched to changes in ion current intensity in the ionization chamber. Although the ionization chamber was built to characterize a commercial ion source, the design may be considered generally applicable to other x-ray sources. (C) 2021 Author(s).
  • Krechmer, Jordan E.; Groessl, Michael; Zhang, Xuan; Junninen, Heikki; Massoli, Paola; Lambe, Andrew T.; Kimmel, Joel R.; Cubison, Michael J.; Graf, Stephan; Lin, Ying-Hsuan; Budisulistiorini, Sri H.; Zhang, Haofei; Surratt, Jason D.; Knochenmuss, Richard; Jayne, John T.; Worsnop, Douglas R.; Jimenez, Jose-Luis; Canagaratna, Manjula R. (2016)
    Measurement techniques that provide molecular-level information are needed to elucidate the multiphase processes that produce secondary organic aerosol (SOA) species in the atmosphere. Here we demonstrate the application of ion mobility spectrometry-mass spectrometry (IMS-MS) to the simultaneous characterization of the elemental composition and molecular structures of organic species in the gas and particulate phases. Molecular ions of gas-phase organic species are measured online with IMS-MS after ionization with a custom-built nitrate chemical ionization (CI) source. This CI-IMS-MS technique is used to obtain time-resolved measurements (5 min) of highly oxidized organic molecules during the 2013 Southern Oxidant and Aerosol Study (SOAS) ambient field campaign in the forested SE US. The ambient IMS-MS signals are consistent with laboratory IMS-MS spectra obtained from single-component carboxylic acids and multicomponent mixtures of isoprene and monoterpene oxidation products. Mass-mobility correlations in the 2-D IMS-MS space provide a means of identifying ions with similar molecular structures within complex mass spectra and are used to separate and identify monoterpene oxidation products in the ambient data that are produced from different chemical pathways. Water-soluble organic carbon (WSOC) constituents of fine aerosol particles that are not resolvable with standard analytical separation methods, such as liquid chromatography (LC), are shown to be separable with IMS-MS coupled to an electrospray ionization (ESI) source. The capability to use ion mobility to differentiate between isomers is demonstrated for organosulfates derived from the reactive uptake of isomers of isoprene epoxydiols (IEPOX) onto wet acidic sulfate aerosol. Controlled fragmentation of precursor ions by collisionally induced dissociation (CID) in the transfer region between the IMS and the MS is used to validate MS peak assignments, elucidate structures of oligomers, and confirm the presence of the organosulfate functional group.
  • Sarnela, Nina; Jokinen, Tuija; Duplissy, Jonathan; Yan, Chao; Nieminen, Tuomo; Ehn, Mikael; Schobesberger, Siegfried; Heinritzi, Martin; Ehrhart, Sebastian; Lehtipalo, Katrianne; Tröstl, Jasmin; Simon, Mario; Kürten, Andreas; Leiminger, Markus; Lawler, Michael J.; Rissanen, Matti P.; Bianchi, Federico; Praplan, Arnaud P.; Hakala, Jani; Amorim, Antonio; Gonin, Marc; Hansel, Armin; Kirkby, Jasper; Dommen, Josef; Curtius, Joachim; Smith, James N.; Petäjä, Tuukka; Worsnop, Douglas R.; Kulmala, Markku; Donahue, Neil M.; Sipilä, Mikko (2018)
    Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate alpha-pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H-2), we were able to investigate the formation of highly oxygenated molecules (HOMs) purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO2) driven by stabilized Criegee intermediates (sCIs). We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5-6.5% for HOM formation and 22-32% for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20-50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.
  • Kürten, A.; Li, C.; Bianchi, F.; Curtius, J.; Dias, A.; Donahue, N. M.; Duplissy, J.; Flagan, R. C.; Hakala, J.; Jokinen, T.; Kirkby, J.; Kulmala, M.; Laaksonen, Ari; Lehtipalo, K.; Makhmutov, V.; Onnela, A.; Rissanen, M. P.; Simon, M.; Sipilä, M.; Stozhkov, Y.; Tröstl, J.; Ye, P.; McMurry, P. H. (2018)
    A recent CLOUD (Cosmics Leaving OUtdoor Droplets) chamber study showed that sulfuric acid and dimethylamine produce new aerosols very efficiently and yield particle formation rates that are compatible with boundary layer observations. These previously published new particle formation (NPF) rates are reanalyzed in the present study with an advanced method. The results show that the NPF rates at 1.7 nm are more than a factor of 10 faster than previously published due to earlier approximations in correcting particle measurements made at a larger detection threshold. The revised NPF rates agree almost perfectly with calculated rates from a kinetic aerosol model at different sizes (1.7 and 4.3 nm mobility diameter). In addition, modeled and measured size distributions show good agreement over a wide range of sizes (up to ca. 30 nm). Furthermore, the aerosol model is modified such that evaporation rates for some clusters can be taken into account; these evaporation rates were previously published from a flow tube study. Using this model, the findings from the present study and the flow tube experiment can be brought into good agreement for the high base-to-acid ratios (similar to 100) relevant for this study. This confirms that nucleation proceeds at rates that are compatible with collision-controlled (a.k.a. kinetically controlled) NPF for the conditions during the CLOUD7 experiment (278 K, 38% relative humidity, sulfuric acid concentration between 1 x 10(6) and 3 x 10(7) cm(-3), and dimethylamine mixing ratio of similar to 40 pptv, i.e., 1 x 10(9) cm(-3)).
  • Rissanen, Matti P. (2018)
    Atmospheric autoxidation of volatile organic compounds (VOC) leads to prompt formation of highly oxidized multifunctional compounds (HOM) that have been found crucial in forming ambient secondary organic aerosol (SOA). As a radical chain reaction mediated by oxidized peroxy (RO2) and alkoxy (RO) radical intermediates, the formation pathways can be intercepted by suitable reaction partners, preventing the production of the highest oxidized reaction products, and thus the formation of the most condensable material. Commonly, NO is expected to have a detrimental effect on RO2 chemistry, and thus on autoxidation, whereas the influence of NO2 is mostly neglected. Here it is shown by dedicated flow tube experiments, how high concentration of NO2 suppresses cyclohexene ozonolysis initiated autoxidation chain reaction. Importantly, the addition of NO2 ceases covalently bound dimer production, indicating their production involving acylperoxy radical (RC(O)OO•) intermediates. In related experiments NO was also shown to strongly suppress the highly oxidized product formation, but due to possibility for chain propagating reactions (as with RO2 and HO2 too), the suppression is not as absolute as with NO2. Furthermore, it is shown how NOx reactions with oxidized peroxy radicals lead into indistinguishable product compositions, complicating mass spectral assignments in any RO2 + NOx system. The present work was conducted with atmospheric pressure chemical ionization mass spectrometry (CIMS) as the detection method for the highly oxidized end-products and peroxy radical intermediates, under ambient conditions and at short few second reaction times. Specifically, the insight was gained by addition of a large amount of NO2 (and NO) to the oxidation system, upon which acylperoxy radicals reacted in RC(O)O2 + NO2 → RC(O)O2NO2 reaction to form peroxyacylnitrates, consequently shutting down the oxidation sequence. Keywords: acylperoxy radicals; Autoxidation; dimers; Highly oxidized multifunctional compounds; Highly oxygenated molecules; HOM; nitrogen oxides; peroxyacylnitrate
  • Kangasluoma, Juha; Cai, Runlong; Jiang, Jingkun; Deng, Chenjuan; Stolzenburg, Dominik; Ahonen, Lauri R.; Chan, Tommy; Fu, Yueyun; Kim, Changhyuk; Laurila, Tiia M.; Zhou, Ying; Dada, Lubna; Sulo, Juha; Flagan, Richard C.; Kulmala, Markku; Petaja, Tuukka; Lehtipalo, Katrianne (2020)
    Interest in understanding gas-to-particle phase transformation in several disciplines such as at-mospheric sciences, material synthesis, and combustion has led to the development of several distinct instruments that can measure the particle size distributions down to the sizes of large molecules and molecular clusters, at which the initial particle formation and growth takes place. These instruments, which include the condensation particle counter battery, a variety of electrical mobility spectrometers and the particle size magnifier, have been usually characterized in lab-oratory experiments using carefully prepared calibration aerosols. They are then applied, alone or in combination, to study the gas-to-particle transition in experiments that produce particles with a wide range of compositions and other properties. Only a few instrument intercomparisons in either laboratory or field conditions have been reported, raising the question: how accurately can the sub-10 nm particle number size distributions be measured with the currently available instrumentation? Here, we review previous studies in which sub-10 nm particle size distributions have been measured with at least two independent instruments. We present recent data from three sites that deploy the current state-of-the-art instrumentation: Hyytiala, Beijing, and the CLOUD chamber. After discussing the status of the sub-10 nm size distribution measurements, we present a comprehensive uncertainty analysis for these methods that suggests that our present understanding on the sources of uncertainties quite well captures the observed deviations be-tween different instruments in the size distribution measurements. Finally, based on present understanding of the characteristics of a number of systems in which gas-to-particle conversion takes place, and of the instrumental limitations, we suggest guidelines for selecting suitable in-struments for various applications.
  • Wang, Sainan; Riva, Matthieu; Yan, Chao; Ehn, Mikael; Wang, Liming (2018)
    It is generally assumed that isoprene-derived secondary organic aerosol (SOA) precursors are mainly formed from the secondary reactions of intermediate products with OH radicals in the gas phase and multiphase oxidation in particles. In this paper, we predicted a theoretical mechanism for the primary formation of highly oxygenated molecules (HOM) in the gas phase through successive intramolecular H-shifts and O-2 addition in the specific Z-delta isomer of hydroxyl-peroxy radicals and alkoxy radicals. The position of O-2 addition is different from that in forming hydroperoxy aldehydes. The prediction was further supported experimentally by successfully identifying a few highly oxidized peroxy radicals and closed-shell products such as C5H9O7,9, C5H10O6,7,8, and C4H8O5 in a flow reactor by chemical ionization mass spectrometry at air pressure. These HOM products could serve as important precursors to isoprene-derived SOA. Further modeling studies on the effect of NO concentration suggested that HOM formation could account for up to, similar to 11% of the branching ratio (similar to 9% from the 4-OH channel and similar to 2% from the 1-OH channel) in the reaction of isoprene with OH when the lifetimes of peroxy radicals due to bimolecular reactions are similar to 100 s, which is typical in forest regions.
  • Bianchi, Federico; Garmash, Olga; He, Xucheng; Yan, Chao; Iyer, Siddharth; Rosendahl, Ida; Xu, Zhengning; Rissanen, Matti P.; Riva, Matthieu; Taipale, Risto; Sarnela, Nina; Petäjä, Tuukka; Worsnop, Douglas R.; Kulmala, Markku; Ehn, Mikael; Junninen, Heikki (2017)
    In order to investigate the negative ions in the boreal forest we have performed measurements to chemically characterise the composition of negatively charged clusters containing highly oxygenated molecules (HOMs). Additionally, we compared this information with the chemical composition of the neutral gas-phase molecules detected in the ambient atmosphere during the same period. The chemical composition of the ions was retrieved using an atmospheric pressure interface time-of-flight mass spectrometer (APiTOF-MS) while the gas-phase neutral molecules (mainly sulfuric acid and HOMs) were characterised using the same mass spectrometer coupled to a nitrate-based chemical ionisation unit (CI-APi-TOF). Overall, we divided the identified HOMs in two classes: HOMs containing only carbon, hydrogen and oxygen and nitrogen-containing HOMs or organonitrates (ONs). During the day, among the ions, in addition to the well-known pure sulfuric acid clusters, we found a large number of HOMs clustered with nitrate (NO3-) or bisulfate (HSO4-), with the first one being more abundant. During the night, the distribution of ions, mainly composed of HOM clustered with NO3-, was very similar to the neutral compounds that are detected in the CI-APi-TOF as adducts with the artificially introduced primary ion (NO3-). For the first time, we identified several clusters containing up to 40 carbon atoms. These ions are formed by up to four oxidised alpha-pinene units clustered with NO3-. While we know that dimers (16-20 carbon atoms) are probably formed by a covalent bond between two alpha-pinene oxidised units, it is still unclear what bonding formed larger clusters. Finally, diurnal profiles of the negative ions were consistent with the neutral compounds revealing that ONs peak during the day while HOMs are more abundant at night-time. However, during the day, a large fraction of the negative charge is taken up by the pure sulfuric acid clusters causing differences between ambient ions and neutral compounds (i.e. less available charge for HOM and ON).
  • Yan, Chao; Yin, Rujing; Lu, Yiqun; Dada, Lubna; Yang, Dongsen; Fu, Yueyun; Kontkanen, Jenni; Deng, Chenjuan; Garmash, Olga; Ruan, Jiaxin; Baalbaki, Rima; Schervish, Meredith; Cai, Runlong; Bloss, Matthew; Chan, Tommy; Chen, Tianzeng; Chen, Qi; Chen, Xuemeng; Chen, Yan; Chu, Biwu; Dällenbach, Kaspar; Foreback, Benjamin; He, Xucheng; Heikkinen, Liine; Jokinen, Tuija; Junninen, Heikki; Kangasluoma, Juha; Kokkonen, Tom; Kurppa, Mona; Lehtipalo, Katrianne; Li, Haiyan; Li, Hui; Li, Xiaoxiao; Liu, Yiliang; Ma, Qingxin; Paasonen, Pauli; Rantala, Pekka; Pileci, Rosaria E.; Rusanen, Anton; Sarnela, Nina; Simonen, Pauli; Wang, Shixian; Wang, Weigang; Wang, Yonghong; Xue, Mo; Yang, Gan; Yao, Lei; Zhou, Ying; Kujansuu, Joni; Petäjä, Tuukka; Nie, Wei; Ma, Yan; Ge, Maofa; He, Hong; Donahue, Neil M.; Worsnop, Douglas R.; Kerminen, Veli-Matti; Wang, Lin; Liu, Yongchun; Zheng, Jun; Kulmala, Markku; Jiang, Jingkun; Bianchi, Federico (2021)
    Intense and frequent new particle formation (NPF) events have been observed in polluted urban environments, yet the dominant mechanisms are still under debate. To understand the key species and governing processes of NPF in polluted urban environments, we conducted comprehensive measurements in downtown Beijing during January-March, 2018. We performed detailed analyses on sulfuric acid cluster composition and budget, as well as the chemical and physical properties of oxidized organic molecules (OOMs). Our results demonstrate that the fast clustering of sulfuric acid (H2SO4) and base molecules triggered the NPF events, and OOMs further helped grow the newly formed particles toward climate- and health-relevant sizes. This synergistic role of H2SO4, base species, and OOMs in NPF is likely representative of polluted urban environments where abundant H2SO4 and base species usually co-exist, and OOMs are with moderately low volatility when produced under high NOx concentrations.