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Springtime Nitrogen Oxide-Influenced Chlorine Chemistry in the Coastal Arctic
Version 2 2020-03-09, 11:35
Version 1 2019-06-26, 14:34
journal contribution
posted on 2019-06-11, 00:00 authored by Stephen
M. McNamara, Angela R. W. Raso, Siyuan Wang, Sham Thanekar, Eric J. Boone, Katheryn R. Kolesar, Peter K. Peterson, William R. Simpson, Jose D. Fuentes, Paul B. Shepson, Kerri A. PrattAtomic
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.