Introducing the Extended Volatility Range Proton-Transfer-Reaction Mass Spectrometer (EVR PTR-MS)

Piel, Felix; Müller, Markus; Winkler, Klaus; Sätra, Jenny Skytte af; Wisthaler, Armin

doi:10.5194/amt-2020-241

Cited by 4 publications

(4 citation statements)

References 24 publications

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“…The PTR-ToF-MS is also interfaced with a particle inlet (Chemical Analysis of Aerosol Online, CHARON), which allows the semi-volatile particle components to be measured. A detailed description of the CHARON-PTR-MS has been provided elsewhere (Müller et al, 2017;Piel et al, 2021). During the period of BCP in- Jaoui et al (2003), + SOA mass wall loss corrected, t following BCP addition calculated assuming a constant BCP addition rate in each experiment, # not detectable due to wall losses, ass assumed to have the same density as at 298 K due to its large measurement uncertainty.…”

Section: Instrumentationmentioning

confidence: 99%

Kinetics, SOA yields, and chemical composition of secondary organic aerosol from β-caryophyllene ozonolysis with and without nitrogen oxides between 213 and 313 K

et al. 2022

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Abstract. β-caryophyllene (BCP) is one of the most important sesquiterpenes (SQTs) in the atmosphere, with a large potential contribution to secondary organic aerosol (SOA) formation mainly from reactions with ozone (O3) and nitrate radicals (NO3). In this work, we study the temperature dependence of the kinetics of BCP ozonolysis, SOA yields, and SOA chemical composition in the dark and in the absence and presence of nitrogen oxides including nitrate radicals (NO3). We cover a temperature range of 213–313 K, representative of tropospheric conditions. The oxidized components in both gas and particle phases were characterized on a molecular level by a chemical ionization mass spectrometer equipped with a filter inlet for gases and aerosols using iodide as the reagent ion (FIGAERO-iodide-CIMS). The batch mode experiments were conducted in the 84.5 m3 aluminium simulation chamber AIDA at the Karlsruhe Institute of Technology (KIT). In the absence of nitrogen oxides, the temperature-dependent rate coefficient of the endocyclic double bond in BCP reacting with ozone between 243–313 K is negatively correlated with temperature, corresponding to the following Arrhenius equation: k= (1.6 ± 0.4) × 10−15 × exp((559 ± 97)/T). The SOA yields increase from 16 ± 5 % to 37 ± 11 %, with temperatures decreasing from 313 to 243 K at a total organic particle mass of 10 µg m−3. The variation in the ozonolysis temperature leads to a substantial impact on the abundance of individual organic molecules. In the absence of nitrogen oxides, monomers C14−15H22−24O3−7 (37.4 %), dimers C28−30H44−48O5−9 (53.7 %), and trimers C41−44H62−66O9−11 (8.6 %) are abundant in the particle phase at 213 K. At 313 K, we observed more oxidized monomers (mainly C14−15H22−24O6−9, 67.5 %) and dimers (mainly C27−29H42−44O9−11, 27.6 %), including highly oxidized molecules (HOMs; C14H22O7,9, C15H22O7,9C15H24O7,9), which can be formed via hydrogen shift mechanisms, but no significant trimers. In the presence of nitrogen oxides, the organonitrate fraction increased from 3 % at 213 K to 12 % and 49 % at 243 and 313 K, respectively. Most of the organonitrates were monomers with C15 skeletons and only one nitrate group. More highly oxygenated organonitrates were observed at higher temperatures, with their signal-weighted O:C atomic ratio increasing from 0.41 to 0.51 from 213 to 313 K. New dimeric and trimeric organic species without nitrogen atoms (C20, C35) were formed in the presence of nitrogen oxides at 298–313 K, indicating potential new reaction pathways. Overall, our results show that increasing temperatures lead to a relatively small decrease in the rate coefficient of the endocyclic double bond in BCP reacting with ozone but to a strong decrease in SOA yields. In contrast, the formation of HOMs and organonitrates increases significantly with temperature.

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Section: Instrumentationmentioning

confidence: 99%

Kinetics, SOA yields, and chemical composition of secondary organic aerosol from β-caryophyllene ozonolysis with and without nitrogen oxides between 213 and 313 K

et al. 2022

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“…We explain this by the total (HT PTR-QMS) and partial (PTR-ToF-MS) evaporation of the aminium salt particle in the heated sampling lines and, in particular, in the drift tubes of the two PTR-MS analyzers. 56 Comparisons of the AMP profiles obtained in the other experiments are presented in Figures S25–S29 . We finally note that the PTR-ToF-MS instrument also exhibits a delayed response to AMPNO 2 ( Figure S30 ).…”

Section: Resultsmentioning

confidence: 99%

Atmospheric Chemistry of 2-Amino-2-methyl-1-propanol: A Theoretical and Experimental Study of the OH-Initiated Degradation under Simulated Atmospheric Conditions

et al. 2021

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The OH-initiated degradation of 2-amino-2-methyl-1-propanol [CH 3 C(NH 2 )(CH 3 )CH 2 OH, AMP] was investigated in a large atmospheric simulation chamber, employing time-resolved online high-resolution proton-transfer reaction-time-of-flight mass spectrometry (PTR-ToF-MS) and chemical analysis of aerosol online PTR-ToF-MS (CHARON-PTR-ToF-MS) instrumentation, and by theoretical calculations based on M06-2X/aug-cc-pVTZ quantum chemistry results and master equation modeling of the pivotal reaction steps. The quantum chemistry calculations reproduce the experimental rate coefficient of the AMP + OH reaction, aligning k ( T ) = 5.2 × 10 –12 × exp (505/ T ) cm 3 molecule –1 s –1 to the experimental value k exp,300K = 2.8 × 10 –11 cm 3 molecule –1 s –1 . The theoretical calculations predict that the AMP + OH reaction proceeds via hydrogen abstraction from the −CH 3 groups (5–10%), −CH 2 – group, (>70%) and −NH 2 group (5–20%), whereas hydrogen abstraction from the −OH group can be disregarded under atmospheric conditions. A detailed mechanism for atmospheric AMP degradation was obtained as part of the theoretical study. The photo-oxidation experiments show 2-amino-2-methylpropanal [CH 3 C(NH 2 )(CH 3 )CHO] as the major gas-phase product and propan-2-imine [(CH 3 ) 2 C=NH], 2-iminopropanol [(CH 3 )(CH 2 OH)C=NH], acetamide [CH 3 C(O)NH 2 ], formaldehyde (CH 2 O), and nitramine 2-methyl-2-(nitroamino)-1-propanol [AMPNO 2 , CH 3 C(CH 3 )(NHNO 2 )CH 2 OH] as minor primary products; there is no experimental evidence of nitrosamine formation. The branching in the initial H abstraction by OH radicals was derived in analyses of the temporal gas-phase product profiles to be B CH 3 / B CH 2 / B NH 2 = 6:70:24. Secondary photo-oxidation products and products resulting from particle and surface processing of the primary gas-phase products were also observed and quantified. All the photo-oxidation experiments were accompanied by extensive particle formation that was initiated by the reaction of AMP with nitric acid and that mainly consisted of this salt. Minor amounts of the gas-phase photo-...

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“…S5). Concentrations of gaseous and particulate compounds shown here included the last 5 min of every gas-/particle-phase working mode, in order to minimize the interferences carried over from the previous working mode by allowing for a sufficient amount of equilibration time in the inlet (Piel et al, 2021). In order to synchronize the gas-and particle-phase data to calculate gas-particle partitioning, the average hourly data were then used for further analysis.…”

Section: Sampling Alternation Between Gas and Particle Phasementioning

confidence: 99%

“…Another potential advantage of CHARON-PTR-ToF-MS is that the chemical information of the collected particles can be studied qualitatively and quantitatively over a chemical composition level, even at sub-nanogram mass concentrations per molecule, owing to the well-studied ionmolecule reaction chemistry in PTR-ToF-MS (Piel et al, 2019). CHARON has shown promising potential in the realtime analysis of the chemical composition and spatiotemporal distributions of aerosols with laboratory-, ground-, and aircraft-based platforms (Piel et al, 2019;Tan et al, 2018;Gkatzelis et al, 2018a, b;Muller et al, 2017;Eichler et al, , 2015Antonsen et al, 2017;Leglise et al, 2019;Piel et al, 2021). As a relatively new technique, the use of CHARON-PTR-ToF-MS to investigate the gas-particle partitioning of organic compounds is still quite limited.…”

Section: Introductionmentioning

confidence: 99%

Real-time measurement of phase partitioning of organic compounds using a proton-transfer-reaction time-of-flight mass spectrometer coupled to a CHARON inlet

et al. 2023

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Abstract. Understanding the gas–particle partitioning of semivolatile organic compounds (SVOCs) is of crucial importance in the accurate representation of the global budget of atmospheric organic aerosols. In this study, we quantified the gas- vs. particle-phase fractions of a large number of SVOCs in real time in an urban area of East China with the use of a CHemical Analysis of aeRosols ONline (CHARON) inlet coupled to a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS). We demonstrated the use of the CHARON inlet for highly efficient collection of particulate SVOCs while maintaining the intact molecular structures of these compounds. The collected month-long dataset with hourly resolution allows us to examine the gas–particle partitioning of a variety of SVOCs under ambient conditions. By comparing the measurements with model predictions using instantaneous equilibrium partitioning theory, we found that the dissociation of large parent molecules during the PTR ionization process likely introduces large uncertainties to the measured gas- vs. particle-phase fractions of less oxidized SVOCs, and therefore, caution should be taken when linking the molecular composition to the particle volatility when interpreting the PTR-ToF-MS data. Our analysis suggests that understanding the fragmentation mechanism of SVOCs and accounting for the neutral losses of small moieties during the molecular feature extraction from the raw PTR mass spectra could reduce, to a large extent, the uncertainties associated with the gas–particle partitioning measurement of SVOCs in the ambient atmosphere.

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Introducing the Extended Volatility Range Proton-Transfer-Reaction Mass Spectrometer (EVR PTR-MS)

Cited by 4 publications

References 24 publications

Kinetics, SOA yields, and chemical composition of secondary organic aerosol from β-caryophyllene ozonolysis with and without nitrogen oxides between 213 and 313 K

Kinetics, SOA yields, and chemical composition of secondary organic aerosol from β-caryophyllene ozonolysis with and without nitrogen oxides between 213 and 313 K

Atmospheric Chemistry of 2-Amino-2-methyl-1-propanol: A Theoretical and Experimental Study of the OH-Initiated Degradation under Simulated Atmospheric Conditions

Real-time measurement of phase partitioning of organic compounds using a proton-transfer-reaction time-of-flight mass spectrometer coupled to a CHARON inlet

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