Methane, tropospheric radical

When NMHC are significant in concentration, differences in their oxidation mechanisms such as how the NMHC chemistry was parameterized, details of R02-/R02 recombination (95), and heterogenous chemistry also contribute to differences in computed [HO ]. Recently, the sensitivity of [HO ] to non-methane hydrocarbon oxidation was studied in the context of the remote marine boundary-layer (156). It was concluded that differences in radical-radical recombination mechanisms (R02 /R02 ) can cause significant differences in computed [HO ] in regions of low NO and NMHC levels. The effect of cloud chemistry in the troposphere has also recently been studied (151,180). The rapid aqueous-phase breakdown of formaldehyde in the presence of clouds reduces the source of HOj due to RIO. In addition, the dissolution in clouds of a NO reservoir (N2O5) at night reduces the formation of HO and CH2O due to R6-RIO and R13. Predictions for HO and HO2 concentrations with cloud chemistry considered compared to predictions without cloud chemistry are 10-40% lower for HO and 10-45% lower for HO2. 

Photolysis of an aqueous solution containing chloroform (314 pmol) and the catalyst [Pt(cohoid)/Ru(bpy) /MV/EDTA] yielded the following products after 15 h (mol detected) chloride ions (852), methane (265), ethylene (0.05), ethane (0.52), and unreacted chloroform (10.5) (Tan and Wang, 1987). In the troposphere, photolysis of chloroform via OH radicals may yield formyl chloride, carbon monoxide, hydrogen chloride, and phosgene as the principal products (Spence et al., 1976). Phosgene is hydrolyzed readily to hydrogen chloride and carbon dioxide (Morrison and Boyd, 1971). 

Madronich, S., and C. Granier, Impact of Recent Total Ozone Changes on Tropospheric Ozone Photodissociation, Hydroxyl Radicals, and Methane Trends, Geophys. Res. Lett., 19, 465-467 (1992). 

Methane is removed continually from the atmosphere by reaction with OH radicals (Section 8.3). In contrast, chlorofluorocarbons and related volatile compounds are inert under the conditions of the lower atmosphere (troposphere), so atmospheric concentrations of these refrigerants and solvents will tend to increase as long as releases continue. The chief concern over chlorofluorocarbons is that they are a major factor in destruction of the stratospheric ozone layer (Section 8.3). They have been banned under the Montreal Protocol of 1988, but it is important that whatever substitutes (inevitably greenhouse active) are introduced to replace them degrade relatively quickly in the troposphere to minimize any contribution they may be capable of making to greenhouse warming. 

Although the troposphere has the characteristic of containing a high relative concentration of water vapor (10 5-10-2), the stratosphere is dry and the water vapor concentration is only a few parts in a million. However, the oxidation of methane by hydroxyl radical must be intro-... 

The atmospheric fate of a halocarbon molecule depends upon whether or not it contains a hydrogen atom. Hydrohalomethanes are oxidized by a series of reactions with radicals prominant in the troposphere, predominantly hydroxyl OH. Fully halogenated methanes are unreactive towards these radicals and consequently are transported up through the troposphere into the stratosphere, where their oxidation is initiated by UV photolysis of a carbon-halogen bond. 

The oxidation scheme for halomethanes not containing a hydrogen atom is similar to that for those which do, except that it is not initiated by tropospheric reaction with hydroxyl radicals, since the fully halogenated methanes are unreactive. Consequently, substantial amounts of CFCs and halons are transported intact up into the stratosphere, where they absorb UV radiation of short wavelength and undergo photodissociation (equation 36) to a halogen atom and a trihalomethyl radical. The halogen atom Y may enter into catalytic cycles for ozone destruction, as discussed in the introduction. 

Hydroxyl radical, OH, is the principal atmospheric oxidant for a vast array of organic and inorganic compounds in the atmosphere. In addition to being the primary oxidant of non-methane hydrocarbons (representative examples of these secondary reactions are given in Table 6), OH radical controls the rate of CO and CH4 oxidation. Furthermore, the OH reaction with ozone also limits the destruction of O3 in the troposphere, it also determines the lifetime of CH3CI, CHsBr, and a wide range of HCFC s, and it controls the rate of NO to HNO3 conversion. Concentration profiles for hydroxyl radical in the atmosphere are shown in Fig. 2. 

A primary example of the interplay between hydroxyl radical and ozone is provided by the photo-induced oxidation of methane in the troposphere. The overall sequence of stoichiometric reactions can be written as ... 

The net result of methane oxidation in the remote troposphere by hydroxyl radical produces 3 molecules of ozone for each molecule oxidized. 

The fraction of 0( D) atoms that form OH is dependent on pressure and the concentration of H2O typically in the marine boundary layer (MBL) about 10% of the 0( D) generate OH. Reactions (2.7 and 2.8) are the primary source of OH in the troposphere, but there are a number of other reactions and photolysis routes capable of forming OH directly or indirectly. As these compounds are often products of OH radical initiated oxidation they are often termed secondary sources of OH and include the photolysis of HONO, HCHO, H2O2 and acetone and the reaction of 0( D) with methane (see Figure 9). Table 2 illustrates the average contribution of various formation routes with altitude in a standard atmosphere. 

The temperature and density structure of the troposphere, along with the concentrations of major constituents, are well documented and altitude profiles have been measured over a wide range of seasons and latitudes for the minor species water, carbon dioxide, and ozone. A few profiles are available for carbon monoxide, nitrous oxide, methane, and molecular hydrogen, while only surface or low-altitude measurements have been made for nitric oxide, nitrogen dioxide, ammonia, sulfur dioxide, hydrogen sulfide, and nonmethane hydrocarbons. No direct measurements of nitric acid and formaldehyde are available, though indirect information does exist. The concentrations of a number of other important species, such as peroxides and oxy and peroxy radicals, have never been determined. Therefore, while considerable information concerning trace constituent concentrations is available, the picture is far from complete. 

On the basis of ratios of C and C present in carbon dioxide, Weinstock (250) estimated a carbon monoxide lifetime of 0.1 year. This was more than an order of magnitude less than previous estimates of Bates and Witherspoon (12) and Robinson and Robbins (214), which were based on calculations of the anthropogenic source of carbon monoxide. Weinstock (250) suggested that if a sufficient concentration of hydroxyl radical were available, the oxidation of carbon monoxide by hydroxyl radical, first proposed by Bates and Witherspoon (12) for the stratosphere, would provide the rapid loss mechanism for carbon monoxide that appeared necessary. By extension of previous stratospheric models of Hunt (104), Leovy (150), Nicolet (180), and others, Levy (152) demonstrated that a large source of hydroxyl radical, the oxidation of water by metastable atomic oxygen, which was itself produced by the photolysis of ozone, existed in the troposphere and that a chain reaction involving the hydroxyl and hydroperoxyl radicals would rapidly oxidize both carbon monoxide and methane. It was then pointed out that all the loss paths for the formaldehyde produced in the methane oxidation led to the production of carbon monoxide [McConnell, McElroy, and Wofsy (171) and Levy (153)1-Similar chain mechanisms were shown to provide tropospheric... 

While Eqn. (1) predicts OH levels in the remote troposphere in reasonably good agreement with the predictions of more elaborate photochemical models which properly treat the HO2/OH coupling, for conditions appropriate for less remote regions where enhanced NOx levels are commonly encountered Eqn. (1) does not accurately calculate the OH concentrations. This is because as NOx levels increase, a greater fraction of the HO2 radicals produced from the methane oxidation reaction sequence react with NO via (R8) to regenerate OH. Thus as illustrated in Figure 4, the levels of OH calculated in a complete photochemical model increase substantially as NOx levels increase from the pptv level (typical of remote marine conditions) to the more polluted ppbv level. For NOx levels in... 

Methane is found throughout the troposphere in concentrations now exceeding 1.6 parts per million by volume (1 ppmv = 10" ), and is the most abundant source of C-H bonds in the atmosphere. Its primary atmospheric removal process is also reaction with HO radicals, as in (6). The atmospheric lifetimes for CHa and CILCCh can be connected through the relative rates of reactions (5) and (6), and the value observed in the laboratory... 

By comparison, the average CO mixing ratio in Earth s troposphere is —0.12 ppmv and it is produced from a variety of anthropogenic and biogenic sources such as fossil fuel combustion, biomass burning, and oxidation of methane and other hydrocarbons. Most of the CO in Earth s troposphere is destroyed by reaction with OH radicals, which are also important for the catalytic... 

Madronich S. and Granier C. (1992) Impact of recent total ozone changes on tropospheric ozone photodissociation, hydroxyl radicals, and methane trends. Geophys. Res. Lett. 19, 465 67. 

There has been considerable debate as to what degree Cl, like Br, radicals might play a role in Arctic springtime tropospheric chemistry. To obtain information on this, Jobson et al. (1994) collected daily air samples at Alert (82.5° N, 62.3° W) from January 21 to April 19, and on an ice floe 150 km north of Alert during April 2-15, 1992. They derived information on the concentrations of OH, Cl, and Br from the different decay rates of a suite of non-methane hydrocarbons the so-called hydrocarbon clock method. Besides some removal of alkanes by reaction with OH during ODEs, additional alkane losses, consistent with removal by reaction with Cl, were measured. 

Methane is the most abundant hydrocarbon in the atmosphere. It plays important roles in atmospheric chemistry and the radiative balance of the Earth. Stratospheric oxidation of CH4 provides a means of introducing water vapor above the tropopause. Methane reacts with atomic chlorine in the stratosphere, forming HCl, a reservoir species for chlorine. Some 90% of the CH4 entering the atmosphere is oxidized through reactions initiated by the OH radical. These reactions are discussed in more detail by Wofsy (1976) and Cicerone and Oremland (1988), and are important in controlling the oxidation state of the atmosphere. Methane absorbs infrared radiation in the troposphere, as do CO2 and H2O, and is an important greenhouse gas (Lacis et al., 1981 Ramanathan et al., 1985). 

Methane is oxidized primarily in the troposphere by reactions involving the hydroxyl radical (OH). Methane is the most abundant hydrocarbon species in the atmosphere, and its oxidation affects atmospheric levels of other important reactive species, including formaldehyde (CH2O), carbon monoxide (CO), and ozone (O3) (Wuebbles and Hayhoe, 2002). The chemistry of these reactions is well known, and the rate of atmospheric CH4 oxidation can be calculated from the temperature and concentrations of the reactants, primarily CH4 and OH (Prinn et al., 1987). Tropospheric OH concentrations are difficult to measure directly, but they are reasonably well constrained by observations of other reactive trace gases (Thompson, 1992 Martinerie et al., 1995 Prinn et al., 1995 Prinn et al., 2001). Thus, rates of tropospheric CH4 oxidation can be estimated from knowledge of atmospheric CH4 concentrations. And because tropospheric oxidation is the primary process by which CH4 is removed from the atmosphere, the estimated rate of CH4 oxidation provides a basis for approximating the total rate of supply of CH4 to the atmosphere from aU sources at steady state (see Section 8.09.2.2) (Cicerone and Oremland, 1988). 

The largest sink for alkanes in the atmosphere is reaction with OH and NO3 radicals. The formation of photochemical smog is described in detail in (Chapter 9.11, Sillman). Mono-aromatic hydrocarbons react only slowly with O3 and NO3 radicals in the troposphere. The only important atmospheric processes for mono-aromatic hydrocarbons, and naphthalene and dinaphthalenes are reactions with OH radicals (Atkinson, 1990). The products of these reactions include aldehydes, cresols, and, in the presence of NO, benzylnitrates. Methane can be an important contributor to ozone formation, especially in the remote troposphere, as described in (Chapter 9.11, Sillman). 

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