Nitrogen oxides tropospheric ozone

The evolution of the emissions of some atmospheric pollutants in Europe (EU-15) in the period 1990-1999 has been presented in the report of Goodwin and Mareckova (2002). The report includes acidifying pollutants (ammonia, sulfur dioxide, and nitrogen oxides), tropospheric ozone precursors, NMVOCs, carbon monoxide, and particulate matter... 

Jaffe, D The Relationship between Anthropogenic Nitrogen Oxides and Ozone Trends in the Arctic Troposphere, in The Tropospheric Chemistry of Ozone in the Polar Regions (H. Niki and... 

Nitrogen oxides also play a significant role in regulating the chemistry of the stratosphere. In the stratosphere, ozone is formed by the same reaction as in the troposphere, the reaction of O2 with an oxygen atom. However, since the concentration of O atoms in the stratosphere is much higher (O is produced from photolysis of O2 at wavelengths less than 242 nm), the concentration of O3 in the stratosphere is much higher. 

Describe the trends in the ozone concentrations in the troposphere and stratosphere, and the total ozone column. What roles do nitrogen oxides play in these changes ... 

Air pollution in cities can be considered to have three components sources, transport and transformations in the troposphere, and receptors. The sources are processes, devices, or activities that emits airborne substances. When the substances are released, they are transported through the atmosphere, and are transformed into different substances. Air pollutants that are emitted directly to the atmosphere are called primary pollutants. Pollutants that are formed in the atmosphere as a result of transformations are called secondary pollutants. The reactants that undergo the transformation are referred to as precursors. An example of a secondary pollutant is troposphere ozone, O3, and its precursors are nitrogen oxides (NO = NO + NO2) and non-methane hydrocarbons, NMHC. The receptors are the person, animal, plant, material, or urban ecosystems affected by the emissions (Wolff, 1999). 

Nitrogen oxides (NO ) are formed during the combustion at high temperature of fossil fuels and of biomasses and are blamed for the production of acid rain, the formation of ozone in the troposphere and of secondary particulate matter and for causing a reduction in breathing functionality and damage to the cardio-circulatory system in humans. 

Oxides of nitrogen play a central role in essentially all facets of atmospheric chemistry. As we have seen, N02 is key to the formation of tropospheric ozone, contributing to acid deposition (some are toxic to humans and plants), and forming other atmospheric oxidants such as the nitrate radical. In addition, in the stratosphere their chemistry and that of halogens interact closely to control the chain length of ozone-destroying reactions. 

As discussed in other chapters of this book and summarized in Chapter 16, the formation of tropospheric ozone from photochemical reactions of volatile organic compounds (VOC) and oxides of nitrogen (NC/) involves many reactions. Concentrations are therefore quite variable geographically, temporally, and altitudinally. Additional complications come from the fact that there are episodic injections of stratospheric 03 into the troposphere as well as a number of sinks for its removal. Because 03 decomposes thermally, particularly on surfaces, it is not preserved in ice cores. All of these factors make the development of a global climatology for 03 in a manner similar to that for N20 and CH4, for example, much more difficult. In addition, the complexity of the chemistry leading to O, formation from VOC and NOx is such that model-predicted ozone concentrations can vary from model to model (e.g., see Olson et al., 1997). 

In short, the concentrations of tropospheric ozone, which is also a greenhouse gas, have also increased over the past century, an increase attributed to increased oxides of nitrogen emissions associated with fossil fuel combustion (e.g., see Volz and Kley, 1988 and Janach, 1989). 

Nitrogen dioxide is about 20 to 50% of the total nitrogen oxides NO, (NO, NOz, HN03, N2Os), while CIO represents about 10 to 15% of the total chlorine species CIO, (Cl, CIO, HCI) at 25 to 30 km. Hence, the rate of ozone removal by CIO, is about equal to that by NO, if the amounts of NO, are equal to those of CIO,. According to a calculation by Turco and Whitten (981), the reduction of ozone in the stratosphere in the year 2022 with a continuous use of chlorofluoromethanes at present levels would be 7%. Rowland and Molina (843) conclude that the ozone depletion level at present is about 1%, but it would increase up to 15 to 20% ifthechlorofluoromethane injection were to continue indefinitely at the present rates. Even if release of chlorofluorocarbons were stopped after a large reduction of ozone were found, it would take 100 or more years for full recovery, since diffusion of chlorofluorocarbons to the stratosphere from the troposphere is a slow process. The only loss mechanism of chlorofluorocarbons is the photolysis in the stratosphere, production of HCI, diffusion back to the troposphere, and rainout. 

Reactions R1 - RIO are also key reactions in determining OH distribution in the troposphere and lower stratosphere. The key point here is that increases in ozone and nitrogen oxides enhances the OH distribution through reactions R1 and RIO, while enhanced carbon monoxide and methane reduces OH through reactions R4 and R6. Furthermore, reactions with OH (R4 and R6) represent the main loss of CO and methane. 

Stevenson D.S., W.J. Collins, C.A. Johnson and RG. Derwent, 1997 The impact of nitrogen oxide emissions on tropospheric ozone studied with a 3-D Lagrangian model including foil diurnal chemistry, Atmos. Env.,31, 1837-1850. 

Although the nitric acid molecule is subject to various reactions and to photodissociation, nevertheless it remains, and it becomes the most important of the molecules containing NO (HN04, N205, NO3,. . . ) in the lower stratosphere. However, it cannot accumulate because it crosses the tropopause into the troposphere, where it rapidly disappears because of its solubility in water. Thus, if N20 is the source of the nitrogen oxides in the stratosphere, nitric acid is the sink that prevents their accumulation beyond certain limits. But it is now known that the sequence of reactions (20), (21), and (22) results in a lower concentration of stratospheric ozone than would be possible in a pure oxygen atmosphere. 

Nitrogen oxide (NOx) The result of photochemical reactions of nitric oxide in ambient air a major component of photochemical smog. It is a product of combustion from transportation and stationary sources and a major contributor to the formation of ozone in the troposphere and to acid deposition. 

Globally, the oxides of nitrogen, NO (nitric oxide), NO2 (nitrogen oxide), and N2O (nitrous oxide), are key species involved in the chemistry of the troposphere and stratosphere. NO and N2O are produced mostly by microbial soil activity, whereas biomass burning is also an important source of NO. Nitric oxide is a species involved in the photochemical production of ozone in the troposphere, is involved in the chemical produaion of nitric acid, and is an important component of acid precipitation. Nitrous oxide plays a key role in stratospheric ozone depletion and is an important greenhouse gas, with a global warming potential more than 200 times that of CO2. 

The hydroxyl radical so produced is the major oxidising species in the troposphere, and a complete picture of its chemistry holds the key to furthering progress in understanding tropospheric chemistry. The chemistry discussed in detail elsewhere, is of course very complex. To take, for example, the cycle of reactions with carbon monoxide, which may be net producers or destroyers of tropospheric ozone depending upon the concentration of oxides of nitrogen present. In the presence of NO, the cycle (16)-(20) occurs, without loss of OH or NO, whereas at low NO concentrations, the cycle (17), (18) and (21), again without loss of OH. 

Definitely yes. In the troposphere, to which I think you may be referring, N2O is relatively inert. It is in the stratosphere where reaction (18) plays such an important role releasing the nitrogen oxides which dominate the catalytic destruction of ozone. 

---