Troposphere hydrogen

Graedel, T.E., B. Kleiner, and G.C. Patterson, Measurements of extreme concentrations of tropospheric hydrogen sulfide. J Geophys Res 79, 4467, 1974. 

Figure 4 shows a simplified mechanism for the oxidation of alkanes in the troposphere. Hydrogen abstraction... 

R is hydrogen, alkenyl, or alkyne. In remote tropospheric air where NO concentrations ate sometimes quite low, HO2 radicals can react with ozone (HO2 + O3 — HO + 2 O2) and result in net ozone destmction rather than formation. The ambient ozone concentration depends on cloud cover, time of day and year, and geographical location. 

NMHC. A large number of hydrocarbons are present in petroleum deposits, and their release during refining or use of fuels and solvents, or during the combustion of fuels, results in the presence of more than a hundred different hydrocarbons in polluted air (43,44). These unnatural hydrocarbons join the natural terpenes such as isoprene and the pinenes in their reactions with tropospheric hydroxyl radical. In saturated hydrocarbons (containing all single carbon-carbon bonds) abstraction of a hydrogen (e,g, R4) is the sole tropospheric reaction, but in unsaturated hydrocarbons HO-addition to a carbon-carbon double bond is usually the dominant reaction pathway. 

Since the recognition of the role of chlorine in catalytic ozone destruction, increasing effort has been devoted to finding replacements. In most cases reported so far, the replacements are partially halogenated molecules that retain one or more hydrogen atoms (HCFCs and HFC s). The presence of H-atoms gives HO a handle (via H-atom abstractions such as R4) for their tropospheric... 

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). 

Photolytic. Irradiation of vinyl chloride in the presence of nitrogen dioxide for 160 min produced formic acid, HCl, carbon monoxide, formaldehyde, ozone, and trace amounts of formyl chloride and nitric acid. In the presence of ozone, however, vinyl chloride photooxidized to carbon monoxide, formaldehyde, formic acid, and small amounts of HCl (Gay et al, 1976). Reported photooxidation products in the troposphere include hydrogen chloride and/or formyl chloride (U.S. EPA, 1985). In the presence of moisture, formyl chloride will decompose to carbon monoxide and HCl (Morrison and Boyd, 1971). Vinyl chloride reacts rapidly with OH radicals in the atmosphere. Based on a reaction rate of 6.6 x lO" cmVmolecule-sec, the estimated half-life for this reaction at 299 K is 1.5 d (Perry et al., 1977). Vinyl chloride reacts also with ozone and NO3 in the gas-phase. Sanhueza et al. (1976) reported a rate constant of 6.5 x 10 cmVmolecule-sec for the reaction with OH radicals in air at 295 K. Atkinson et al. (1988) reported a rate constant of 4.45 X 10cmVmolecule-sec for the reaction with NO3 radicals in air at 298 K. 

Hydrogen sulfide occurs in natural gas. It also is found in many sewer gases. It is a by-product of many industrial processes. Trace amounts of dissolved H2S are found in wastewaters in equilibrium with dissolved sulfides and hydrosulfides. It also is found in volcanic eruptions, hot springs and in troposphere. The average concentration of H2S in the air is about 0.05 ppb. 

Figure 4.33 shows the absorption cross sections of HC1 and HBr at room temperature (DeMore et al., 1997 Huebert and Martin, 1968). Neither absorb above 290 nm, so their major tropospheric fates are deposition or reaction with OH. Even in the stratosphere, photolysis is sufficiently slow that these hydrogen halides act as temporary halogen reservoirs (see Chapter 12). 

As seen in Table 6.1, the reactions of the nitrate radical with the simple aromatic hydrocarbons are generally too slow to be important in the tropospheric decay of the organic. However, one of the products of the aromatic reactions, the cresols, reacts quite rapidly with NO,. o-Cresol, for example, reacts with N03 with a room temperature rate constant of 1.4 X 10 " cm3 molecule-1 s-1, giving a lifetime for the cresol of only 1 min at 50 ppt N03. This rapid reaction is effectively an overall hydrogen abstraction from the pheno-... 

Since it varies with the square root of the hydrogen ion concentration, it has a weak pH dependence. However, as we shall see, this uncatalyzed reaction is too slow to be of importance under typical tropospheric conditions. 

Sauer, F., S. Limbach, and G. K. Moortgat, Measurements of Hydrogen Peroxide and Individual Organic Peroxides in the Marine Troposphere, Atmos. Environ., 31, 1173-1184 (1997). 

Tremmel, H. G., W. Junkermann, and F. Slemr, On the Distribution of Hydrogen Peroxide in the Lower Troposphere over the Northeastern United States during Late Summer 1988, J. Geophys. Res., 98, 1083-1099 (1993). 

Zander, R., C. P. Rinsland, C. B. Farmer, J. Namkung, R. H. Norton, and J. M. Russell III, Concentrations of Carbonyl Sulfide and Hydrogen Cyanide in the Free Upper Troposphere and Lower Stratosphere Deduced from ATMOS/Spacelab 3 Infrared Solar Occultation Spectra, . /. Geophys. Res., 93, 1669-1678(1988). 

While there are a variety of other chlorinated organics such as methylchloroform (CH3CC13) that are emitted, these have relatively short tropospheric lifetimes because they have an abstractable hydrogen atom (e.g., see WMO, 1995). For example, while the stratospheric lifetime of methylchloroform is estimated to be 34 7 years (Volk et al., 1997), its overall atmospheric lifetime is only 5-6 years, primarily due to the removal by OH in the troposphere (toii 6.6 years), with a much smaller contribution from uptake by the ocean (roi i an 85 years) (WMO, 1995). 

The replacements and alternates for the CFCs (Table 13.1) are characterized by having abstractable hydrogen atoms, and hence they are removed to varying extents by reaction with OH in the troposphere before reaching the stratosphere. The HFCs do not contain chlorine at all, so that their ODPs are very small, essentially zero (Table 13.3). In this section we discuss briefly the tropospheric chemistry of HCFCs and HFCs. 

Because many of the alternates and replacements for CFCs have an abstractable hydrogen atom, reaction with OH in the troposphere dominates their loss. Table 13.4 gives some rate constants for the reaction of OH with these compounds the kinetics summary of De-More et al. (1997) should be consulted for other compounds. It is seen that the rate constants at 298 K are typically in the range of 10-l3-10-ls cm3 molecule-1 s-1, depending on the degree of halogen substitution and the nature of the halogen, e.g., F, Cl, or Br. Typical A factors are of the order of 1 X 10 12 cm3 molecule-1 s-1 per H atom (DeMore, 1996). 

Because HC(0)CFC12 has an abstractable hydrogen atom, it reacts with OH in the troposphere ... 

The reason that the ODPs of these CFC replacements are much smaller than those of the original CFCs is the presence of an abstractable hydrogen with which OH can react. However, this also means that they can also contribute to ozone formation in the troposphere. Hayman and Derwent (1997) have used their photochemical trajectory model to calculate tropospheric ozone-forming potentials of some of these CFC replacements. Table 13.10 summarizes these relative ozone-forming potentials, expressed taking that for ethene as 100. Clearly, although they react in the troposphere, their contribution to tropospheric ozone formation is expected to be very small. 

One of the approaches to the development of alternate CFCs is to use compounds with one or more abstractable hydrogen atoms so that their tropospheric lifetimes are reduced and less reaches the stratosphere. 

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