Interferences with aerosol acidity quantification due to gas-phase ammonia uptake onto acidic sulfate filter samples

Benjamin A Nault,Pedro Campuzano-Jost,Jason C Schroder,Weiwei Hu,Brett B Palm,Anne V Handschy,Douglas A Day,Hongyu Guo,Michael J Cubison,Jack E Dibb,Demetrios Pagonis,Jose L Jimenez,Melinda K Schueneman,Duseong S Jo,Alma Hodzic

doi:10.5194/amt-13-6193-2020

Abstract

Abstract. Measurements of the mass concentration and chemical speciation of aerosols are important to investigate their chemical and physical processing from near emission sources to the most remote regions of the atmosphere. A common method to analyze aerosols is to collect them onto filters and analyze the filters offline; however, biases in some chemical components are possible due to changes in the accumulated particles during the handling of the samples. Any biases would impact the measured chemical composition, which in turn affects our understanding of numerous physicochemical processes and aerosol radiative properties. We show, using filters collected onboard the NASA DC-8 and NSF C-130 during six different aircraft campaigns, a consistent, substantial difference in ammonium mass concentration and ammonium-to-anion ratios when comparing the aerosols collected on filters versus an Aerodyne aerosol mass spectrometer (AMS). Another online measurement is consistent with the AMS in showing that the aerosol has lower ammonium-to-anion ratios than obtained by the filters. Using a gas uptake model with literature values for accommodation coefficients, we show that for ambient ammonia mixing ratios greater than 10 ppbv, the timescale for ammonia reacting with acidic aerosol on filter substrates is less than 30 s (typical filter handling time in the aircraft) for typical aerosol volume distributions. Measurements of gas-phase ammonia inside the cabin of the DC-8 show ammonia mixing ratios of 45±20 ppbv, consistent with mixing ratios observed in other indoor environments. This analysis enables guidelines for filter handling to reduce ammonia uptake. Finally, a more meaningful limit of detection for University of New Hampshire Soluble Acidic Gases and Aerosol (SAGA) filters collected during airborne campaigns is ∼0.2 µg sm−3 of ammonium, which is substantially higher than the limit of detection of ion chromatography. A similar analysis should be conducted for filters that collect inorganic aerosol and do not have ammonia scrubbers and/or are handled in the presence of human ammonia emissions.

Highlights

Particulate matter (PM), or aerosol, impacts human health, ecosystem health, visibility, climate, cloud formation and lifetime, and atmospheric chemistry (Meskhidze et al, 2003; Abbatt et al, 2006; Seinfeld and Pandis, 2006; Jimenez et al, 2009; Myhre et al, 2013; Cohen et al, 2017; Hodzic and Duvel, 2018; Heald and Kroll, 2020; Pye et al, 2020)
Collection of aerosols onto filters to the measure aerosol mass concentration and composition is valuable for improving our understanding of the emissions and chemistry of inorganic aerosol; long-standing, multi-decadal, filter-based records of atmospheric composition are invaluable to analyze atmospheric change
As has been discussed in earlier studies, acidic aerosols collected on filters are susceptible to uptake of gas-phase ammonia, which interacts with the acidic aerosol to form an ammonium salt

Summary

Introduction

Particulate matter (PM), or aerosol, impacts human health, ecosystem health, visibility, climate, cloud formation and lifetime, and atmospheric chemistry (Meskhidze et al, 2003; Abbatt et al, 2006; Seinfeld and Pandis, 2006; Jimenez et al, 2009; Myhre et al, 2013; Cohen et al, 2017; Hodzic and Duvel, 2018; Heald and Kroll, 2020; Pye et al, 2020). Each method has different advantages and disadvantages (e.g., time resolution, sample preparation, range of species identified, cost, and personnel needs). These results, in turn, have been used to inform and improve the results of CTMs, influencing our understanding of processes such as the direct radiative effect (Wang et al, 2008b), transport of ammonia in deep convection (Ge et al, 2018), aerosol pH (Pye et al, 2020; Zakoura et al, 2020) and subsequent chemistry, and precursor emissions (Henze et al, 2009; Heald et al, 2012; Walker et al, 2012; Mezuman et al, 2016)

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Results

Conclusion