Airborne flux measurements of ammonia over the Southern Great Plains using chemical ionization mass spectrometry

Schobesberger, Siegfried; D'Ambro, Emma L.; Vettikkat, Lejish; Lee, Ben H.; Peng, Qiaoyun; Bell, David M.; Shilling, John E.; Shrivastava, Manish; Pekour, Mikhail; Fast, Jerome; Thornton, Joel A.

doi:10.5194/amt-2022-244

Title: Airborne flux measurements of ammonia over the Southern Great Plains using chemical ionization mass spectrometry

Full Record
Other Related Research

Abstract

Ammonia (NH₃) is an abundant trace gas in the atmosphere and an important player in atmospheric chemistry, aerosol formation and the atmosphere-surface exchange of nitrogen. It is recognized as a major source of aerosol pollution, and it may limit the formation of cloud nuclei in remote or cold parts of the atmosphere. For soil and plants, NH₃-mediated nitrogen can act as a harmful pollutant or as a desirable nutrient, mostly in natural and agricultural settings, respectively. Agriculture is also the main source of atmospheric NH₃ via volatilization from fertilizers and manure processing in livestock farming. The accurate determination of NH₃ emission rates remains a challenge, partly due to the propensity of NH₃ to interact with instrument surfaces leading to high detection limits and slow response times. In this paper, we present a new method for quantifying ambient NH₃, using chemical ionization mass spectrometry (CIMS) with deuterated benzene cations as reagents. The setup aimed at limiting sample-surface interactions and achieved a 1-σ precision of 10–20 pptv and an immediate 1/e response rate < 0.4 s, which compares favorably to the existing state of the art. The sensitivity exhibited an inverse humidity dependence, in particular in relatively dry conditions. Background of upmore »« less

Authors:

^[1];

^[2];

^[3]; Lee, Ben H. ^[2]; Peng, Qiaoyun ^[2]; Bell, David M. ^[4];

^[5];

^[5]; Fast, Jerome ^[5]; Thornton, Joel A. ^[2]

University of Washington, Seattle, WA (United States); University of Eastern Finland, Kuopio (Finland); University of Helsinki (Finland)
University of Washington, Seattle, WA (United States)
University of Eastern Finland, Kuopio (Finland)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Paul Scherrer Institute (PSI), Villigen (Switzerland)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Publication Date:: Wed Sep 07 00:00:00 EDT 2022

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Atmospheric Radiation Measurement (ARM) Data Center; Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Biological and Environmental Research (BER); European Commission (EC); Academy of Finland; Marie Skłodowska-Curie Actions; National Science Foundation (NSF)

OSTI Identifier:: 1922384

Grant/Contract Number:: SC0021097; AC05-76RL01830; SC0011791; 701958; 310682; 337550; 243766; 276416; DGE-1256082

Resource Type:: Accepted Manuscript

Journal Name:: Atmospheric Measurement Techniques (Online)

Additional Journal Information:: Journal Name: Atmospheric Measurement Techniques (Online); Journal Volume: 16; Journal Issue: 2; Journal ID: ISSN 1867-8548

Publisher:: Copernicus Publications, EGU

Country of Publication:: United States

Language:: English

Subject:: 54 ENVIRONMENTAL SCIENCES

Citation Formats


                    Schobesberger, Siegfried, D'Ambro, Emma L., Vettikkat, Lejish, Lee, Ben H., Peng, Qiaoyun, Bell, David M., Shilling, John E., Shrivastava, Manish, Pekour, Mikhail, Fast, Jerome, and Thornton, Joel A. Airborne flux measurements of ammonia over the Southern Great Plains using chemical ionization mass spectrometry.  United States: N. p., 2022. 
Web.  doi:10.5194/amt-2022-244.

Copy to clipboard


                    Schobesberger, Siegfried, D'Ambro, Emma L., Vettikkat, Lejish, Lee, Ben H., Peng, Qiaoyun, Bell, David M., Shilling, John E., Shrivastava, Manish, Pekour, Mikhail, Fast, Jerome, & Thornton, Joel A. Airborne flux measurements of ammonia over the Southern Great Plains using chemical ionization mass spectrometry.  United States.  https://doi.org/10.5194/amt-2022-244

Copy to clipboard


                    Schobesberger, Siegfried, D'Ambro, Emma L., Vettikkat, Lejish, Lee, Ben H., Peng, Qiaoyun, Bell, David M., Shilling, John E., Shrivastava, Manish, Pekour, Mikhail, Fast, Jerome, and Thornton, Joel A. Wed .  
"Airborne flux measurements of ammonia over the Southern Great Plains using chemical ionization mass spectrometry".  United States.  https://doi.org/10.5194/amt-2022-244.  https://www.osti.gov/servlets/purl/1922384.

Copy to clipboard


                    
@article{osti_1922384,

  title        = {Airborne flux measurements of ammonia over the Southern Great Plains using chemical ionization mass spectrometry},

  author       = {Schobesberger, Siegfried and D'Ambro, Emma L. and Vettikkat, Lejish and Lee, Ben H. and Peng, Qiaoyun and Bell, David M. and Shilling, John E. and Shrivastava, Manish and Pekour, Mikhail and Fast, Jerome and Thornton, Joel A.},

  abstractNote = {Ammonia (NH3) is an abundant trace gas in the atmosphere and an important player in atmospheric chemistry, aerosol formation and the atmosphere-surface exchange of nitrogen. It is recognized as a major source of aerosol pollution, and it may limit the formation of cloud nuclei in remote or cold parts of the atmosphere. For soil and plants, NH3-mediated nitrogen can act as a harmful pollutant or as a desirable nutrient, mostly in natural and agricultural settings, respectively. Agriculture is also the main source of atmospheric NH3 via volatilization from fertilizers and manure processing in livestock farming. The accurate determination of NH3 emission rates remains a challenge, partly due to the propensity of NH3 to interact with instrument surfaces leading to high detection limits and slow response times. In this paper, we present a new method for quantifying ambient NH3, using chemical ionization mass spectrometry (CIMS) with deuterated benzene cations as reagents. The setup aimed at limiting sample-surface interactions and achieved a 1-σ precision of 10–20 pptv and an immediate 1/e response rate < 0.4 s, which compares favorably to the existing state of the art. The sensitivity exhibited an inverse humidity dependence, in particular in relatively dry conditions. Background of up to 10 % of the total signal required consideration as well, as it responded on the order of a few minutes. To showcase the method’s capabilities, we quantified NH3 mixing ratios from measurements obtained during deployment on a Gulfstream I aircraft during the HI-SCALE (Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems) field campaign in rural Oklahoma during May 2016. Typical mixing ratios were 1–10 parts per billion by volume (ppbv) for the boundary layer and 0.1–1 ppbv in the lower free troposphere. Sharp plumes of up to 10s of ppbv of NH3 were encountered as well. We identified two of their sources as a large fertilizer plant and a cattle farm, and our mixing ratio measurements yielded upper bounds of 350 ± 50 and 0.6 kg NH3 h–1 for their respective momentary source rates. The fast response of the CIMS also allowed us to derive vertical NH3 fluxes within the turbulent boundary layer via eddy covariance, for which we chiefly used the continuous wavelet transform technique. As expected for a region dominated by agriculture, we observed predominantly upward fluxes, implying net NH3 emissions from surface. The corresponding analysis focused on the most suitable flight, which contained two straight-and-level legs at ~300 m above ground. We derived NH3 fluxes between –4 and 18 mol km–2 h–1 for these legs, at an effective spatial resolution of 1–2 km. The analysis demonstrated how flux measurements benefit from suitably arranged flight tracks with sufficiently long straight-and-level legs, and explores the detrimental effect of measurement discontinuities. Following flux footprint estimations, comparison to the NH3 area emissions inventory provided by the US Environmental Protection Agency indicated overall agreement, but also the absence of some sources, for instance the identified cattle farm. Our study concludes that high-precision CIMS measurements are a powerful tool for in-situ measurements of ambient NH3 mixing ratios, and even allow for the airborne mapping of the air-surface exchange of NH3.},

  doi          = {10.5194/amt-2022-244},

  journal      = {Atmospheric Measurement Techniques (Online)},

  number       = 2,

  volume       = 16,

  place        = {United States},

  year         = {Wed Sep 07 00:00:00 EDT 2022},

  month        = {Wed Sep 07 00:00:00 EDT 2022}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.5194/amt-2022-244

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Airborne flux measurements of ammonia over the southern Great Plains using chemical ionization mass spectrometry

Journal Article Schobesberger, Siegfried ; D'Ambro, Emma L. ; Vettikkat, Lejish ; ... - Atmospheric Measurement Techniques (Online)

Ammonia (NH₃) is an abundant trace gas in the atmosphere and an important player in atmospheric chemistry, aerosol formation and the atmosphere–surface exchange of nitrogen. The accurate determination of NH₃ emission rates remains a challenge, partly due to the propensity of NH₃ to interact with instrument surfaces, leading to high detection limits and slow response times. In this paper, we present a new method for quantifying ambient NH₃, using chemical ionization mass spectrometry (CIMS) with deuterated benzene cations as reagents. The setup aimed at limiting sample–surface interactions and achieved a 1σ precision of 10–20 pptv and an immediate 1/e responsemore »« less
https://doi.org/10.5194/amt-16-247-2023
Modeling the Sources and Transport Processes During Extreme Ammonia Episodes in the U.S. Corn Belt

Journal Article Hu, Cheng ; Griffis, Timothy J. ; Baker, John M. ; ... - Journal of Geophysical Research: Atmospheres

Abstract Atmospheric ammonia (NH ₃ ) is the primary form of reactive nitrogen (N _r ) and a precursor of ammonium (NH ₄ ⁺ ) aerosols. Ammonia has been linked to adverse impacts on human health, the loss of ecosystem biodiversity, and plays a key role in aerosol radiative forcing. The midwestern United States is the major NH ₃ source in North America because of dense livestock operations and the high use of synthetic nitrogen fertilizers. Here, we combine tall‐tower (100 m) observations in Minnesota and Weather Research and Forecasting model coupled with Chemistry (WRF‐Chem) modeling to investigate high andmore »« less
Cited by 6
https://doi.org/10.1029/2019JD031207
Fine Aerosol Acidity and Water during Summer in the Eastern North Atlantic

Journal Article Nah, Theodora ; Yang, Junwei ; Wang, Jian ; ... - Atmosphere (Basel)

Aerosol pH governs many important atmospheric processes that occur in the marine boundary layer, including regulating halogen and sulfur chemistries, and nutrient fertilization of surface ocean waters. In this study, we investigated the acidity of PM₁ over the eastern North Atlantic during the Aerosol and Cloud Experiments in Eastern North Atlantic (ACE-ENA) aircraft campaign. The ISORROPIA-II thermodynamic model was used to predict PM₁ pH and water. We first investigated the sensitivities of PM₁ pH and water predictions to gas-phase NH₃ and HNO₃ concentrations. Our sensitivity analysis indicated that even though NH₃ and HNO₃ were present at very low concentrations in the eastern North Atlantic during the campaign, PM₁ pH calculations can still be sensitive to NH₃ concentrations. Specifically, NH₃ was needed to constrain the pH of populations of PM₁ that had low mass concentrations of NH_4⁺ and non-volatile cations (NVCs). We next assumed that gas-phase NH₃ and HNO₃ concentrations during the campaign were 0.15 and 0.09 µg m^-3, respectively, based on previous measurements conducted in the eastern North Atlantic. Using the assumption that PM₁ were internally mixed (i.e., bulk PM₁), we determined that PM₁ pH ranged from 0.3–8.6, with a mean pH of 5.0 ± 2.3. The pH depended on bothmore »« less
https://doi.org/10.3390/atmos12081040
Measurements of Ammonia at Blodgett Forest

Technical Report Fischer, Marc L ; Littlejohn, David

Ammonia is a reactive trace gas that is emitted in large quantities by animal agriculture and other sources in California, which subsequently forms aerosol particulate matter, potentially affecting visibility, climate, and human health. We performed initial measurements of NH{sub 3} at the Blodgett Forest Research Station (BFRS) during a 3 week study in June, 2006. The site is used for ongoing air quality research and is a relatively low-background site in the foothills of the Sierra Nevada. Measured NH{sub 3} mixing ratios were quite low (< 1 to {approx}2 ppb), contrasting with typical conditions in many parts of the Centralmore »« less
https://doi.org/10.2172/922828

Full Text Available
Ammonia at Blodgett Forest, Sierra Nevada, USA

Journal Article Fischer, Marc L ; Littlejohn, David - Atmospheric Chemistry and Physics Discussions

Ammonia is a reactive trace gas that is emitted in large quantities by animal agriculture and other sources in California, which subsequently forms aerosol particulate matter, potentially affecting visibility, climate, and human health. We performed initial measurements of NH{sub 3} at the Blodgett Forest Research Station (BFRS) during a two week study in June, 2006. The site is used for ongoing air quality research and is a relatively low-background site in the foothills of the Sierra Nevada. Measured NH{sub 3} mixing ratios were quite low (< 1 to {approx} 2 ppb), contrasting with typical conditions in many parts of themore »« less
Full Text Available

Similar Records