scholarly journals Coupling of organic and inorganic aerosol systems and the effect on gas–particle partitioning in the southeastern US

2018 ◽  
Vol 18 (1) ◽  
pp. 357-370 ◽  
Author(s):  
Havala O. T. Pye ◽  
Andreas Zuend ◽  
Juliane L. Fry ◽  
Gabriel Isaacman-VanWertz ◽  
Shannon L. Capps ◽  
...  
Keyword(s):  
Gas Phase ◽  
Organic Compounds ◽  
Thermodynamic Model ◽  
Ambient Air ◽  
Particle Phase ◽  
Organic System ◽  
Pure Species ◽  
Southeastern Us ◽  
Model Predictions ◽  
Total Ammonia

Abstract. Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phases for conditions in the southeastern US during summer 2013. Existing equilibrium models and frameworks were found to be sufficient, although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.6 to 1.8 (ratio of ammonium to 2  ×  sulfate, RN∕2S  ≈  0.8 to 0.9) with approximately 70 % of total ammonia and ammonium (NHx) in the particle. Southeastern Aerosol Research and Characterization Network (SEARCH) gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for AeRosols and Gases in Ambient air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to a factor of 3 overestimate of the nonvolatile cations. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and aerosol mass spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent in the same phase as inorganic constituents, modifying their activity and resulting in a decrease in [H+]air (H+ in µg m−3 air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid–liquid phase separation. In addition, accounting for nonideal mixing modified the pH such that a fully interactive inorganic–organic system had a pH roughly 0.7 units higher than predicted using traditional methods (pH  =  1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O : C  ≥  0.6) compounds including several isoprene-derived tracers as well as levoglucosan but decrease particle-phase partitioning for low O : C, monoterpene-derived species.

scholarly journals Coupling of organic and inorganic aerosol systems and the effect on gas-particle partitioning in the southeastern United States

2017 ◽  
Author(s):  
Havala O. T. Pye ◽  
Andreas Zuend ◽  
Juliane L. Fry ◽  
Gabriel Isaacman-VanWertz ◽  
Shannon L. Capps ◽  
...  
Keyword(s):  
United States ◽  
Gas Phase ◽  
Organic Compounds ◽  
Thermodynamic Model ◽  
Southeastern United States ◽  
Particle Phase ◽  
Organic System ◽  
Pure Species ◽  
Model Predictions ◽  
Total Ammonia

Abstract. Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phase for conditions in the southeastern United States during summer 2013. Existing equilibrium models and frameworks were found to be sufficient although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.6 to 1.8 (Ratio of ammonium to 2 × sulfate, RN/2S ≈ 0.8 to 0.9) with approximately 70 % of total ammonia and ammonium (NHx) in the particle. Southeastern Aerosol Research and Characterization (SEARCH) network gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for Aerosols and Gases in Air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to biases in the nonvolatile cations that resulted from either overestimated emissions and/or underestimated mixing. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and Aerosol Mass Spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent in the same phase as inorganic constituents, modifying their activity and resulting in a decrease in [H+]air (H+ in μg m−3 air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid-liquid phase separation. In addition, accounting for non-ideal mixing modified the pH such that a fully interactive inorganic-organic system had a pH roughly 0.7 units higher than predicted by traditional methods (pH = 1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O : C ≥ 0.6) compounds including several isoprene-derived tracers as well as levoglucosan, but decrease particle-phase partitioning for low O : C, monoterpene-derived species.

scholarly journals Emissions of intermediate-volatility and semi-volatile organic compounds from domestic fuels used in Delhi, India

2021 ◽  
Vol 21 (4) ◽  
pp. 2407-2426 ◽  
Author(s):  
Gareth J. Stewart ◽  
Beth S. Nelson ◽  
W. Joe F. Acton ◽  
Adam R. Vaughan ◽  
Naomi J. Farren ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Municipal Solid Waste ◽  
Solid Waste ◽  
Gas Phase ◽  
Organic Compounds ◽  
Ambient Air ◽  
Emission Factors ◽  
Cow Dung ◽  
Particle Phase ◽  
Volatile Organic

Abstract. Biomass burning emits significant quantities of intermediate-volatility and semi-volatile organic compounds (I/SVOCs) in a complex mixture, probably containing many thousands of chemical species. These components are significantly more toxic and have poorly understood chemistry compared to volatile organic compounds routinely quantified in ambient air; however, analysis of I/SVOCs presents a difficult analytical challenge. The gases and particles emitted during the test combustion of a range of domestic solid fuels collected from across Delhi were sampled and analysed. Organic aerosol was collected onto Teflon (PTFE) filters, and residual low-volatility gases were adsorbed to the surface of solid-phase extraction (SPE) discs. A new method relying on accelerated solvent extraction (ASE) coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC–ToF-MS) was developed. This highly sensitive and powerful analytical technique enabled over 3000 peaks from I/SVOC species with unique mass spectra to be detected. A total of 15 %–100 % of gas-phase emissions and 7 %–100 % of particle-phase emissions were characterised. The method was analysed for suitability to make quantitative measurements of I/SVOCs using SPE discs. Analysis of SPE discs indicated phenolic and furanic compounds were important for gas-phase I/SVOC emissions and levoglucosan to the aerosol phase. Gas- and particle-phase emission factors for 21 polycyclic aromatic hydrocarbons (PAHs) were derived, including 16 compounds listed by the US EPA as priority pollutants. Gas-phase emissions were dominated by smaller PAHs. The new emission factors were measured (mg kg−1) for PAHs from combustion of cow dung cake (615), municipal solid waste (1022), crop residue (747), sawdust (1236), fuelwood (247), charcoal (151) and liquefied petroleum gas (56). The results of this study indicate that cow dung cake and municipal solid waste burning are likely to be significant PAH sources, and further study is required to quantify their impact alongside emissions from fuelwood burning.

scholarly journals Polyfluoroalkyl compounds in the Canadian Arctic atmosphere

2011 ◽  
Vol 8 (4) ◽  
pp. 399 ◽  
Author(s):  
Lutz Ahrens ◽  
Mahiba Shoeib ◽  
Sabino Del Vento ◽  
Garry Codling ◽  
Crispin Halsall
Keyword(s):  
Gas Phase ◽  
Environmental Concern ◽  
Canadian Arctic ◽  
High Volume ◽  
Ambient Air ◽  
Coast Guard ◽  
The Arctic ◽  
Particle Phase ◽  
Method Performance ◽  
Arctic Atmosphere

Environmental contextPerfluoroalkyl compounds are of rising environmental concern because of their ubiquitous distribution in remote regions like the Arctic. The present study quantifies these contaminants in the gas and particle phases of the Canadian Arctic atmosphere. The results demonstrate the important role played by gas–particle partitioning in the transport and fate of perfluoroalkyl compounds in the atmosphere. AbstractPolyfluoroalkyl compounds (PFCs) were determined in high-volume air samples during a ship cruise onboard the Canadian Coast Guard Ship Amundsen crossing the Labrador Sea, Hudson Bay and the Beaufort Sea of the Canadian Arctic. Five PFC classes (i.e. perfluoroalkyl carboxylates (PFCAs), polyfluoroalkyl sulfonates (PFSAs), fluorotelomer alcohols (FTOHs), fluorinated sulfonamides (FOSAs), and sulfonamidoethanols (FOSEs)) were analysed separately in the gas phase collected on PUF/XAD-2 sandwiches and in the particle phase on glass-fibre filters (GFFs). The method performance of sampling, extraction and instrumental analysis were compared between two research groups. The FTOHs were the dominant PFCs in the gas phase (20–138 pg m–3), followed by the FOSEs (0.4–23 pg m–3) and FOSAs (0.5–4.7 pg m–3). The PFCAs could only be quantified in the particle phase with low levels (<0.04–0.18 pg m–3). In the particle phase, the dominant PFC class was the FOSEs (0.3–8.6 pg m–3). The particle-associated fraction followed the general trend of: FOSEs (~25 %) > FOSAs (~9 %) > FTOHs (~1 %). Significant positive correlation between ∑FOSA concentrations in the gas phase and ambient air temperature indicate that cold Arctic surfaces, such as the sea-ice snowpack and surface seawater could be influencing FOSAs in the atmosphere.

scholarly journals Importance of biogenic volatile organic compounds to acyl peroxy nitrates (APN) production in the southeastern US during SOAS 2013

2019 ◽  
Vol 19 (3) ◽  
pp. 1867-1880 ◽  
Author(s):  
Shino Toma ◽  
Steve Bertman ◽  
Christopher Groff ◽  
Fulizi Xiong ◽  
Paul B. Shepson ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Gas Phase ◽  
Organic Compounds ◽  
Model Simulation ◽  
Statistical Correlation ◽  
Organic Nitrates ◽  
Biogenic Volatile Organic Compounds ◽  
The North ◽  
Southeastern Us ◽  
Volatile Organic

Abstract. Gas-phase atmospheric concentrations of peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), and peroxymethacryloyl nitrate (MPAN) were measured on the ground using a gas chromatograph electron capture detector (GC-ECD) during the Southern Oxidants and Aerosols Study (SOAS) 2013 campaign (1 June to 15 July 2013) in Centreville, Alabama, in order to study biosphere–atmosphere interactions. Average levels of PAN, PPN, and MPAN were 169, 5, and 9 pptv, respectively, and the sum accounts for an average of 16 % of NOy during the daytime (10:00 to 16:00 local time). Higher concentrations were seen on average in air that came to the site from the urban NOx sources to the north. PAN levels were the lowest observed in ground measurements over the past two decades in the southeastern US. A multiple regression analysis indicates that biogenic volatile organic compounds (VOCs) account for 66 % of PAN formation during this study. Comparison of this value with a 0-D model simulation of peroxyacetyl radical production indicates that at least 50 % of PAN formation is due to isoprene oxidation. MPAN has a statistical correlation with isoprene hydroxynitrates (IN). Organic aerosol mass increases with gas-phase MPAN and IN concentrations, but the mass of organic nitrates in particles is largely unrelated to MPAN.

scholarly journals Mapping gas-phase organic reactivity and concomitant secondary organic aerosol formation: chemometric dimension reduction techniques for the deconvolution of complex atmospheric data sets

2015 ◽  
Vol 15 (14) ◽  
pp. 8077-8100 ◽  
Author(s):  
K. P. Wyche ◽  
P. S. Monks ◽  
K. L. Smallbone ◽  
J. F. Hamilton ◽  
M. R. Alfarra ◽  
...  
Keyword(s):  
Phase Composition ◽  
Dimension Reduction ◽  
Gas Phase ◽  
Secondary Organic Aerosol ◽  
Ambient Air ◽  
Organic Aerosol ◽  
Chemical Mechanism ◽  
Particle Phase ◽  
Aerosol Formation ◽  
Holistic View

Abstract. Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modelling in order to ultimately identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least-squares discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Results show that "model" biogenic oxidative systems can be successfully separated and classified according to their oxidation products. Furthermore, a holistic view of results obtained across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidised gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i.e. toluene) oxidation and "more realistic" plant mesocosm systems, demonstrates that such an ensemble of chemometric mapping has the potential to be used for the classification of more complex spectra of unknown origin. More specifically, the addition of mesocosm data from fig and birch tree experiments shows that isoprene and monoterpene emitting sources, respectively, can be mapped onto the statistical model structure and their positional vectors can provide insight into their biological sources and controlling oxidative chemistry. The potential to extend the methodology to the analysis of ambient air is discussed using results obtained from a zero-dimensional box model incorporating mechanistic data obtained from the Master Chemical Mechanism (MCMv3.2). Such an extension to analysing ambient air would prove a powerful asset in assisting with the identification of SOA sources and the elucidation of the underlying chemical mechanisms involved.

scholarly journals Model for acid-base chemistry in nanoparticle growth (MABNAG)

2013 ◽  
Vol 13 (3) ◽  
pp. 7175-7222 ◽  
Author(s):  
T. Yli-Juuti ◽  
K. Barsanti ◽  
L. Hildebrandt Ruiz ◽  
A.-J. Kieloaho ◽  
U. Makkonen ◽  
...  
Keyword(s):  
Particle Size ◽  
Sulfuric Acid ◽  
Gas Phase ◽  
Organic Compounds ◽  
Particle Growth ◽  
Particle Phase ◽  
Vapor Pressures ◽  
Salt Formation ◽  
Acid Base ◽  
Nanoparticle Growth

Abstract. Climatic effects of newly-formed atmospheric secondary aerosol particles are to a large extent determined by their condensational growth rates. However, all the vapors condensing on atmospheric nanoparticles and growing them to climatically relevant sizes are not identified yet and the effects of particle phase processes on particle growth rates are poorly known. Besides sulfuric acid, organic compounds are known to contribute significantly to atmospheric nanoparticle growth. In this study a particle growth model MABNAG (Model for Acid-Base chemistry in NAnoparticle Growth) was developed to study the effect of salt formation on nanoparticle growth, which has been proposed as a potential mechanism lowering the equilibrium vapor pressures of organic compounds through dissociation in the particle phase and thus preventing their evaporation. MABNAG is a model for monodisperse aqueous particles and it couples dynamics of condensation to particle phase chemistry. Non-zero equilibrium vapor pressures, with both size and composition dependence, are considered for condensation. The model was applied for atmospherically relevant systems with sulfuric acid, one organic acid, ammonia, one amine and water in the gas phase allowed to condense on 3–20 nm particles. The effect of dissociation of the organic acid was found to be small under ambient conditions typical for a boreal forest site, but considerable for base-rich environments (gas phase concentrations of about 1010 cm−3 for the sum of the bases). The contribution of the bases to particle mass decreased as particle size increased, except at very high gas phase concentrations of the bases. The relative importance of amine versus ammonia did not change significantly as a function of particle size. While our results give a reasonable first estimate on the maximum contribution of salt formation to nanoparticle growth, further studies on, e.g. the thermodynamic properties of the atmospheric organics, concentrations of low-volatility organic acids and amines, along with studies investigating the applicability of thermodynamics for the smallest nanoparticles are needed to truly understand the acid-base chemistry of atmospheric nanoparticles.

Fine particle pH and gas-particle partitioning during winter fog in Delhi, India

2021 ◽  
Author(s):  
Prodip Acharja ◽  
Sachin Ghude ◽  
Kaushar Ali ◽  
Ismail Gultepe
Keyword(s):  
Gas Phase ◽  
Fine Particle ◽  
Chemical Constituents ◽  
Fundamental Property ◽  
Ambient Air ◽  
Water Volume ◽  
Winter Period ◽  
Particle Phase ◽  
Fine Particulates ◽  
High Particle

&lt;p&gt;Comprehensive measurements were conducted to simultaneously monitor the trace gases (HCl, HONO, HNO&lt;sub&gt;3&lt;/sub&gt;, SO&lt;sub&gt;2&lt;/sub&gt;, and NH&lt;sub&gt;3&lt;/sub&gt;) and inorganic chemical constituents (Cl&lt;sup&gt;-&lt;/sup&gt;, NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt;, SO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;2-&lt;/sup&gt;, Na&lt;sup&gt;+&lt;/sup&gt;, NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;, K&lt;sup&gt;+&lt;/sup&gt;, Ca&lt;sup&gt;2+&lt;/sup&gt;, and Mg&lt;sup&gt;2+&lt;/sup&gt;) of fine particulates (PM&lt;sub&gt;1&lt;/sub&gt; and PM&lt;sub&gt;2.5&lt;/sub&gt;) at hourly resolution during the Winter Fog Experiment (WIFEX) field campaign, Delhi, India, for the winter period of 2017-2018. The measurements were performed using the instrument called Monitor for AeRosols and Gases in Ambient air (MARGA-2S) to study the role of chemical composition and gas-particle interplay chemistry in the life cycle of fog, i.e., formation, development, and dissipation phase. In the past, the variation of fine particle acidity (pH) and its impact on fog has not been studied explicitly and quantitatively over Delhi. The pH is a fundamental property of aerosol that plays a significant role in the chemical behavior and composition of particles, but it is very challenging and difficult to measure directly. Particulate water is also a significant component of aerosol and can serve as a medium for aqueous-phase reactions under foggy conditions. The pH depends on the particle water amount, as pH represents the concentration of H&lt;sup&gt;+&lt;/sup&gt; per liquid water volume (i.e., particulate water). Whereas, H&lt;sup&gt;+&lt;/sup&gt; concentration per unit volume of air is defined as the particulate proton loading.&lt;/p&gt;&lt;p&gt;Using the measured gas-phase and particle-phase concentrations and meteorological observations (T, RH), the particulate water and pH were estimated from the thermodynamic model ISORROPIA-II. In this study, the gas phase NH&lt;sub&gt;3&lt;/sub&gt;, HNO&lt;sub&gt;3&lt;/sub&gt;, and HCl and particle-phase NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;, NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt;, Cl&lt;sup&gt;-&lt;/sup&gt;, and SO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;2-&lt;/sup&gt; species were estimated using ISORROPIA-II, and model predictions of these species were validated by using the measured gas and particle-phase species. The predictions were confirmed by a good agreement between predicted and measured ammonia concentrations (r=0.94) and aerosol species concentrations ammonium (r=0.97) chloride (r=0.61), nitrate (r=0.61), and sulfate (r=0.74). The predicted PM&lt;sub&gt;2.5&lt;/sub&gt; pH ranged from 2.55 to 6.54, with mean pH of 4.55 &amp;#177; 0.51. This was consistent with the findings of previous studies. It is concluded that high particle water content, higher acidic pH, and abundant ammonia concentrations can promote the gas-particle partitioning and formation of more secondary particles under foggy conditions. The scattering cross-section of these secondary fine hygroscopic particles increases under high humidity conditions due to water uptake, resulting in visibility degradation.&lt;/p&gt;

Strong deviations from thermodynamically expected phase partitioning of organic acids during one year of rural field measurements 

2021 ◽  
Author(s):  
Andreas Tilgner ◽  
Bastian Stieger ◽  
Dominik van Pinxteren ◽  
Gerald Spindler ◽  
Laurent Poulain ◽  
...  
Keyword(s):  
Organic Acids ◽  
Gas Phase ◽  
Methanesulfonic Acid ◽  
Field Measurements ◽  
Ambient Air ◽  
Water Soluble ◽  
Particle Phase ◽  
Organic Salts ◽  
Phase Partitioning ◽  
One Year

&lt;p&gt;Organic acids are ubiquitous compounds in the troposphere and can affect human health, the climate, air quality, and the linked ecosystems. Depending on their solubility and volatility, they can partition in both gas phase and in the particle phase. In the particle phase, organic acids partly represent about 10% of the water-soluble organic matter. However, their partitioning between different phases is not fully understood yet. Therefore, an upgraded monitor for aerosols and gases in ambient air (MARGA) was applied for one year at the Central European TROPOS research site Melpitz to study the gas- and particle-phase partitioning of formic, acetic, propionic, butyric, glycolic, pyruvic, oxalic, malonic, succinic, malic, and methanesulfonic acid (MSA). Measured gas- and PM&lt;sub&gt;10&lt;/sub&gt; particle-phase mean concentrations were 12&amp;#8722;445 and 7&amp;#8722;31 ng m&lt;sup&gt;-3&lt;/sup&gt; for monocarboxylic acids (MCAs), between 0.6&amp;#8722;8 and 4&amp;#8722;31 ng m&lt;sup&gt;-3&lt;/sup&gt; for dicarboxylic acids (DCAs), and 2 and 31 ng m&lt;sup&gt;-3&lt;/sup&gt; for MSA, respectively. Assuming full dissolution in nonideal aerosol solutions, empirical noneffective Henry&amp;#8217;s law constants (H&lt;sub&gt;emp&lt;/sub&gt;) were calculated and compared with literature values (H&lt;sub&gt;lit&lt;/sub&gt;). Calculated mean H&lt;sub&gt;emp&lt;/sub&gt; were 4.5 &amp;#215; 10&lt;sup&gt;9&lt;/sup&gt;&amp;#8722;2.2 &amp;#215; 10&lt;sup&gt;10&lt;/sup&gt; mol L&lt;sup&gt;&amp;#8722;1&lt;/sup&gt; atm&lt;sup&gt;&amp;#8722;1&lt;/sup&gt; for MCAs, 3.6 &amp;#215; 10&lt;sup&gt;10&lt;/sup&gt;&amp;#8722;7.5 &amp;#215; 10&lt;sup&gt;11&lt;/sup&gt; mol L&lt;sup&gt;&amp;#8722;1&lt;/sup&gt; atm&lt;sup&gt;&amp;#8722;1&lt;/sup&gt; for DCAs, and 7.5 &amp;#215; 10&lt;sup&gt;7&lt;/sup&gt; mol L&lt;sup&gt;&amp;#8722;1&lt;/sup&gt; atm&lt;sup&gt;&amp;#8722;1&lt;/sup&gt; for MSA and, thus, factors of 5.1 &amp;#215; 10&lt;sup&gt;3&lt;/sup&gt;&amp;#8722;9.1 &amp;#215; 10&lt;sup&gt;5&lt;/sup&gt; and 2.5&amp;#8722;20.3 higher than their corresponding H&lt;sub&gt;lit&lt;/sub&gt; for MCAs and DCAs, respectively, and 9.0 &amp;#215; 10&lt;sup&gt;&amp;#8722;5&lt;/sup&gt; lower than H&lt;sub&gt;lit,MSA&lt;/sub&gt;. Data analyses and thermodynamic calculations implicate that the formation of chemical association complexes and organic salts inhibits the partitioning of organic acids toward the gas phase and, thus, at least partly explains higher H&lt;sub&gt;emp&lt;/sub&gt;&amp;#160;values for both MCAs and summertime DCAs. Low H&lt;sub&gt;emp,MSA&lt;/sub&gt; are also unexpected because of the high MSA solubility and are reported for the first time in this study. Overall, the results of the present study implicate that processes responsible for the observed stronger partitioning of carboxylic acids toward the particle phase need to be further investigated and accounted for in complex multiphase chemistry models as they affect the contribution of organic acids to secondary organic aerosol mass, their chemical processing, and lifetime.&lt;/p&gt; &lt;p&gt;&amp;#160;&lt;/p&gt; &lt;p&gt;&amp;#160;&lt;/p&gt;

scholarly journals Model for acid-base chemistry in nanoparticle growth (MABNAG)

2013 ◽  
Vol 13 (24) ◽  
pp. 12507-12524 ◽  
Author(s):  
T. Yli-Juuti ◽  
K. Barsanti ◽  
L. Hildebrandt Ruiz ◽  
A.-J. Kieloaho ◽  
U. Makkonen ◽  
...  
Keyword(s):  
Particle Size ◽  
Sulfuric Acid ◽  
Gas Phase ◽  
Organic Compounds ◽  
Growth Rates ◽  
Particle Growth ◽  
Particle Phase ◽  
Salt Formation ◽  
Acid Base ◽  
Nanoparticle Growth

Abstract. Climatic effects of newly-formed atmospheric secondary aerosol particles are to a large extent determined by their condensational growth rates. However, all the vapours condensing on atmospheric nanoparticles and growing them to climatically relevant sizes are not identified yet and the effects of particle phase processes on particle growth rates are poorly known. Besides sulfuric acid, organic compounds are known to contribute significantly to atmospheric nanoparticle growth. In this study a particle growth model MABNAG (Model for Acid-Base chemistry in NAnoparticle Growth) was developed to study the effect of salt formation on nanoparticle growth, which has been proposed as a potential mechanism lowering the equilibrium vapour pressures of organic compounds through dissociation in the particle phase and thus preventing their evaporation. MABNAG is a model for monodisperse aqueous particles and it couples dynamics of condensation to particle phase chemistry. Non-zero equilibrium vapour pressures, with both size and composition dependence, are considered for condensation. The model was applied for atmospherically relevant systems with sulfuric acid, one organic acid, ammonia, one amine and water in the gas phase allowed to condense on 3–20 nm particles. The effect of dissociation of the organic acid was found to be small under ambient conditions typical for a boreal forest site, but considerable for base-rich environments (gas phase concentrations of about 1010 cm−3 for the sum of the bases). The contribution of the bases to particle mass decreased as particle size increased, except at very high gas phase concentrations of the bases. The relative importance of amine versus ammonia did not change significantly as a function of particle size. While our results give a reasonable first estimate on the maximum contribution of salt formation to nanoparticle growth, further studies on, e.g. the thermodynamic properties of the atmospheric organics, concentrations of low-volatility organics and amines, along with studies investigating the applicability of thermodynamics for the smallest nanoparticles are needed to truly understand the acid-base chemistry of atmospheric nanoparticles.

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