scholarly journals Analysis of high mass resolution PTR-TOF mass spectra from 1,3,5-trimethylbenzene (TMB) environmental chamber experiments

2012 ◽  
Vol 12 (2) ◽  
pp. 829-843 ◽  
Author(s):  
M. Müller ◽  
M. Graus ◽  
A. Wisthaler ◽  
A. Hansel ◽  
A. Metzger ◽  
...  
Keyword(s):  
Gas Phase ◽  
Proton Transfer Reaction ◽  
Chemical Mechanism ◽  
Oxidation States ◽  
High Mass ◽  
Carbon Oxidation ◽  
Environmental Chamber ◽  
Photo Oxidation ◽  
High Mass Resolution ◽  
Paul Scherrer

Abstract. A series of 1,3,5-trimethylbenzene (TMB) photo-oxidation experiments was performed in the 27-m3 Paul Scherrer Institute environmental chamber under various NOx conditions. A University of Innsbruck prototype high resolution Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOF) was used for measurements of gas and particulate phase organics. The gas phase mass spectrum displayed ~200 ion signals during the TMB photo-oxidation experiments. Molecular formulas CmHnNoOp were determined and ion signals were separated and grouped according to their C, O and N numbers. This allowed to determine the time evolution of the O:C ratio and of the average carbon oxidation state OSC of the reaction mixture. Both quantities were compared with master chemical mechanism (MCMv3.1) simulations. The O:C ratio in the particle phase was about twice the O:C ratio in the gas phase. Average carbon oxidation states of secondary organic aerosol (SOA) samples OSCSOA were in the range of −0.34 to −0.31, in agreement with expected average carbon oxidation states of fresh SOA (OSC = −0.5–0).

scholarly journals Analysis of high mass resolution PTR-TOF mass spectra from 1,3,5-trimethylbenzene (TMB) environmental chamber experiments

2011 ◽  
Vol 11 (9) ◽  
pp. 25871-25907
Author(s):  
M. Müller ◽  
M. Graus ◽  
A. Wisthaler ◽  
A. Hansel ◽  
A. Metzger ◽  
...  
Keyword(s):  
Gas Phase ◽  
Proton Transfer Reaction ◽  
Chemical Mechanism ◽  
Oxidation States ◽  
High Mass ◽  
Carbon Oxidation ◽  
Environmental Chamber ◽  
Photo Oxidation ◽  
High Mass Resolution ◽  
Paul Scherrer

Abstract. A series of 1,3,5-trimethylbenzene (TMB) photo-oxidation experiments was performed in the 27-m3 Paul Scherrer Institute environmental chamber under various NOx conditions. A University of Innsbruck prototype high resolution Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOF) was used for measurements of gas and particulate phase organics. The gas phase mass spectrum displayed ~200 ion signals during the TMB photo-oxidation experiments. Molecular formulas CNmHnNoOp were determined and ion signals were separated and grouped according to their C, O and N numbers. This allowed to determine the time evolution of the O:C ratio and of the average carbon oxidation state OSC of the reaction mixture. Both quantities were compared with master chemical mechanism (MCMv3.1) simulations. The O:C ratio in the particle phase was about twice the O:C ratio in the gas phase. Average carbon oxidation states of secondary organic aerosol (SOA) samples OSCSOA were in the range of −0.34 to −0.31, in agreement with expected average carbon oxidation states of fresh SOA (OSC = −0.5 − 0).

scholarly journals Evaluation of 1,3,5 trimethylbenzene degradation in the detailed tropospheric chemistry mechanism, MCMv3.1, using environmental chamber data

2008 ◽  
Vol 8 (21) ◽  
pp. 6453-6468 ◽  
Author(s):  
A. Metzger ◽  
J. Dommen ◽  
K. Gaeggeler ◽  
J. Duplissy ◽  
A. S. H. Prevot ◽  
...  
Keyword(s):  
Degradation Mechanism ◽  
Reactive Systems ◽  
Tropospheric Chemistry ◽  
Chemical Mechanism ◽  
Oh Radicals ◽  
Environmental Chamber ◽  
Photo Oxidation ◽  
Trimethyl Benzene ◽  
Using Data ◽  
Paul Scherrer

Abstract. The degradation mechanism of 1,3,5-trimethyl- benzene (TMB) as implemented in the Master Chemical Mechanism version 3.1 (MCM) was evaluated using data from the environmental chamber at the Paul Scherrer Institute. The results show that the MCM provides a consistent description of the photo-oxidation of TMB/NOx mixtures for a range of conditions. In all cases the agreement between the measurement and the simulation decreases with decreasing VOC-NOx ratio and in addition with increasing precursor concentration. A significant underestimation of the decay rate of TMB and thus underestimation of reactivity in the system, consistent with results from previous appraisals of the MCM, was observed. Much higher nitrous acid (HONO) concentrations compared to simulations and expected from chamber characterization experiments were measured during these smog chamber experiments. A light induced NO2 to HONO conversion at the chamber walls is suggested to occur. This photo-enhanced NO2 to HONO conversion with subsequent HONO photolysis enhances the reactivity of the system. After the implementation of this reaction in the model it describes the decay of TMB properly. Nevertheless, the model still over-predicts ozone at a later stage of the experiment. This can be attributed to a too slow removal of NO2. It is also shown that this photo-enhanced HONO formation is not restricted to TMB photo-oxidation but also occurs in other chemical systems (e.g. α-pinene). However, the influence of HONO as a source of OH radicals is less important in these more reactive systems and therefore the importance of the HONO chemistry is less obvious.

scholarly journals Evaluation of 1,3,5 trimethylbenzene degradation in the detailed tropospheric chemistry mechanism, MCMv3.1, using environmental chamber data

2008 ◽  
Vol 8 (3) ◽  
pp. 11567-11607 ◽  
Author(s):  
A. Metzger ◽  
J. Dommen ◽  
K. Gaeggeler ◽  
J. Duplissy ◽  
A. S. H. Prevot ◽  
...  
Keyword(s):  
Degradation Mechanism ◽  
Reactive Systems ◽  
Tropospheric Chemistry ◽  
Chemical Mechanism ◽  
Oh Radicals ◽  
Environmental Chamber ◽  
Chemical Systems ◽  
Photo Oxidation ◽  
Using Data ◽  
Paul Scherrer

Abstract. The degradation mechanism of 1,3,5-trimethylbenzene (TMB) as implemented in the Master Chemical Mechanism version 3.1 (MCM) was evaluated using data from the environmental chamber at the Paul Scherrer Institute. The results show that the MCM provides a consistent description of the photo-oxidation of TMB/NOx mixtures for a range of conditions. In all cases the agreement between the measurement and the simulation decreases with decreasing VOC-NOx ratio and in addition with increasing precursor concentration. A significant underestimation of the decay rate of TMB and thus underestimation of reactivity in the system, consistent with results from previous appraisals of the MCM, was observed. Much higher nitrous acid (HONO) concentrations compared to simulations and expected from chamber characterization experiments were measured during these smog chamber experiments. A light induced NO2 to HONO conversion at the chamber walls is suggested to occur. This photo-enhanced NO2 to HONO conversion with subsequent HONO photolysis enhances the reactivity of the system. After the implementation of this reaction in the model it describes the decay of TMB properly. Nevertheless, the model still over-predicts ozone at a later stage of the experiment. This can be attributed to a too slow removal of NO2. It is also shown that this photo-enhanced HONO formation is not restricted to TMB photo-oxidation but also occurs in other chemical systems (e.g. α-pinene). However, the influence of HONO as a source of OH radicals is less important in these more reactive systems and therefore the importance of the HONO chemistry is less obvious.

scholarly journals Evaluation of the chemical composition of gas- and particle-phase products of aromatic oxidation

2020 ◽  
Vol 20 (16) ◽  
pp. 9783-9803
Author(s):  
Archit Mehra ◽  
Yuwei Wang ◽  
Jordan E. Krechmer ◽  
Andrew Lambe ◽  
Francesca Majluf ◽  
...  
Keyword(s):  
Gas Phase ◽  
Mass Spectrometer ◽  
Urban Areas ◽  
Minor Component ◽  
Proton Transfer Reaction ◽  
Chemical Mechanism ◽  
Particle Phase ◽  
Experimental Conditions ◽  
Radical Oxidation ◽  
Product Ions

Abstract. Aromatic volatile organic compounds (VOCs) are key anthropogenic pollutants emitted to the atmosphere and are important for both ozone and secondary organic aerosol (SOA) formation in urban areas. Recent studies have indicated that aromatic hydrocarbons may follow previously unknown oxidation chemistry pathways, including autoxidation that can lead to the formation of highly oxidised products. In this study we evaluate the gas- and particle-phase ions measured by online mass spectrometry during the hydroxyl radical oxidation of substituted C9-aromatic isomers (1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, propylbenzene and isopropylbenzene) and a substituted polyaromatic hydrocarbon (1-methylnaphthalene) under low- and medium-NOx conditions. A time-of-flight chemical ionisation mass spectrometer (ToF-CIMS) with iodide–anion ionisation was used with a filter inlet for gases and aerosols (FIGAERO) for the detection of products in the particle phase, while a Vocus proton-transfer-reaction mass spectrometer (Vocus-PTR-MS) was used for the detection of products in the gas phase. The signal of product ions observed in the mass spectra were compared for the different precursors and experimental conditions. The majority of mass spectral product signal in both the gas and particle phases comes from ions which are common to all precursors, though signal distributions are distinct for different VOCs. Gas- and particle-phase composition are distinct from one another. Ions corresponding to products contained in the near-explicit gas phase Master Chemical Mechanism (MCM version 3.3.1) are utilised as a benchmark of current scientific understanding, and a comparison of these with observations shows that the MCM is missing a range of highly oxidised products from its mechanism. In the particle phase, the bulk of the product signal from all precursors comes from ring scission ions, a large proportion of which are more oxidised than previously reported and have undergone further oxidation to form highly oxygenated organic molecules (HOMs). Under the perturbation of OH oxidation with increased NOx, the contribution of HOM-ion signals to the particle-phase signal remains elevated for more substituted aromatic precursors. Up to 43 % of product signal comes from ring-retaining ions including HOMs; this is most important for the more substituted aromatics. Unique products are a minor component in these systems, and many of the dominant ions have ion formulae concurrent with other systems, highlighting the challenges in utilising marker ions for SOA.

scholarly journals Analysis of the chemical composition of organic aerosol at the Mt. Sonnblick observatory using a novel high mass resolution thermal-desorption proton-transfer-reaction mass-spectrometer (hr-TD-PTR-MS)

2010 ◽  
Vol 10 (6) ◽  
pp. 13969-14011 ◽  
Author(s):  
R. Holzinger ◽  
A. Kasper-Giebl ◽  
M. Staudinger ◽  
G. Schauer ◽  
T. Röckmann
Keyword(s):  
Proton Transfer ◽  
Mass Spectrometer ◽  
Thermal Desorption ◽  
Organic Nitrogen ◽  
Transfer Reaction ◽  
Proton Transfer Reaction ◽  
Reaction Mass ◽  
High Mass ◽  
Nitrogen Compounds ◽  
High Mass Resolution

Abstract. For the first time a high mass resolution thermal desorption proton transfer reaction mass spectrometer (hr-TD-PTR-MS) was deployed in the field to analyze the composition of the organic fraction of aerosols. We report on measurements from the remote Mt. Sonnblick observatory in the Austrian alps (3108 m a.s.l.) during a 7 week period in summer 2009. A total of 638 mass peaks in the range 18–392 Da were detected and quantified in aerosols. An empirical formula was tentatively attributed to 464 of these compounds by custom-made data analysis routines which consider compounds containing C, H, O, N, and S atoms. Most of the other (unidentified) compounds must contain other elements – most likely halogenated compounds. The mean total concentration of all detected compounds was 1.1 μg m−3. Oxygenated hydrocarbons constitute the bulk of the aerosol mass (75%) followed by organic nitrogen compounds (9%), inorganic compounds (mostly NH3, 8%), unidentified/halogenated (3.8%), hydrocarbons (2.7%), and organic sulfur compounds (0.8%). The measured O/C ratios are lower than expected and suggest a significant effect from charring. A significant part of the organic nitrogen compounds is non volatile. Organic carbon concentrations measured with TD-PTR-MS were about 25% lower than measurements on high volume filter samples.

scholarly journals Kinetic modeling of formation and evaporation of secondary organic aerosol from NO<sub>3</sub> oxidation of pure and mixed monoterpenes

2020 ◽  
Vol 20 (24) ◽  
pp. 15513-15535
Author(s):  
Thomas Berkemeier ◽  
Masayuki Takeuchi ◽  
Gamze Eris ◽  
Nga L. Ng
Keyword(s):  
Kinetic Model ◽  
Gas Phase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Chemical Mechanism ◽  
Phase Reaction ◽  
Particle Phase ◽  
Environmental Chamber ◽  
Gas Phase Chemistry ◽  
Phase Chemistry

Abstract. Organic aerosol constitutes a major fraction of the global aerosol burden and is predominantly formed as secondary organic aerosol (SOA). Environmental chambers have been used extensively to study aerosol formation and evolution under controlled conditions similar to the atmosphere, but quantitative prediction of the outcome of these experiments is generally not achieved, which signifies our lack in understanding of these results and limits their portability to large-scale models. In general, kinetic models employing state-of-the-art explicit chemical mechanisms fail to describe the mass concentration and composition of SOA obtained from chamber experiments. Specifically, chemical reactions including the nitrate radical (NO3) are a source of major uncertainty for assessing the chemical and physical properties of oxidation products. Here, we introduce a kinetic model that treats gas-phase chemistry, gas–particle partitioning, particle-phase oligomerization, and chamber vapor wall loss and use it to describe the oxidation of the monoterpenes α-pinene and limonene with NO3. The model can reproduce aerosol mass and nitration degrees in experiments using either pure precursors or their mixtures and infers volatility distributions of products, branching ratios of reactive intermediates and particle-phase reaction rates. The gas-phase chemistry in the model is based on the Master Chemical Mechanism (MCM) but trades speciation of single compounds for the overall ability of quantitatively describing SOA formation by using a lumped chemical mechanism. The complex branching into a multitude of individual products in MCM is replaced in this model with product volatility distributions and detailed peroxy (RO2) and alkoxy (RO) radical chemistry as well as amended by a particle-phase oligomerization scheme. The kinetic parameters obtained in this study are constrained by a set of SOA formation and evaporation experiments conducted in the Georgia Tech Environmental Chamber (GTEC) facility. For both precursors, we present volatility distributions of nitrated and non-nitrated reaction products that are obtained by fitting the kinetic model systematically to the experimental data using a global optimization method, the Monte Carlo genetic algorithm (MCGA). The results presented here provide new mechanistic insight into the processes leading to formation and evaporation of SOA. Most notably, the model suggests that the observed slow evaporation of SOA could be due to reversible oligomerization reactions in the particle phase. However, the observed non-linear behavior of precursor mixtures points towards a complex interplay of reversible oligomerization and kinetic limitations of mass transport in the particle phase, which is explored in a model sensitivity study. The methodologies described in this work provide a basis for quantitative analysis of multi-source data from environmental chamber experiments but also show that a large data pool is needed to fully resolve uncertainties in model parameters.

scholarly journals Development and chamber evaluation of the MCM v3.2 degradation scheme for β-caryophyllene

2012 ◽  
Vol 12 (1) ◽  
pp. 2891-2974 ◽  
Author(s):  
M. E. Jenkin ◽  
K. P. Wyche ◽  
C. J. Evans ◽  
T. Carr ◽  
P. S. Monks ◽  
...  
Keyword(s):  
Gas Phase ◽  
Degradation Mechanism ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Oh Radicals ◽  
Photo Oxidation ◽  
Primary Yield ◽  
Chamber Studies ◽  
The Impact ◽  
Tof Ms

Abstract. A degradation mechanism for β-caryophyllene has recently been released as part of version 3.2 of the Master Chemical Mechanism (MCM v3.2), describing the gas phase oxidation initiated by reaction with ozone, OH radicals and NO3 radicals. A detailed overview of the construction methodology is given, within the context of reported experimental and theoretical mechanistic appraisals. The performance of the mechanism has been evaluated in chamber simulations in which the gas phase chemistry was coupled to a representation of the gas-to-aerosol partitioning of 280 multi-functional oxidation products. This evaluation exercise considered data from a number of chamber studies of either the ozonolysis of β-caryophyllene, or the photo-oxidation of β-caryophyllene/NOx mixtures, in which detailed product distributions have been reported. This includes the results of a series of photo-oxidation experiments performed in the University of Manchester aerosol chamber, also reported here, in which a comprehensive characterization of the temporal evolution of the organic product distribution in the gas phase was carried out, using Chemical Ionisation Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS), in conjunction with measurements of NOx, O3 and SOA mass loading. The CIR-TOF-MS measurements allowed approximately 45 time-resolved product ion signals to be detected, which were assigned on the basis of the simulated temporal profiles of the more abundant MCM v3.2 species, and their probable fragmentation patterns. The evaluation studies demonstrate that the MCM v3.2 mechanism provides a generally acceptable description of β-caryophyllene degradation, under the chamber conditions considered, and a reliable basis for simulations where a representation of chemical detail is required. The studies have also highlighted a number of areas of uncertainty, where further investigation would be valuable to help interpret the results of chamber studies and improve detailed mechanistic understanding. These particularly include: (i) quantification of the yield and stability of the secondary ozonide (denoted BCSOZ in MCM v3.2), formed from β-caryophyllene ozonolysis, and elucidation of the details of its further oxidation, including whether the products retain the "ozonide" functionality; (ii) investigation of the impact of NOx on the β-caryophyllene ozonolysis mechanism, in particular its effect on the formation of β-caryophyllinic acid (denoted C137CO2H in MCM v3.2), and elucidation of its formation mechanism; (iii) routine independent identification of β-caryophyllinic acid, and its potentially significant isomer β-nocaryophyllonic acid (denoted C131CO2H in MCM v3.2); (iv) more precise quantification of the primary yield of OH (and other radicals) from β-caryophyllene ozonolysis; (v) quantification of the yields of the first-generation hydroxy nitrates (denoted BCANO3, BCBNO3 and BCCNO3 in MCM v3.2) from the OH-initiated chemistry in the presence of NOx; and (vi) further studies in general to improve the identification and quantification of products formed from both ozonolysis and photo-oxidation, including confirmation of the simulated formation of multifunctional species containing hydroperoxide groups, and their important contribution to SOA under NOx-free conditions.

scholarly journals Analysis of the chemical composition of organic aerosol at the Mt. Sonnblick observatory using a novel high mass resolution thermal-desorption proton-transfer-reaction mass-spectrometer (hr-TD-PTR-MS)

2010 ◽  
Vol 10 (20) ◽  
pp. 10111-10128 ◽  
Author(s):  
R. Holzinger ◽  
A. Kasper-Giebl ◽  
M. Staudinger ◽  
G. Schauer ◽  
T. Röckmann
Keyword(s):  
Proton Transfer ◽  
Mass Spectrometer ◽  
Thermal Desorption ◽  
Transfer Reaction ◽  
Proton Transfer Reaction ◽  
Reaction Mass ◽  
Mass Resolution ◽  
High Mass ◽  
High Mass Resolution ◽  
Custom Made

Abstract. For the first time a high mass resolution thermal desorption proton transfer reaction mass spectrometer (hr-TD-PTR-MS) was deployed in the field to analyze the composition of the organic fraction of aerosols. We report on measurements from the remote Mt. Sonnblick observatory in the Austrian alps (3108 m a.s.l.) during a 7 week period in summer 2009. A total of 638 mass peaks in the range 18–392 Da were detected and quantified in aerosols. An empirical formula was tentatively attributed to 464 of these compounds by custom-made data analysis routines which consider compounds containing C, H, O, N, and S atoms. Most of the other (unidentified) compounds must contain other elements – most likely halogenated compounds. The mean total concentration of all detected compounds was 1.1 μg m−3. Oxygenated hydrocarbons constitute the bulk of the aerosol mass (75%) followed by organic nitrogen compounds (9%), inorganic compounds (mostly NH3, 8%), unidentified/halogenated (3.8%), hydrocarbons (2.7%), and organic sulfur compounds (0.8%). The measured O/C ratios are lower than expected and suggest a significant effect from charring. Organic carbon concentrations measured with TD-PTR-MS were about 25% lower than measurements on high volume filter samples.

scholarly journals Kinetic modelling of formation and evaporation of SOA from NO<sub>3</sub> oxidation of pure and mixed monoterpenes

2020 ◽  
Author(s):  
Thomas Berkemeier ◽  
Masayuki Takeuchi ◽  
Gamze Eris ◽  
Nga L. Ng
Keyword(s):  
Kinetic Model ◽  
Gas Phase ◽  
Organic Aerosol ◽  
Chemical Mechanism ◽  
Phase Reaction ◽  
Particle Phase ◽  
Aerosol Formation ◽  
Environmental Chamber ◽  
Gas Phase Chemistry ◽  
Phase Chemistry

Abstract. Organic aerosol constitutes a major fraction of the global aerosol burden and is predominantly formed as secondary organic aerosol (SOA). Environmental chambers have been used extensively to study aerosol formation and evolution under controlled conditions similar to the atmosphere, but quantitative prediction of the outcome of these experiments is generally not achieved, which signifies our lack in understanding of these results and limits their portability to large scale models. In general, kinetic models employing state-of-the-art explicit chemical mechanisms fail to describe the mass concentration and composition of SOA obtained from chamber experiments. Specifically, chemical reactions involving nitrate radical (NO3) oxidation of volatile organic compounds (VOCs) are a source of major uncertainty for assessing the chemical and physical properties of oxidation products. Here, we introduce a kinetic model that treats gas-phase chemistry, gas-particle partitioning, particle-phase oligomerization, and chamber wall loss and use it to describe the oxidation of the monoterpenes α-pinene and limonene with NO3. The model can reproduce aerosol mass and nitration degrees in experiments using either pure precursors or their mixtures and infers volatility distributions of products, branching ratios of reactive intermediates as well as particle-phase reaction rates. The gas-phase chemistry in the model is based on the Master Chemical Mechanism (MCM), but trades speciation of single compounds for the overall ability of quantitatively describing SOA formation by using a lumped chemical mechanism. The complex branching into a multitude of individual products in MCM is replaced in this model with product volatility distributions, detailed peroxy (RO2) and alkoxy (RO) radical chemistry and amended by a particle-phase oligomerization scheme. The kinetic parameters obtained in this study are constrained by a set of SOA formation and evaporation experiments conducted in the Georgia Tech Environmental Chamber (GTEC) facility. For both precursors, we present volatility distributions of nitrated and non-nitrated reaction products that are obtained by fitting the kinetic model systematically to the experimental data using a global optimization method, the Monte Carlo Genetic Algorithm (MCGA). The results presented here provide new mechanistic insight into the processes leading to formation and evaporation of SOA. Most notably, much of the non-linear behavior of precursor mixtures can be understood by RO2 fate and reversible oligomerization reactions in the particle phase, but some effects could be accredited to kinetic limitations of mass transport in the particle phase. The methodologies described in this work provide a basis for quantitative analysis of multi-source data from environmental chamber experiments with manageable computational effort.

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