Nitryl chloride, an active halogen, can be produced through the night-time reaction of dinitrogen pentoxide with chloride-containing aerosol in the polluted marine boundary, and has been measured at levels that are sufficient to affect the photochemistry of oxidants off the southwestern US coast and near Houston, Texas.

High levels of nitryl chloride in the polluted subtropical marine boundary layer

The nitrate radical, NO3, is photochemically unstable but is one of the most chemically important species in the nocturnal atmosphere. It is accompanied by the presence of dinitrogen pentoxide, N2O5, with which it is in rapid thermal equilibrium at lower tropospheric temperatures. These two nitrogen oxides participate in numerous atmospheric chemical systems. NO3 reactions with VOCs and organic sulphur species are important, or in some cases even dominant, oxidation pathways, impacting the budgets of these species and their degradation products. These oxidative reactions, together with the ozonolysis of alkenes, are also responsible for the nighttime production and cycling of OH and peroxy (HO2 + RO2) radicals. In addition, reactions of NO3 with biogenic hydrocarbons are particularly efficient and are responsible for the production of organic nitrates and secondary organic aerosol. Heterogeneous chemistry of N2O5 is one of the major processes responsible for the atmospheric removal of nitrogen oxides as well as the cycling of halogen species though the production of nitryl chloride, ClNO2. The chemistry of NO3 and N2O5 is also important to the regulation of both tropospheric and stratospheric ozone. Here we review the essential features of this atmospheric chemistry, along with field observations of NO3, N2O5, nighttime peroxy and OH radicals, and related compounds. This review builds on existing reviews of this chemistry, and encompasses field, laboratory and modelling work spanning more than three decades.

Nighttime radical observations and chemistry

. Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

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Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

Optical properties of secondary organic aerosols and their changes by chemical processes.

Data from the oil- and gas-producing basin of northeastern Utah and a box model are used to assess the photochemical reactions of nitrogen oxides and volatile organic compounds that lead to excessive atmospheric ozone pollution in winter. The US experience with air quality degradation from shale gas extraction presents a measurement and modelling framework relevant to similar developments in other regions projected for the near future. High ozone mixing ratios have been observed in oil and gas producing basins in the United States during winter, but the underlying chemistry involved is not fully understood. This study presents a quantitative assessment of the underlying chemistry responsible for the winter ozone pollution events based on data from an oil and gas basin in Utah and a chemical 'box model' simulation. The results show that very high volatile organic carbon concentrations optimize the ozone production efficiency of nitrogen oxides with carbonyl photolysis as a dominant oxidant source. The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality1 to the influence of increased methane leakage on climate2, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides3,4 (NOx = NO + NO2) and volatile organic compounds5,6,7 (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects8. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter9,10,11,12,13. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts and provide broader insight into the response of winter ozone to primary pollutants.

High winter ozone pollution from carbonyl photolysis in an oil and gas basin

This article describes a cavity ring-down spectrometer (CaRDS) specifically designed and constructed for installation on the NOAA WP-3D Orion (P-3) aircraft for sensitive, rapid in situ measurement of NO3 and N2O5. While similar to our previously described CaRDS instrument, this instrument has significant improvements in the signal-to-noise ratio, the time resolution, and in overall size and weight. Additionally, the instrument utilizes a custom-built, automated filter changer that was designed and constructed to meet the requirement for removal of particulate matter in the airflow while allowing fully autonomous instrument operation. The CaRDS instrument has a laboratory detection sensitivity of 4×10−11cm−1 in absorbance or 0.1pptv (pptv denotes parts per trillion volume) of NO3 in a 1s average, although the typical detection sensitivities encountered in the field were 0.5pptv for NO3 and 1pptv for N2O5. The instrument accuracy is 25% for NO3 and 20%–40% for N2O5, limited mainly by the uncertainty in the...

Maya R. Nunley

Papers

Aircraft instrument for simultaneous, in situ measurement of NO3 and N2O5 via pulsed cavity ring-down spectroscopy