Abstract

Abstract. Reactive nitrogen (Nr = NO, NO2, HONO) and volatile organic carbon emissions from oil and gas extraction activities play a major role in wintertime ground-level ozone exceedance events of up to 140 ppb in the Uintah Basin in eastern Utah. Such events occur only when the ground is snow covered, due to the impacts of snow on the stability and depth of the boundary layer and ultraviolet actinic flux at the surface. Recycling of reactive nitrogen from the photolysis of snow nitrate has been observed in polar and mid-latitude snow, but snow-sourced reactive nitrogen fluxes in mid-latitude regions have not yet been quantified in the field. Here we present vertical profiles of snow nitrate concentration and nitrogen isotopes (δ15N) collected during the Uintah Basin Winter Ozone Study 2014 (UBWOS 2014), along with observations of insoluble light-absorbing impurities, radiation equivalent mean ice grain radii, and snow density that determine snow optical properties. We use the snow optical properties and nitrate concentrations to calculate ultraviolet actinic flux in snow and the production of Nr from the photolysis of snow nitrate. The observed δ15N(NO3−) is used to constrain modeled fractional loss of snow nitrate in a snow chemistry column model, and thus the source of Nr to the overlying boundary layer. Snow-surface δ15N(NO3−) measurements range from −5 to 10 ‰ and suggest that the local nitrate burden in the Uintah Basin is dominated by primary emissions from anthropogenic sources, except during fresh snowfall events, where remote NOx sources from beyond the basin are dominant. Modeled daily averaged snow-sourced Nr fluxes range from 5.6 to 71 × 107 molec cm−2 s−1 over the course of the field campaign, with a maximum noontime value of 3.1 × 109 molec cm−2 s−1. The top-down emission estimate of primary, anthropogenic NOx in Uintah and Duchesne counties is at least 300 times higher than the estimated snow NOx emissions presented in this study. Our results suggest that snow-sourced reactive nitrogen fluxes are minor contributors to the Nr boundary layer budget in the highly polluted Uintah Basin boundary layer during winter 2014.

Highlights

  • Ozone (O3) has adverse respiratory effects, is an effective greenhouse gas (UNEP, 2011), and, through formation of the hydroxyl radical, influences the oxidizing capacity of the atmosphere (Thompson, 1992)

  • Our results suggest that snow-sourced reactive nitrogen fluxes are minor contributors to the Nr boundary layer budget in the highly polluted Uintah Basin boundary layer during winter 2014

  • Atmospheric measurements in the Uintah Basin during UBWOS2012, UBWOS2013, and UBWOS2014 reveal that the total reactive nitrogen abundances (NOy = NO + NO2 + HNO3 + PAN + N2O5 + NO3 + ClNO2 + organic nitrates) are highest (12–24 ppbv) in 2013 due to persistent shallow inversion layers triggered by stagnant air masses and snow cover, lowest in 2012 (4–9 ppbv) when no snow covered the ground, and in between (8–18 ppbv) in winter 2014, with the highest NOy values generally in midday (Wild et al, 2016)

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Summary

Introduction

Ozone (O3) has adverse respiratory effects, is an effective greenhouse gas (UNEP, 2011), and, through formation of the hydroxyl radical, influences the oxidizing capacity of the atmosphere (Thompson, 1992). Atmospheric measurements in the Uintah Basin during UBWOS2012, UBWOS2013, and UBWOS2014 reveal that the total reactive nitrogen abundances (NOy = NO + NO2 + HNO3 + PAN + N2O5 + NO3 + ClNO2 + organic nitrates) are highest (12–24 ppbv) in 2013 due to persistent shallow inversion layers triggered by stagnant air masses and snow cover, lowest in 2012 (4–9 ppbv) when no snow covered the ground, and in between (8–18 ppbv) in winter 2014, with the highest NOy values generally in midday (Wild et al, 2016). In addition to aiding in the formation and maintenance of a stable air mass with enhanced UV radiation, snow may recycle reactive nitrogen oxides (Nr = NOx, HONO) between the snow surface and the overlying atmosphere, effectively increasing the atmospheric lifetime of Nr. The major sink of Nr in the atmosphere is the formation and deposition of nitrate (particulate NO−3 plus HNO3(g)).

UBWOS 2014 field site description and meteorological conditions
Snow pit measurements and snow sample preparation
Optical measurements
Chemical concentration and nitrate isotopic measurements
Snow radiative transfer model
Snow-sourced reactive nitrogen flux calculations
Observations
31 January
Calculations of snow actinic flux profiles and flux of snow-sourced Nr
22 January 31 January 4 February
Snow photochemistry column model
Impact of snow-sourced Nr on the boundary layer reactive nitrogen budget
Full Text
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