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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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Discussion papers | Copyright
https://doi.org/10.5194/amt-2018-299
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 12 Oct 2018

Research article | 12 Oct 2018

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This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Measurement Techniques (AMT).

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

Bastian Stieger1, Gerald Spindler1, Dominik van Pinxteren1, Achim Grüner1, Markus Wallasch2, and Hartmut Herrmann1 Bastian Stieger et al.
  • 1Atmospheric Chemistry Department (ACD), Leibniz Institute for Tropospheric Research (TROPOS), Permoserstraße 15, 04318 Leipzig, Germany
  • 2German Federal Environment Agency, Wörlitzer Platz 1, 06844 Dessau-Roßlau, Germany

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 7.1ngm−3 for methanesulfonate and 150.3ngm−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=0.950.99). Organic acid concentrations from May 2017 as an example period are presented. Monocarboxylic acids were dominant in the gas phase with mean concentrations of 553ngm−3 for acetic acid, followed by formic (286ngm−3), pyruvic acid (182ngm−3), propionic (179ngm−3), butyric (98ngm−3) and glycolic (71ng m−3). Particulate glycolate, oxalate and methanesulfonate were quantified with mean concentrations of 63ng m−3, 74ngm−3 and 35ngm−3, respectively. Elevated concentrations in the late afternoon of gas phase formic acid and particulate oxalate indicate a photochemical formation.

Bastian Stieger et al.
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Short summary
A MARGA was combined with an additional ion chromatography system specialized for the two-hourly online quantification of 12 low-molecular weight organic acids in the gas and particle phase. Low limits of detection and good precisions were achieved. The suitability for field measurements was shown. This setup reduces laboratory work and filter sampling artifacts. Diurnal profiles, sources and phase distributions of these compounds improve the knowledge of the tropospheric multiphase chemistry.
A MARGA was combined with an additional ion chromatography system specialized for the two-hourly...
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