14 Jun 2022
14 Jun 2022
Status: a revised version of this preprint is currently under review for the journal ACP.

Ammonium-adduct chemical ionization to investigate anthropogenic oxygenated gas-phase organic compounds in urban air

Peeyush Khare1,a, Jordan E. Krechmer2, Jo Ellen Machesky1, Tori Hass-Mitchell1, Cong Cao3, Junqi Wang1, Francesca Majluf2,b, Felipe Lopez-Hilfiker4, Sonja Malek1, Will Wang1, Karl Seltzer5, Havala O. T. Pye6, Roisin Commane7, Brian C. McDonald8, Ricardo Toledo-Crow9, John E. Mak3, and Drew R. Gentner1,10 Peeyush Khare et al.
  • 1Department of Chemical and Environmental Engineering, Yale University, New Haven CT-06511 USA
  • 2Aerodyne Research Inc. Billerica MA- 02181 USA
  • 3School of Marine and Atmospheric Science, Stony Brook University, Stony Brook NY-11794 USA
  • 4Tofwerk AG, CH-3600 Thun, Switzerland
  • 5Office of Air and Radiation, Environmental Protection Agency, Research Triangle Park, NC-27711 USA
  • 6Office of Research and Development, Environmental Protection Agency, Research Triangle Park, NC-27711 USA
  • 7Department of Earth and Environmental Sciences, Lamont-Doherty Earth Observatory, Columbia University, New York, NY-10027 USA
  • 8Chemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder CO- USA
  • 9Advanced Science Research Center, City University of New York, New York, NY-10031 USA
  • 10School of the Environment, Yale University, New Haven CT-06511 USA
  • anow at: Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen AG-5232 Switzerland
  • bnow at: Franklin W. Olin College of Engineering

Abstract. Volatile chemical products (VCPs) and other non-combustion-related sources have become important for urban air quality, and bottom-up calculations report emissions of a variety of functionalized compounds that remain understudied and uncertain in emissions estimates. Using a new instrumental configuration, we present online measurements of oxygenated VCPs in a U.S. megacity over a 10-day wintertime sampling period, when biogenic sources and photochemistry were less active. Measurements were conducted at a rooftop observatory in upper Manhattan, New York City, USA using a Vocus chemical ionization time-of-flight mass spectrometer with ammonium (NH4+) as the reagent ion operating at 1 Hz. The range of observations spanned volatile, intermediate-volatility, and semi-volatile organic compounds with targeted analyses of ~150 ions whose likely assignments included a range of functionalized compound classes such as glycols, glycol ethers, acetates, acids, alcohols, acrylates, esters, ethanolamines, and ketones that are found in various consumer, commercial, and industrial products. Their concentrations varied as a function of wind direction with enhancements over the highly-populated areas of the Bronx, Manhattan, and parts of New Jersey, and included abundant concentrations of acetates, acrylates, ethylene glycol, and other commonly-used oxygenated compounds. The results provide top-down constraints on wintertime emissions of these oxygenated/functionalized compounds with ratios to common anthropogenic marker compounds and compares their relative abundances to two regionally-resolved emissions inventories used in urban air quality models.

Peeyush Khare et al.

Status: final response (author comments only)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on acp-2022-421', Anonymous Referee #1, 04 Jul 2022
  • RC2: 'Comment on acp-2022-421', Anonymous Referee #2, 08 Jul 2022
  • RC3: 'Comment on acp-2022-421', Anonymous Referee #3, 08 Jul 2022
  • AC1: 'Response to referee comments on acp-2022-421', Peeyush Khare, 22 Sep 2022

Peeyush Khare et al.

Peeyush Khare et al.


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Latest update: 06 Oct 2022
Short summary
Urban ambient measurements via ammonium-adduct (NH4+) time-of-flight mass spectrometry explore the diverse mix of compounds emitted from volatile chemical products that include volatile to semi-volatile organic compounds across various chemical classes (e.g. glycols, glycol ethers, acetates, acrylates) with concentrations ranging from parts per trillion to parts per billion levels. The results are used to evaluate state-of-the-art regionally-resolved emission inventories.