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Atmosphere 2015, 6(10), 1487-1506; doi:10.3390/atmos6101487

Inland Concentrations of Cl2 and ClNO2 in Southeast Texas Suggest Chlorine Chemistry Significantly Contributes to Atmospheric Reactivity

Center for Energy and Environmental Resources, The University of Texas at Austin, Austin, TX 78758, USA
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Academic Editor: Armin Sorooshian
Received: 31 August 2015 / Revised: 7 October 2015 / Accepted: 8 October 2015 / Published: 14 October 2015
(This article belongs to the Special Issue Atmospheric Composition Observations)
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Abstract

Measurements of molecular chlorine (Cl2), nitryl chloride (ClNO2), and dinitrogen pentoxide (N2O5) were taken as part of the DISCOVER-AQ Texas 2013 campaign with a High Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS) using iodide (I-) as a reagent ion. ClNO2 concentrations exceeding 50 ppt were regularly detected with peak concentrations typically occurring between 7:00 a.m. and 10:00 am. Hourly averaged Cl2 concentrations peaked daily between 3:00 p.m. and 4:00 p.m., with a 29-day average of 0.9 ± 0.3 (1σ) ppt. A day-time Cl2 source of up to 35 ppt∙h−1 is required to explain these observations, corresponding to a maximum chlorine radical (Cl) production rate of 70 ppt∙h−1. Modeling of the Cl2 source suggests that it can enhance daily maximum O3 and RO2concentrations by 8%–10% and 28%–50%, respectively. Modeling of observed ClNO2 assuming a well-mixed nocturnal boundary layer indicates O3 and RO2 enhancements of up to 2.1% and 38%, respectively, with a maximum impact in the early morning. These enhancements affect the formation of secondary organic aerosol and compliance with air quality standards for ozone and particulate matter. View Full-Text
Keywords: ambient observations; air quality; photochemistry; atomic chlorine; molecular chlorine; nitryl chloride ambient observations; air quality; photochemistry; atomic chlorine; molecular chlorine; nitryl chloride
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Faxon, C.B.; Bean, J.K.; Ruiz, L.H. Inland Concentrations of Cl2 and ClNO2 in Southeast Texas Suggest Chlorine Chemistry Significantly Contributes to Atmospheric Reactivity. Atmosphere 2015, 6, 1487-1506.

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