scholarly journals Measurement-model comparison of stabilized Criegee Intermediate and Highly Oxygenated Molecule production in the CLOUD chamber

2017 ◽  
Author(s):  
Nina Sarnela ◽  
Tuija Jokinen ◽  
Jonathan Duplissy ◽  
Chao Yan ◽  
Tuomo Nieminen ◽  
...  
Keyword(s):  
Sulphuric Acid ◽  
Model Comparison ◽  
Cloud Condensation Nuclei ◽  
Measurement Model ◽  
Cloud Chamber ◽  
Oxidation Products ◽  
Atmospheric Oxidation ◽  
European Organization ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

Abstract. Atmospheric oxidation is an important phenomenon, which produces large quantities of low-volatile compounds such as sulphuric acid and oxidised organic compounds. Such species may be involved in nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate α-pinene, the most abundant monoterpene globally, and its oxidation products formed through the ozonolysis in the Cosmic Leaving OUtdoors Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H2), we were able to investigate the formation of Highly Oxygenated Molecules (HOM) purely driven by ozonolysis, and study the oxidation of sulphur dioxide (SO2) driven by stabilized Criegee Intermediates (sCI). We measured the concentrations of HOM and sulphuric 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 dynamic model. We found molar yields in the range of 3.5–6.5 % for the HOM formation and 22–32 % for the formation of stabilized Criegee Intermediates by fitting our model to the measured concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulphuric acid formation was faster than simulated. 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 to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.

scholarly journals Measurement–model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber

2018 ◽  
Vol 18 (4) ◽  
pp. 2363-2380 ◽  
Author(s):  
Nina Sarnela ◽  
Tuija Jokinen ◽  
Jonathan Duplissy ◽  
Chao Yan ◽  
Tuomo Nieminen ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Model Comparison ◽  
Cloud Condensation Nuclei ◽  
Measurement Model ◽  
Cloud Chamber ◽  
Oxidation Products ◽  
Atmospheric Oxidation ◽  
European Organization ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

Abstract. 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 α-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 (H2), 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.

scholarly journals Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO<sub>2</sub> and organic acids

2014 ◽  
Vol 14 (22) ◽  
pp. 12143-12153 ◽  
Author(s):  
M. Sipilä ◽  
T. Jokinen ◽  
T. Berndt ◽  
S. Richters ◽  
R. Makkonen ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Relative Humidity ◽  
Organic Acids ◽  
Rate Coefficient ◽  
Atmospheric Oxidation ◽  
Minor Importance ◽  
General Role ◽  
Oxidation Processes ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

Abstract. Oxidation processes in Earth's atmosphere are tightly connected to many environmental and human health issues and are essential drivers for biogeochemistry. Until the recent discovery of the atmospheric relevance of the reaction of stabilized Criegee intermediates (sCIs) with SO2, atmospheric oxidation processes were thought to be dominated by a few main oxidants: ozone, hydroxyl radicals (OH), nitrate radicals and, e.g. over oceans, halogen atoms such as chlorine. Here, we report results from laboratory experiments at 293 K and atmospheric pressure focusing on sCI formation from the ozonolysis of isoprene and the most abundant monoterpenes (α-pinene and limonene), and subsequent reactions of the resulting sCIs with SO2 producing sulfuric acid (H2SO4). The measured total sCI yields were (0.15 ± 0.07), (0.27 ± 0.12) and (0.58 ± 0.26) for α-pinene, limonene and isoprene, respectively. The ratio between the rate coefficient for the sCI loss (including thermal decomposition and the reaction with water vapour) and the rate coefficient for the reaction of sCI with SO2, k(loss) /k(sCI + SO2), was determined at relative humidities of 10 and 50%. Observed values represent the average reactivity of all sCIs produced from the individual alkene used in the ozonolysis. For the monoterpene-derived sCIs, the relative rate coefficients k(loss) / k(sCI + SO2) were in the range (2.0–2.4) × 1012 molecules cm−3 and nearly independent of the relative humidity. This fact points to a minor importance of the sCI + H2O reaction in the case of the sCI arising from α-pinene and limonene. For the isoprene sCIs, however, the ratio k(loss) / k(sCI + SO2) was strongly dependent on the relative humidity. To explore whether sCIs could have a more general role in atmospheric oxidation, we investigated as an example the reactivity of acetone oxide (sCI from the ozonolysis of 2,3-dimethyl-2-butene) toward small organic acids, i.e. formic and acetic acid. Acetone oxide was found to react faster with the organic acids than with SO2; k(sCI + acid) / k(sCI + SO2) = (2.8 ± 0.3) for formic acid, and k(sCI + acid) / k(sCI + SO2) = (3.4 ± 0.2) for acetic acid. This finding indicates that sCIs can play a role in the formation and loss of other atmospheric constituents besides SO2.

scholarly journals Evolution of particle composition in CLOUD nucleation experiments

2012 ◽  
Vol 12 (12) ◽  
pp. 31071-31105 ◽  
Author(s):  
H. Keskinen ◽  
A. Virtanen ◽  
J. Joutsensaari ◽  
G. Tsagkogeorgas ◽  
J. Duplissy ◽  
...  
Keyword(s):  
Sulphuric Acid ◽  
Mass Spectrometer ◽  
Volume Fraction ◽  
Cloud Condensation Nuclei ◽  
Time Of Flight ◽  
Particle Diameter ◽  
Particle Growth ◽  
Oxidation Products ◽  
Ion Composition ◽  
Differential Mobility

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 chamber experiments at CERN. The investigation is 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 Zdanovski-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.

scholarly journals Evolution of particle composition in CLOUD nucleation experiments

2013 ◽  
Vol 13 (11) ◽  
pp. 5587-5600 ◽  
Author(s):  
H. Keskinen ◽  
A. Virtanen ◽  
J. Joutsensaari ◽  
G. Tsagkogeorgas ◽  
J. Duplissy ◽  
...  
Keyword(s):  
Sulphuric Acid ◽  
Mass Spectrometer ◽  
Volume Fraction ◽  
Cloud Condensation Nuclei ◽  
Time Of Flight ◽  
Particle Diameter ◽  
Particle Growth ◽  
Oxidation Products ◽  
Ion Composition ◽  
Differential Mobility

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.

scholarly journals Reactivity of stabilized Criegee intermediates (sCI) from isoprene and monoterpene ozonolysis toward SO<sub>2</sub> and organic acids

2014 ◽  
Vol 14 (2) ◽  
pp. 3071-3098 ◽  
Author(s):  
M. Sipilä ◽  
T. Jokinen ◽  
T. Berndt ◽  
S. Richters ◽  
R. Makkonen ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Relative Humidity ◽  
Organic Acids ◽  
Rate Coefficient ◽  
Atmospheric Oxidation ◽  
Minor Importance ◽  
General Role ◽  
Oxidation Processes ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

Abstract. Oxidation processes in Earth's atmosphere are tightly connected to many environmental and human health issues and are essential drivers for biogeochemistry. Until the recent discovery of the atmospheric relevance of stabilized Criegee intermediates (sCI), atmospheric oxidation processes were thought to be dominated by few main oxidants: ozone, hydroxyl radicals (OH), nitrate radicals and, e.g. over oceans, halogen atoms such as chlorine. Here, we report results from laboratory experiments at 293 K and atmospheric pressure focusing on sCI formation from the ozonolysis of isoprene and the most abundant monoterpenes (α-pinene and limonene), and subsequent reactions of the resulting sCIs with SO2 producing sulphuric acid (H2SO4). The measured sCI yields were (0.15 ± 0.07), (0.27 ± 0.12) and (0.58 ± 0.26) for the ozonolysis of α-pinene, limonene and isoprene, respectively. The ratio between the rate coefficient for the sCI loss (including thermal decomposition and the reaction with water vapour) and the rate coefficient for the reaction of sCI with SO2, k(loss) / k(sCI + SO2), was determined at relative humidities of 10% and 50%. Observed values represent the average reactivity of all sCIs produced from the individual alkene used in the ozonolysis. For the monoterpene derived sCIs, the relative rate coefficients k(loss) / k(sCI + SO2) were in the range (2.0–2.4) × 1012 molecule cm−3 and nearly independent on the relative humidity. This fact points to a minor importance of the sCI + H2O reaction in the case of the sCI arising from α-pinene and limonene. For the isoprene sCIs, however, the ratio k(loss) / k(sCI + SO2) was strongly dependent on the relative humidity. To explore whether sCIs could have a more general role in atmospheric oxidation, we investigated as an example the reactivity of acetone oxide (sCI from the ozonolysis of 2,3-dimethyl-2-butene) toward small organic acids, i.e. formic and acetic acid. Acetone oxide was found to react faster with the organic acids than with SO2; k(sCI + acid) / k(sCI + SO2) = (2.8 ± 0.3) for formic acid and k(sCI + acid) / k(sCI + SO2) = (3.4 ± 0.2) for acetic acid. This finding suggests that sCIs can play a role in the formation and loss of several atmospheric constituents besides SO2.

scholarly journals Contribution from biogenic organic compounds to particle growth during the 2010 BEACHON-ROCS campaign in a Colorado temperate needle leaf forest

2015 ◽  
Vol 15 (6) ◽  
pp. 9033-9075 ◽  
Author(s):  
L. Zhou ◽  
R. Gierens ◽  
A. Sogachev ◽  
D. Mogensen ◽  
J. Ortega ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Ultrafine Particles ◽  
Cloud Condensation Nuclei ◽  
Sulfuric Acid Concentration ◽  
Particle Growth ◽  
Reaction Rates ◽  
Oxidation Products ◽  
Growth Step ◽  
Criegee Intermediates ◽  
Western Us

Abstract. New particle formation (NPF) is an important atmospheric phenomenon. During a NPF event, molecular clusters first form by nucleation and then grow further by condensation of vapors. The growth step is crucial because it controls the number of particles that can become cloud condensation nuclei. In order to better understand the influence of biogenic emissions on particle growth, we carried out modeling studies of NPF events during the BEACHON-ROCS campaign at Manitou Experimental Forest Observatory in Colorado, USA. The site is representative of the semi-arid Western US. The implemented chemistry scheme with the latest Criegee intermediates reaction rates underestimates sulfuric acid concentration by 50%, suggesting missing atmospheric sulfuric acid sources. The results emphasize the contribution from biogenic volatile organic compound emissions to particle growth by demonstrating the effects of the oxidation products of monoterpenes and 2-Methyl-3-buten-2-ol (MBO). Monoterpene oxidation products are shown to influence the nighttime particle loadings significantly while their concentrations are insufficient to grow the particles during the day. The growth of ultrafine particles in daytime appears to be closely related to the OH oxidation products of MBO.

scholarly journals A chamber study of the influence of boreal BVOC emissions and sulphuric acid on nanoparticle formation rates at ambient concentrations

2014 ◽  
Vol 14 (22) ◽  
pp. 31319-31360 ◽  
Author(s):  
M. Dal Maso ◽  
L. Liao ◽  
J. Wildt ◽  
A. Kiendler-Scharr ◽  
E. Kleist ◽  
...  
Keyword(s):  
Sulphuric Acid ◽  
Cloud Condensation Nuclei ◽  
Formation Rate ◽  
Particle Growth ◽  
Oxidation Products ◽  
Aerosol Formation ◽  
Nanoparticle Formation ◽  
Aerosol Nanoparticles ◽  
Chamber Study ◽  
Vapor Mixtures

Abstract. Aerosol formation from biogenic and anthropogenic precursor trace gases in continental background areas affects climate via altering the amount of available cloud condensation nuclei. Significant uncertainty still exists regarding the agents controlling the formation of aerosol nanoparticles. We have performed experiments in the Jülich Plant-Atmosphere Simulation Chamber with instrumentation for the detection of sulphuric acid and nanoparticles, and present the first simultaneous chamber observations of nanoparticles, sulphuric acid, and realistic levels and mixtures of biogenic volatile compounds (BVOC). We present direct laboratory observations of nanoparticle formation from sulphuric acid and realistic BVOC precursor vapor mixtures performed at atmospherically relevant concentration levels. We directly measured particle formation rates separately from particle growth rates. From this, we established that in our experiments, the formation rate was proportional to the product of sulphuric acid and biogenic VOC emission strength. The formation rates were consistent with a mechanism in which nucleating BVOC oxidation products are rapidly formed and activate with sulphuric acid. The growth rate of nanoparticles immediately after birth was best correlated with estimated products resulting from BVOC ozonolysis.

scholarly journals Chemistry of stabilized Criegee intermediates in the CLOUD chamber

2013 ◽  
Author(s):  
Nina Sarnela ◽  
Mikko Sipilä ◽  
Tuija Jokinen ◽  
Heikki Junninen ◽  
CLOUD Collaboration
Keyword(s):  
Cloud Chamber ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

scholarly journals Molecular Insights into New Particle Formation in Barcelona, Spain

2020 ◽  
Author(s):  
James Brean ◽  
David C. S. Beddows ◽  
Zongbo Shi ◽  
Brice Temime-Roussel ◽  
Nicolas Marchand ◽  
...  
Keyword(s):  
Sulphuric Acid ◽  
Atmospheric Aerosols ◽  
Radiative Forcing ◽  
Cloud Condensation Nuclei ◽  
Particle Formation ◽  
Oxidation Products ◽  
Acid Water ◽  
Necessary Condition ◽  
New Particle Formation ◽  
High Concentrations

Abstract. Atmospheric aerosols contribute some of the greatest uncertainties to estimates of global radiative forcing, and have significant effects on human health. New particle formation (NPF) is the process by which new aerosols of sub-2 nm diameter form from gas-phase precursors and contributes significantly to particle numbers in the atmosphere, accounting for approximately 50 % of cloud condensation nuclei globally. Here, we study summertime NPF in urban Barcelona in NE Spain. The rate of formation of new particles is seen to increase linearly with sulphuric acid concentration in a manner similar to systems studied in chamber studies involving sulphuric acid, water and dimethylamine (DMA), as well as sulphuric acid, water and the oxidation products of pinanediol. The sulphuric acid dimer : monomer ratio is significantly lower than that seen in experiments involving sulphuric acid and DMA in chambers, indicating that stabilization of sulphuric acid clusters by bases is weaker in this dataset than in chambers, and thus another mechanism, likely involving the plentiful highly oxygenated organic molecules (HOMs) is plausible. The high concentrations of HOMs arise largely from both alkylbenzene and monoterpene oxidation, with the former providing greater concentrations of HOMs due to significant local sources. The concentration of these HOMs shows a dependence on both temperature and precursor VOC concentration. New particle formation without growth past 10 nm is also observed, and on these days the highly oxygenated organic compound concentration is significantly lower than on days with growth, and thus high concentrations of low volatility oxygenated organics appear to be a necessary condition for the growth of newly formed particles in Barcelona. These results are consistent with prior observations of new particle formation in both chambers and the real atmosphere, and these results are likely representative of the urban background of many European Mediterranean cities.

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