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

<p>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<sub>10</sub> particle-phase mean concentrations were 12−445 and 7−31 ng m<sup>-3</sup> for monocarboxylic acids (MCAs), between 0.6−8 and 4−31 ng m<sup>-3</sup> for dicarboxylic acids (DCAs), and 2 and 31 ng m<sup>-3</sup> for MSA, respectively. Assuming full dissolution in nonideal aerosol solutions, empirical noneffective Henry’s law constants (H<sub>emp</sub>) were calculated and compared with literature values (H<sub>lit</sub>). Calculated mean H<sub>emp</sub> were 4.5 × 10<sup>9</sup>−2.2 × 10<sup>10</sup> mol L<sup>−1</sup> atm<sup>−1</sup> for MCAs, 3.6 × 10<sup>10</sup>−7.5 × 10<sup>11</sup> mol L<sup>−1</sup> atm<sup>−1</sup> for DCAs, and 7.5 × 10<sup>7</sup> mol L<sup>−1</sup> atm<sup>−1</sup> for MSA and, thus, factors of 5.1 × 10<sup>3</sup>−9.1 × 10<sup>5</sup> and 2.5−20.3 higher than their corresponding H<sub>lit</sub> for MCAs and DCAs, respectively, and 9.0 × 10<sup>−5</sup> lower than H<sub>lit,MSA</sub>. 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<sub>emp</sub> values for both MCAs and summertime DCAs. Low H<sub>emp,MSA</sub> 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.</p> <p> </p> <p> </p>

scholarly journals Development of an online-coupled MARGA upgrade for the two-hourly quantification of low-molecular weight organic acids in the gas and particle-phase

2018 ◽  
Author(s):  
Bastian Stieger ◽  
Gerald Spindler ◽  
Dominik van Pinxteren ◽  
Achim Grüner ◽  
Markus Wallasch ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Organic Acids ◽  
Organic Acid ◽  
Gas Phase ◽  
Solid Phase ◽  
Ambient Air ◽  
Low Molecular Weight ◽  
Gradient System ◽  
Particle Phase ◽  
Separation Columns

Abstract. A method is presented to quantify the low-molecular weight organic acids formic, acetic, propionic, butyric, pyruvic, glycolic, oxalic, malonic, succinic, malic, glutaric, and methanesulfonic acid in the atmospheric gas and particle phase in a two-hourly time resolution, based on a combination of the Monitor for AeRosols and Gases in ambient Air (MARGA) and an additional ion chromatography (IC) instrument. A proper separation of the organic target acids was initially tackled by a laboratory IC optimization study, testing different separation columns, eluent compositions and eluent flow rates both for isocratic and for gradient elution. Satisfactory resolution of all compounds was achieved using a gradient system with two coupled anion exchange separation columns. Online pre-concentration with an enrichment factor of approximately 400 was achieved by solid phase extraction consisting of a methacrylate polymer based sorbent with quaternary ammonium groups. The limits of detection of the method range between 7.1 ng m−3 for methanesulfonate and 150.3 ng m−3 for pyruvate. Precisions are below 1.0 %, except for glycolate (2.9 %) and succinate (1.0 %). Comparisons of inorganic anions measured at the TROPOS research site in Melpitz, Germany, by the original MARGA and the additional organic acid IC systems are in agreement with each other (R2 = 0.95 − 0.99). Organic acid concentrations from May 2017 as an example period are presented. Monocarboxylic acids were dominant in the gas phase with mean concentrations of 553 ng m−3 for acetic acid, followed by formic (286 ng m−3), pyruvic acid (182 ng m−3), propionic (179 ng m−3), butyric (98 ng m−3) and glycolic (71 ng  m−3). Particulate glycolate, oxalate and methanesulfonate were quantified with mean concentrations of 63 ng  m−3, 74 ng m−3 and 35 ng m−3, respectively. Elevated concentrations in the late afternoon of gas phase formic acid and particulate oxalate indicate a photochemical formation.

scholarly journals Online measurements of water-soluble organic acids in the gas and aerosol phase from the photooxidation of 1,3,5-trimethylbenzene

2014 ◽  
Vol 14 (1) ◽  
pp. 985-1018
Author(s):  
A. P. Praplan ◽  
K. Hegyi-Gaeggeler ◽  
P. Barmet ◽  
L. Pfaffenberger ◽  
J. Dommen ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Organic Acids ◽  
Gas Phase ◽  
Water Soluble ◽  
Precursor Concentration ◽  
Smog Chamber ◽  
Particle Phase ◽  
Online Measurements ◽  
Paul Scherrer ◽  
Chamber Gas

Abstract. The formation of organic acids during photooxidation of 1,3,5-trimethylbenzene (TMB) was investigated with an online ion chromatography (IC) instrument coupled to a mass spectrometer (MS) at the Paul Scherrer Institute (PSI) smog chamber. Gas and aerosol phase were both sampled. Molecular formulae were attributed to twelve compounds with the help of high resolution MS data from filter extracts (two compounds in the gas phase only, two in the aerosol phase only and eight in both). Seven of those species could be identified unambiguously (each of them present in gas and aerosol phase): formic acid, acetic acid, glycolic acid, butyric acid, pyruvic acid, lactic acid and methylmaleic acid. The influence of the precursor concentration (TMB: 1200 and 600 ppbv) and of the presence of 2 ppbv of sulphur dioxide (SO2) on aerosol and gas phase products were further investigated. While the organic acid fraction present in the aerosol phase does not strongly depend on the precursor concentration (6 to 14%), the presence of SO2 reduces this amount to less than 3% for both high and low precursor concentration scenarios. The addition of acetic acid during the experiments indicated that the presence of small acids in the particle phase might not be due to partitioning effects.

scholarly journals Development of an online-coupled MARGA upgrade for the 2 h interval quantification of low-molecular-weight organic acids in the gas and particle phases

2019 ◽  
Vol 12 (1) ◽  
pp. 281-298 ◽  
Author(s):  
Bastian Stieger ◽  
Gerald Spindler ◽  
Dominik van Pinxteren ◽  
Achim Grüner ◽  
Markus Wallasch ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Organic Acids ◽  
Gas Phase ◽  
Solid Phase ◽  
Methanesulfonic Acid ◽  
Ambient Air ◽  
Gradient Elution ◽  
Low Molecular Weight ◽  
Gradient System ◽  
Separation Columns

Abstract. A method is presented to quantify the low-molecular-weight organic acids such as formic, acetic, propionic, butyric, pyruvic, glycolic, oxalic, malonic, succinic, malic, glutaric, and methanesulfonic acid in the atmospheric gas and particle phases, based on a combination of the Monitor for AeRosols and Gases in ambient Air (MARGA) and an additional ion chromatography (Compact IC) instrument. Therefore, every second hourly integrated MARGA gas and particle samples were collected and analyzed by the Compact IC, resulting in 12 values per day for each phase. A proper separation of the organic target acids was initially tackled by a laboratory IC optimization study, testing different separation columns, eluent compositions and eluent flow rates for both isocratic and gradient elution. Satisfactory resolution of all compounds was achieved using a gradient system with two coupled anion-exchange separation columns. Online pre-concentration with an enrichment factor of approximately 400 was achieved by solid-phase extraction consisting of a methacrylate-polymer-based sorbent with quaternary ammonium groups. The limits of detection of the method range between 0.5 ng m−3 for malonate and 17.4 ng m−3 for glutarate. Precisions are below 1.0 %, except for glycolate (2.9 %) and succinate (1.0 %). Comparisons of inorganic anions measured at the TROPOS research site in Melpitz, Germany, by the original MARGA and the additional Compact IC are in agreement with each other (R2 = 0.95–0.99). Organic acid concentrations from May 2017 as an example period are presented. Monocarboxylic acids were dominant in the gas phase with mean concentrations of 306 ng m−3 for acetic acid, followed by formic (199 ng m−3), propionic (83 ng m−3), pyruvic (76 ng m−3), butyric (34 ng m−3) and glycolic acid (32 ng m−3). Particulate glycolate, oxalate and methanesulfonate were quantified with mean concentrations of 26, 31 and 30 ng m−3, respectively. Elevated concentrations of gas-phase formic acid and particulate oxalate in the late afternoon indicate photochemical formation as a source.

scholarly journals Characterization of Aerosol Composition, Aerosol Acidity and Organic Acid Partitioning at an Agriculture-Intensive Rural Southeastern U.S. Site

2018 ◽  
Author(s):  
Theodora Nah ◽  
Hongyu Guo ◽  
Amy P. Sullivan ◽  
Yunle Chen ◽  
David J. Tanner ◽  
...  
Keyword(s):  
Oxalic Acid ◽  
Organic Acids ◽  
Organic Acid ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Molar Concentration ◽  
Particle Phase ◽  
Aerosol Composition ◽  
Phase Water ◽  
Acetic Acids

Abstract. The implementation of stringent emission regulations has resulted in the decline of anthropogenic pollutants including sulfur dioxide (SO2), nitrogen oxides (NOx) and carbon monoxide (CO). In contrast, ammonia (NH3) emissions are largely unregulated, with emissions projected to increase in the future. We present real-time aerosol and gas measurements from a field study conducted in an agricultural-intensive region in the southeastern U.S. during the fall of 2016 to investigate how NH3 affects particle acidity and SOA formation via the gas-particle partitioning of semi-volatile organic acids. Particle water and pH were determined using the ISORROPIA-II thermodynamic model and validated by comparing predicted inorganic HNO3-NO3− and NH3-NH4+ gas-particle partitioning ratios with measured values. Our results showed that despite the high NH3 concentrations (study average 8.1 ± 5.2 ppb), PM1 were highly acidic with pH values ranging from 0.9 to 3.8, and a study-averaged pH of 2.2 ± 0.6. PM1 pH varied by approximately 1.4 units diurnally. Formic and acetic acids were the most abundant gas-phase organic acids, and oxalate was the most abundant particle-phase water-soluble organic acid anion. Measured particle-phase water-soluble organic acids were on average 6 % of the total non-refractory PM1 organic aerosol mass. The measured molar fraction of oxalic acid in the particle phase (i.e., particle-phase oxalic acid molar concentration divided by the total oxalic acid molar concentration) ranged between 47 and 90 % for PM1 pH 1.2 to 3.4. The measured oxalic acid gas-particle partitioning ratios were in good agreement with their corresponding thermodynamic predictions, calculated based on oxalic acid’s physicochemical properties, ambient temperature, particle water and pH. In contrast, gas-particle partitioning of formic and acetic acids were not well predicted for reasons currently unknown. For this study, higher NH3 concentrations relative to what has been measured in the region in previous studies had minor effects on PM1 organic acids and their influence on the overall organic aerosol and PM1 mass concentrations.

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.

Production of Amino and Organic Acids from Protein Using Sub-Critical Water Technology

2013 ◽  
Vol 11 (1) ◽  
pp. 369-384 ◽  
Author(s):  
Wael Abdelmoez ◽  
Hiroyuki Yoshida
Keyword(s):  
Organic Acids ◽  
Gas Phase ◽  
Solid Phase ◽  
Water Soluble ◽  
Water Soluble Protein ◽  
Study Results ◽  
Temperature Ranges ◽  
Aggregation Step ◽  
Hydrolysis Of ◽  
Protein Bovine Serum Albumin

Abstract This work presents the hydrolysis of a water-soluble protein, bovine serum albumin (BSA), for the production of both amino and organic acids under the sub-critical water condition in the temperature range of 200–300°C. The products of the reaction were a water-insoluble solid phase, an aqueous phase, and an insignificant gas phase which was neglected in this study. Results have shown that BSA passes through an aggregation step, followed by a gel formation process which results in the formation of insoluble solid aggregates. Then, such formed solids unfolded with releasing polypeptides as an intermediate product then finally hydrolyzed to produce low molecular mass products such as amino and organic acids. It was found that there were insignificant amino acids produced in the temperature ranges of 200–225°C within 2 min and 275–300°C within 0.5 min. However, by extending the reaction time, the protein transferred to both amino and organic acids.

scholarly journals Aqueous chemistry and its role in secondary organic aerosol (SOA) formation

2010 ◽  
Vol 10 (21) ◽  
pp. 10521-10539 ◽  
Author(s):  
Y. B. Lim ◽  
Y. Tan ◽  
M. J. Perri ◽  
S. P. Seitzinger ◽  
B. J. Turpin
Keyword(s):  
Organic Acids ◽  
Gas Phase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Base Catalysis ◽  
Radical Reactions ◽  
Oh Radicals ◽  
Aqueous Chemistry ◽  
Radical Chemistry

Abstract. There is a growing understanding that secondary organic aerosol (SOA) can form through reactions in atmospheric waters (i.e., clouds, fogs, and aerosol water). In clouds and wet aerosols, water-soluble organic products of gas-phase photochemistry dissolve into the aqueous phase where they can react further (e.g., with OH radicals) to form low volatility products that are largely retained in the particle phase. Organic acids, oligomers and other products form via radical and non-radical reactions, including hemiacetal formation during droplet evaporation, acid/base catalysis, and reaction of organics with other constituents (e.g., NH4+). This paper provides an overview of SOA formation through aqueous chemistry, including atmospheric evidence for this process and a review of radical and non-radical chemistry, using glyoxal as a model precursor. Previously unreported analyses and new kinetic modeling are reported herein to support the discussion of radical chemistry. Results suggest that reactions with OH radicals tend to be faster and form more SOA than non-radical reactions. In clouds these reactions yield organic acids, whereas in wet aerosols they yield large multifunctional humic-like substances formed via radical-radical reactions and their O/C ratios are near 1.

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.

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