TY - JOUR
T1 - Springtime nitrogen oxide-influenced chlorine chemistry in the coastal arctic
AU - McNamara, Stephen M.
AU - Raso, Angela R.W.
AU - Wang, Siyuan
AU - Thanekar, Sham
AU - Boone, Eric J.
AU - Kolesar, Katheryn R.
AU - Peterson, Peter K.
AU - Simpson, William R.
AU - Fuentes, Jose D.
AU - Shepson, Paul B.
AU - Pratt, Kerri A.
N1 - Funding Information:
Financial support was provided by the National Science Foundation Arctic Natural Sciences program (PLR-1417668, PLR-1417906, PLR-1417914) and the National Aeronautics and Space Administration Earth Science Program (NNX14AP44G). We thank Ukpeaġvik Iñupiat Corporation-Science and PolarField Services, as well as Dandan Wei and Jesus Ruiz-Plancarte (Pennsylvania State University), for fieldwork support in Utqiaġvik. The NOAA ESRL GMD ( http://esrl.noaa.gov/gmd/ ) is acknowledged for wind and solar radiation data from the Barrow Observatory. Surface albedo data were obtained from the NSA ARM Climate Research Facility, a U.S. DOE Office of Science user facility sponsored by the Office of Biological and Environmental Research. We thank Hans Osthoff (University of Calgary) for discussions of the ClNO calibration, L. Gregory Huey and David Tanner (Georgia Institute of Technology) for loan of the NO analyzer, and Tom Ryerson and Chelsea Thompson (NOAA) for loan of the NO converter used for CIMS calibrations. 2 2
Funding Information:
Financial support was provided by the National Science Foundation Arctic Natural Sciences program (PLR-1417668, PLR-1417906, PLR-1417914) and the National Aeronautics and Space Administration Earth Science Program (NNX14AP44G). We thank Ukpeagvik Iñupiat Corporation-Science and PolarField Services, as well as Dandan Wei and Jesus Ruiz-Plancarte (Pennsylvania State University), for fieldwork support in Utqiagvik. The NOAA ESRL GMD (http://esrl.noaa.gov/gmd/) is acknowledged for wind and solar radiation data from the Barrow Observatory. Surface albedo data were obtained from the NSA ARM Climate Research Facility, a U.S. DOE Office of Science user facility sponsored by the Office of Biological and Environmental Research. We thank Hans Osthoff (University of Calgary) for discussions of the ClNO2 calibration, L. Gregory Huey and David Tanner (Georgia Institute of Technology) for loan of the NO analyzer, and Tom Ryerson and Chelsea Thompson (NOAA) for loan of the NO2 converter used for CIMS calibrations.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/7/16
Y1 - 2019/7/16
N2 - Atomic chlorine (Cl) is a strong atmospheric oxidant that shortens the lifetimes of pollutants and methane in the springtime Arctic, where the molecular halogens Cl2 and BrCl are known Cl precursors. Here, we quantify the contributions of reactive chlorine trace gases and present the first observations, to our knowledge, of ClNO2 (another Cl precursor), N2O5, and HO2NO2 in the Arctic. During March - May 2016 near Utqiaġvik, Alaska, up to 21 ppt of ClNO2, 154 ppt of Cl2, 27 ppt of ClO, 71 ppt of N2O5, 21 ppt of BrCl, and 153 ppt of HO2NO2 were measured using chemical ionization mass spectrometry. The main Cl precursor was calculated to be Cl2 (up to 73%) in March, while BrCl was a greater contributor (63%) in May, when total Cl production was lower. Elevated levels of ClNO2, N2O5, Cl2, and HO2NO2 coincided with pollution influence from the nearby town of Utqiaġvik and the North Slope of Alaska (Prudhoe Bay) Oilfields. We propose a coupled mechanism linking NOx with Arctic chlorine chemistry. Enhanced Cl2 was likely the result of the multiphase reaction of Cl- (aq) with ClONO2, formed from the reaction of ClO and NO2. In addition to this NOx-enhanced chlorine chemistry, Cl2 and BrCl were observed under clean Arctic conditions from snowpack photochemical production. These connections between NOx and chlorine chemistry, and the role of snowpack recycling, are important given increasing shipping and fossil fuel extraction predicted to accompany Arctic sea ice loss.
AB - Atomic chlorine (Cl) is a strong atmospheric oxidant that shortens the lifetimes of pollutants and methane in the springtime Arctic, where the molecular halogens Cl2 and BrCl are known Cl precursors. Here, we quantify the contributions of reactive chlorine trace gases and present the first observations, to our knowledge, of ClNO2 (another Cl precursor), N2O5, and HO2NO2 in the Arctic. During March - May 2016 near Utqiaġvik, Alaska, up to 21 ppt of ClNO2, 154 ppt of Cl2, 27 ppt of ClO, 71 ppt of N2O5, 21 ppt of BrCl, and 153 ppt of HO2NO2 were measured using chemical ionization mass spectrometry. The main Cl precursor was calculated to be Cl2 (up to 73%) in March, while BrCl was a greater contributor (63%) in May, when total Cl production was lower. Elevated levels of ClNO2, N2O5, Cl2, and HO2NO2 coincided with pollution influence from the nearby town of Utqiaġvik and the North Slope of Alaska (Prudhoe Bay) Oilfields. We propose a coupled mechanism linking NOx with Arctic chlorine chemistry. Enhanced Cl2 was likely the result of the multiphase reaction of Cl- (aq) with ClONO2, formed from the reaction of ClO and NO2. In addition to this NOx-enhanced chlorine chemistry, Cl2 and BrCl were observed under clean Arctic conditions from snowpack photochemical production. These connections between NOx and chlorine chemistry, and the role of snowpack recycling, are important given increasing shipping and fossil fuel extraction predicted to accompany Arctic sea ice loss.
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U2 - 10.1021/acs.est.9b01797
DO - 10.1021/acs.est.9b01797
M3 - Article
C2 - 31184868
AN - SCOPUS:85069948590
SN - 0013-936X
VL - 53
SP - 8057
EP - 8067
JO - Environmental Science & Technology
JF - Environmental Science & Technology
IS - 14
ER -