scholarly journals Pyruvic acid, an efficient catalyst in SO<sub>3</sub> hydrolysis and effective clustering agent in sulfuric acid-based new particle formation

2021 ◽  
Author(s):  
Narcisse Tsona Tchinda ◽  
Lin Du ◽  
Ling Liu ◽  
Xiuhui Zhang
Keyword(s):  
Sulfuric Acid ◽  
Aerosol Particle ◽  
Pyruvic Acid ◽  
Cluster Formation ◽  
Formation Rate ◽  
Hydrolysis Product ◽  
Particle Formation ◽  
Free Energy Barrier ◽  
Aerosol Formation ◽  
Net Flux

Abstract. The role of pyruvic acid (PA), one of the most abundant α-keto carboxylic acids in the atmosphere, was investigated both in the SO3 hydrolysis reaction to form sulfuric acid (SA) and in SA-based aerosol particle formation using quantum chemical calculations and a cluster dynamics model. We found that the PA-catalyzed SO3 hydrolysis is a thermodynamically driven transformation process, proceeding with a negative Gibbs free energy barrier, ca. −1 kcal mol−1 at 298 K, ~6.50 kcal mol−1 lower than that in the water-catalyzed SO3 hydrolysis. Results indicated that the PA-catalyzed reaction can potentially compete with the water-catalyzed SO3 reaction in SA production, especially in dry and polluted areas, where it is found to be ~two orders of magnitude more efficient that the water-catalyzed reaction. Given the effective stabilization of the PA-catalyzed SO3 hydrolysis product as SA•PA cluster, we proceeded to examine the PA clustering efficiency in sulfuric acid-pyruvic acid-ammonia (SA-PA-NH3) system. Our thermodynamic data used in the Atmospheric Cluster Dynamics Code indicated that under relevant tropospheric temperatures and concentrations of SA (106 cm3), PA (1010 cm3) and NH3 (1011 and 5 × 1011 cm3), of the PA-containing clusters, only clusters with one PA molecule, namely (SA)2•PA•(NH3)2, can participate to the particle formation, contributing by ~100 % to the net flux to aerosol particle formation at 238 K, exclusively. At higher temperatures (258 K and 278 K), however, the net flux to the particle formation is dominated by pure SA-NH3 clusters, while PA would rather evaporate from the clusters at high temperatures and not contribute to the particle formation. The enhancing effect of PA of examined by evaluating the ratio of the ternary SA-PA-NH3 cluster formation rate to binary SA-NH3 cluster formation rate. Our results show that while the enhancement factor of PA to the particle formation rate is almost insensitive to investigated temperatures and concentrations, it can be as high as 4.7 × 102 at 238 K and [NH3] = 1.3 × 1011 molecule cm−3. This indicates that PA may actively participate in aerosol formation, only in cold regions of the troposphere and highly NH3-polluted environments. The inclusion of this mechanism in aerosol models may definitely reduce uncertainties that prevail in modeling the aerosol impact on climate.

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

2016 ◽  
Vol 16 (4) ◽  
pp. 1955-1970 ◽  
Author(s):  
M. Dal Maso ◽  
L. Liao ◽  
J. Wildt ◽  
A. Kiendler-Scharr ◽  
E. Kleist ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Cloud Condensation Nuclei ◽  
Formation Rate ◽  
Particle Growth ◽  
Oxidation Products ◽  
Aerosol Formation ◽  
Nanoparticle Formation ◽  
Aerosol Nanoparticles ◽  
Chamber Study ◽  
Ambient Concentrations

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 sulfuric acid and nanoparticles, and present the first simultaneous chamber observations of nanoparticles, sulfuric acid, and realistic levels and mixtures of biogenic volatile compounds (BVOCs). We present direct laboratory observations of nanoparticle formation from sulfuric acid and realistic BVOC precursor vapour 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 sulfuric 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 sulfuric acid. The growth rate of nanoparticles immediately after birth was best correlated with estimated products resulting from BVOC ozonolysis.

New Particle Formation Involving Charged Sulfuric Acid – Ammonia Clusters

2020 ◽  
Author(s):  
Vitus Besel ◽  
Jakub Kubečka ◽  
Theo Kurtén ◽  
Hanna Vehkamäki
Keyword(s):  
Sulfuric Acid ◽  
Computational Study ◽  
Cluster Formation ◽  
Chem Phys ◽  
Particle Formation ◽  
Empirical Method ◽  
Particle Nucleation ◽  
New Particle Formation ◽  
Charged Clusters ◽  
Ammonia Clusters

&lt;div&gt; &lt;p&gt;The bulk of aerosol particles in the atmosphere are formed by gas-to-particle nucleation (Merikanto et al., 2009). However, the exact process of single molecules forming cluster, which subsequently can grow into particles, remains largely unknown. Recently, sulfuric acid has been identified to play a key role in this new particle formation enhanced by other compounds such as organic acids (Zhang, 2010) or ammonia (Anttila et al., 2005). To identify the characteristics of cluster formation and nucleation involving sulfuric acid and ammonia in neutral, positive and negative modes, we conducted a computational study. We used a layered approach for configurational sampling of the molecular clusters starting from utilizing a genetic algorithm in order to explore the whole potential energy surface (PES) with all plausible geometrical minima, however, with very unreliable energies. The structures were further optimized with a semi-empirical method and, then, at the &amp;#969;B97X-D DFT level of theory. After each step, the optimized geometries were filtered to obtain the global minimum configuration. Further, a high level of theory (DLPNO-CCSD(T)) was used for obtaining the electronic energies, in addition to performing DFT frequency analysis, to calculate the Gibbs free energies of formation. These were passed to the Atmospheric Cluster Dynamics Code (ACDC) (McGrath et al., 2012) for studying the evolution of cluster populations. We determined the global minima for the following sulfuric acid - ammonia clusters: (H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;m&lt;/sub&gt;(NH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;n&lt;/sub&gt; with m=n, m=n+1 and n=m+1 for neutral clusters, (H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;m&lt;/sub&gt;(HSO&lt;sub&gt;4&lt;/sub&gt;)&lt;sup&gt;&amp;#8722;&lt;/sup&gt;(NH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;n&lt;/sub&gt; with m=n and n=m+1 for positively charged clusters, and (H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;m&lt;/sub&gt;(NH&lt;sub&gt;4&lt;/sub&gt;)&lt;sup&gt;+&lt;/sup&gt;(NH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;n&lt;/sub&gt; with m=n and m=n+1 for negatively charged clusters. Further, we present the formation rates, steady state concentrations and fluxes of these clusters calculated using ACDC and discuss how a new configurational sampling procedure, more precise quantum chemistry methods and parameters, such as symmetry and a quasiharmonic approach, impact these ACDC results in comparison to previous studies.&lt;/p&gt; &lt;/div&gt;&lt;div&gt; &lt;p&gt;&lt;em&gt;References:&lt;br&gt;&lt;/em&gt;&lt;em&gt;J. Merikanto, D. V. Spracklen, G. W. Mann, S. J. Pickering, and K. S. Carslaw (2009). Atmos. Chem.&amp;#160; Phys., 9, 8601-8616. &lt;br&gt;R. Zhang (2010). Science, 328, 1366-1367. &lt;br&gt;T. Anttila, H. Vehkam&amp;#228;ki, I. Napari, M. Kulmala (2005). Boreal Env. Res., 10, 523. &lt;br&gt;M.J. McGrath, T. Olenius, I.K. Ortega, V. Loukonen, P.&amp;#160; Paasonen, T. Kurten, M. Kulmala (2012). Atmos. Chem. Phys., 12, 2355. &lt;br&gt;&lt;/em&gt;&lt;/p&gt; &lt;/div&gt;

scholarly journals The roles of sulfuric acid in new particle formation and growth in the mega-city of Beijing

2010 ◽  
Vol 10 (10) ◽  
pp. 4953-4960 ◽  
Author(s):  
D. L. Yue ◽  
M. Hu ◽  
R. Y. Zhang ◽  
Z. B. Wang ◽  
J. Zheng ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Organic Compounds ◽  
Dominant Role ◽  
Formation Rate ◽  
Particle Growth ◽  
Particle Formation ◽  
New Particle Formation ◽  
Average Formation ◽  
Subsequent Neutralization

Abstract. Simultaneous measurements of gaseous sulfuric acid and particle number size distributions were performed to investigate aerosol nucleation and growth during CAREBeijing-2008. The analysis of the measured aerosols and sulfuric acid with an aerosol dynamic model shows the dominant role of sulfuric acid in new particle formation (NPF) process but also in the subsequent growth in Beijing. Based on the data of twelve NPF events, the average formation rates (2–13 cm−3 s−1) show a linear correlation with the sulfuric acid concentrations (R2=0.85). Coagulation seems to play a significant role in reducing the number concentration of nucleation mode particles with the ratio of the coagulation loss to formation rate being 0.41±0.16. The apparent growth rates vary from 3 to 11 nm h−1. Condensation of sulfuric acid and its subsequent neutralization by ammonia and coagulation contribute to the apparent particle growth on average 45±18% and 34±17%, respectively. The 30% higher concentration of sulfate than organic compounds in particles during the seven sulfur-rich NPF events but 20% lower concentration of sulfate during the five sulfur-poor type suggest that organic compounds are an important contributor to the growth of the freshly nucleated particles, especially during the sulfur-poor cases.

Composition and concentrations of aerosol precursor gases in the sub-Arctic boreal forest

2021 ◽  
Author(s):  
Tuija Jokinen ◽  
Katrianne Lehtipalo ◽  
Kimmo Neitola ◽  
Nina Sarnela ◽  
Totti Laitinen ◽  
...  
Keyword(s):  
Seasonal Variation ◽  
Sulfuric Acid ◽  
Ambient Air ◽  
Particle Formation ◽  
The Arctic ◽  
New Particle Formation ◽  
Aerosol Formation ◽  
Iodic Acid ◽  
Field Station

&lt;p&gt;One way to form aerosol particles is the condensation of oxidized atmospheric trace gases, such as sulfuric acid (SA) into small molecular clusters. After growing to larger particles by condensation of low volatile gases, they can affect the planets climate directly by scattering light and indirectly by acting as cloud condensation nuclei. Observations of low-volatility aerosol precursor gases have been reported around the world but long-term measurement series and Arctic data sets showing seasonal variation are close to non-existent. In here, we present ~7 months of aerosol precursor gas measurements performed with the nitrate based chemical ionization mass spectrometer (CI-APi-TOF). We deployed our measurements ~250 km above the Arctic Circle at the Finnish sub-Arctic field station, SMEAR I in V&amp;#228;rri&amp;#246;. We report concentration measurements of the most common new particle formation related compounds; sulfuric acid, methanesulfonic acid (MSA), iodic acid (IA) and highly oxygenated organic compounds, HOMs. At this remote measurement site, surrounded by a strict nature preserve, that gets occasional pollution from a Russian city of Murmansk, SA is originated both from anthropogenic and biological sources and has a clear diurnal cycle but no significant seasonal variation, while MSA as an oxidation product of purely biogenic sources is showing a more distinct seasonal cycle. Iodic acid concentrations are the most stable throughout the measurement period, showing almost identical peak concentrations for spring, summer and autumn. HOMs are abundant during the summer months and due to their high correlation with ambient air temperature, we suggest that most of HOMs are products of monoterpene oxidation. New particle formation events at SMEAR I happen under relatively low temperatures, low relative humidity, high ozone concentration, high SA concentration in the morning and high MSA concentrations in the afternoon. The role of HOMs in aerosol formation will be discussed. All together, these are the first long term measurements of aerosol forming precursor from the sub-arctic region helping us to understand atmospheric chemical processes and aerosol formation in the rapidly changing Arctic.&lt;/p&gt;&lt;p&gt;&amp;#160;&lt;/p&gt;&lt;p&gt;&amp;#160;&lt;/p&gt;

scholarly journals Observation of aerosol size distribution and new particle formation at a mountain site in subtropical Hong Kong

2012 ◽  
Vol 12 (20) ◽  
pp. 9923-9939 ◽  
Author(s):  
H. Guo ◽  
D. W. Wang ◽  
K. Cheung ◽  
Z. H. Ling ◽  
C. K. Chan ◽  
...  
Keyword(s):  
Growth Rate ◽  
Hong Kong ◽  
Sulfuric Acid ◽  
Size Distribution ◽  
Formation Rate ◽  
Particle Formation ◽  
Aerosol Size Distribution ◽  
New Particle Formation ◽  
Average Growth ◽  
Nucleation Mode

Abstract. In order to investigate the formation and growth processes of nucleation mode particles, and to quantify the particle number (PN) concentration and size distributions in Hong Kong, an intensive field measurement was conducted from 25 October to 29 November in 2010 near the mountain summit of Tai Mo Shan, a suburban site approximately the geographical centre of the New Territories in Hong Kong. Based on observations of the particle size distribution, new particle formation (NPF) events were found on 12 out of 35 days with the estimated formation rate J5.5 from 0.97 to 10.2 cm−3 s−1, and the average growth rates from 1.5 to 8.4 nm h−1. The events usually began at 10:00–11:00 LT characterized by the occurrence of a nucleation mode with a peak diameter of 6–10 nm. Solar radiation, wind speed, sulfur dioxide (SO2) and ozone (O3) concentrations were on average higher, whereas temperature, relative humidity and daytime nitrogen dioxide (NO2) concentration were lower on NPF days than on non-NPF days. Back trajectory analysis suggested that in majority of the NPF event days, the air masses originated from the northwest to northeast directions. The concentrations of gaseous sulfuric acid (SA) showed good power-law relationship with formation rates, with exponents ranging from 1 to 2. The result suggests that the cluster activation theory and kinetic nucleation could potentially explain the observed NPF events in this mountainous atmosphere of Hong Kong. Meanwhile, in these NPF events, the contribution of sulfuric acid vapor to particle growth rate (GR5.5–25) ranged from 9.2 to 52.5% with an average of 26%. Measurement-based calculated oxidation rates of monoterpenes (i.e. α-pinene, β-pinene, myrcene and limonene) by O3 positively correlated with the GR5.5–25 (R = 0.80, p < 0.05). The observed associations of the estimated formation rate J5.5 and the growth rate GR5.5–25 with gaseous sulfuric acid and volatile organic compounds (VOCs) suggested the critical roles of sulfuric acid and biogenic VOCs (e.g. α-pinene and β-pinene) in these NPF events.

scholarly journals Trends in new particle formation in eastern Lapland, Finland: effect of decreasing sulfur emissions from Kola Peninsula

2014 ◽  
Vol 14 (9) ◽  
pp. 4383-4396 ◽  
Author(s):  
E.-M. Kyrö ◽  
R. Väänänen ◽  
V.-M. Kerminen ◽  
A. Virkkula ◽  
T. Petäjä ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Kola Peninsula ◽  
Formation Rate ◽  
Particle Formation ◽  
The Arctic ◽  
Late Winter ◽  
Rapid Decline ◽  
New Particle Formation ◽  
Sulfur Species ◽  
Sulfur Emissions

Abstract. The smelter industry in Kola Peninsula is the largest source of anthropogenic SO2 in the Arctic part of Europe and one of the largest within the Arctic domain. Due to socio-economic changes in Russia, the emissions have been decreasing especially since the late 1990s resulting in decreased SO2 concentrations close to Kola in eastern Lapland, Finland. At the same time, the frequency of new particle formation days has been decreasing distinctively at SMEAR I station in eastern Lapland, especially during spring and autumn. We show that sulfur species, namely sulfur dioxide and sulfuric acid, have an important role in both new particle formation and subsequent growth and that the decrease in new particle formation days is a result of the reduction of sulfur emissions originating from Kola Peninsula. In addition to sulfur species, there are many other quantities, such as formation rate of aerosol particles, condensation sink and nucleation mode particle number concentration, which are related to the number of observed new particle formation (NPF) days and need to be addressed when linking sulfur emissions and NPF. We show that while most of these quantities exhibit statistically significant trends, the reduction in Kola sulfur emissions is the most obvious reason for the rapid decline in NPF days. Sulfuric acid explains approximately 20–50% of the aerosol condensational growth observed at SMEAR I, and there is a large seasonal variation with highest values obtained during spring and autumn. We found that (i) particles form earlier after sunrise during late winter and early spring due to high concentrations of SO2 and H2SO4; (ii) several events occurred during the absence of light, and they were connected to higher than average concentrations of SO2; and (iii) high SO2 concentrations could advance the onset of nucleation by several hours. Moreover, air masses coming over Kola Peninsula seemed to favour new particle formation.

scholarly journals Influence of atmospheric conditions on the role of trifluoroacetic acid in atmospheric sulfuric acid–dimethylamine nucleation

2021 ◽  
Vol 21 (8) ◽  
pp. 6221-6230
Author(s):  
Ling Liu ◽  
Fangqun Yu ◽  
Kaipeng Tu ◽  
Zhi Yang ◽  
Xiuhui Zhang
Keyword(s):  
Sulfuric Acid ◽  
Trifluoroacetic Acid ◽  
Density Functional ◽  
Cluster Formation ◽  
Formation Rate ◽  
Urban Environments ◽  
Nucleation Process ◽  
Atmospheric Conditions ◽  
Wide Range

Abstract. Ambient measurements combined with theoretical simulations have shown evidence that the tropospheric degradation end-products of Freon alternatives, trifluoroacetic acid (TFA), one of the most important and abundant atmospheric organic substances, can enhance the nucleation process based on sulfuric acid (SA) and dimethylamine (DMA) in urban environments. However, TFA is widespread all over the world under different atmospheric conditions, such as temperature and nucleation precursor concentration, which are the most important factors potentially influencing the atmospheric nucleation process and thus inducing different nucleation mechanisms. Herein, using the density functional theory combined with the Atmospheric Cluster Dynamics Code, the influence of temperature and nucleation precursor concentrations on the role of TFA in the SA–DMA nucleation has been investigated. The results indicate that the growth trends of clusters involving TFA can increase with the decrease in temperature. The enhancement on particle formation rate by TFA and the contributions of the SA–DMA–TFA cluster to the cluster formation pathways can be up to 227-fold and 95 %, respectively, at relatively low temperature, low SA concentration, high TFA concentration, and high DMA concentration, such as in winter, at the relatively high atmospheric boundary layer, or in megacities far away from industrial sources of sulfur-containing pollutants. These results provide the perspective of the realistic role of TFA in different atmospheric environments, revealing the potential influence of the tropospheric degradation of Freon alternatives under a wide range of atmospheric conditions.

scholarly journals A look at aerosol formation using data mining techniques

2005 ◽  
Vol 5 (12) ◽  
pp. 3345-3356 ◽  
Author(s):  
S. Hyvönen ◽  
H. Junninen ◽  
L. Laakso ◽  
M. Dal Maso ◽  
T. Grönholm ◽  
...  
Keyword(s):  
Data Mining ◽  
Relative Humidity ◽  
Aerosol Particle ◽  
Atmospheric Aerosol ◽  
Particle Surface ◽  
Particle Formation ◽  
High Water Content ◽  
Aerosol Formation ◽  
Data Mining Techniques ◽  
Condensation Sink

Abstract. Atmospheric aerosol particle formation is frequently observed throughout the atmosphere, but despite various attempts of explanation, the processes behind it remain unclear. In this study data mining techniques were used to find the key parameters needed for atmospheric aerosol particle formation to occur. A dataset of 8 years of 80 variables collected at the boreal forest station (SMEAR II) in Southern Finland was used, incorporating variables such as radiation, humidity, SO2, ozone and present aerosol surface area. This data was analyzed using clustering and classification methods. The aim of this approach was to gain new parameters independent of any subjective interpretation. This resulted in two key parameters, relative humidity and preexisting aerosol particle surface (condensation sink), capable in explaining 88% of the nucleation events. The inclusion of any further parameters did not improve the results notably. Using these two variables it was possible to derive a nucleation probability function. Interestingly, the two most important variables are related to mechanisms that prevent the nucleation from starting and particles from growing, while parameters related to initiation of particle formation seemed to be less important. Nucleation occurs only with low relative humidity and condensation sink values. One possible explanation for the effect of high water content is that it prevents biogenic hydrocarbon ozonolysis reactions from producing sufficient amounts of low volatility compounds, which might be able to nucleate. Unfortunately the most important biogenic hydrocarbon compound emissions were not available for this study. Another effect of water vapour may be due to its linkage to cloudiness which may prevent the formation of nucleating and/or condensing vapours. A high number of preexisting particles will act as a sink for condensable vapours that otherwise would have been able to form sufficient supersaturation and initiate the nucleation process.

scholarly journals The Hohenpeissenberg aerosol formation experiment (HAFEX): a long-term study including size-resolved aerosol, H<sub>2</sub>SO<sub>4</sub>, OH, and monoterpenes measurements

2003 ◽  
Vol 3 (2) ◽  
pp. 361-376 ◽  
Author(s):  
W. Birmili ◽  
H. Berresheim ◽  
C. Plass-Dülmer ◽  
T. Elste ◽  
S. Gilge ◽  
...  
Keyword(s):  
Formation Rate ◽  
Particle Surface ◽  
Particle Growth ◽  
Cold Season ◽  
Particle Formation ◽  
Oxidation Products ◽  
Aerosol Formation ◽  
Particle Surface Area ◽  
Nucleation Mode ◽  
Long Term Study

Abstract. Ambient aerosol size distributions (>3 nm) and OH, H2SO4, and terpene concentrations were measured from April 1998 to August 2000 at a rural continental site in southern Germany. New particle formation (NPF) events were detected on 18% of all days, typically during midday hours under sunny and dry conditions. The number of newly formed particles correlated significantly with solar irradiance and ambient levels of H2SO4. A pronounced anti-correlatation of NPF events with the pre-existing particle surface area was identified in the cold season, often associated with the advection of dry and relatively clean air masses from southerly directions (Alps). Estimates of the particle formation rate based on observations were around 1 cm-3 s-1, being in agreement with the predictions of ternary homogeneous H2SO4-NH3-H2O nucleation within a few orders of magnitude. The experimentally determined nucleation mode particle growth rates were on average 2.6 nm h-1, with a fraction of 0.7 nm h-1 being attributed to the co-condensation of H2SO4-H2O-NH3. The magnitude of nucleation mode particle growth was neither significantly correlated to H2SO4, nor to the observed particle formation rate. Turn-over rate calculations of measured monoterpenes and aromatic hydrocarbons suggest that especially the oxidation products of monoterpenes have the capacity to contribute to the growth of nucleation mode particles. Although a large number of precursor gases, aerosol and meteorological parameters were measured, the ultimate key factors controlling the occurence of NPF events could not be identified.

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