The oxidation of ammonia, hydrogen sulfide, and methane in nonurban tropospheres

Graedel, T. E.

doi:10.1029/jc082i037p05917

Cited by 22 publications

(8 citation statements)

References 33 publications

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“…Reaction with O8 is found by this method to be the principal chemical removal mechanism for all of the terpenes with measured O8 rate constants. A more detailed calculation, however [Graedel, 1977], suggests that on sunny summer days reaction with HO. may be dominant during the midday hours.…”

Section: Rate Constants For Birnolecular Reactionsmentioning

confidence: 92%

Terpenoids in the atmosphere

Graedel¹

1979

Reviews of Geophysics

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139

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Terpenoids (terpenes and their oxygenated derivatives) are common tropospheric species. Information concerning the terpenoids and assessing their importance in atmospheric processes is sparse and widely distributed, however. This review presents chemical structure, physical property, and source information for 45 terpenoids known to be emitted into the atmosphere. Rate constants for the reactions of the terpenoids with atmospheric scavengers are presented, and typical terpenoid lifetimes are derived. Chemical product studies are used to derive plausible reaction mechanisms for selected acyclic, monocyclic, and bicyclic terpenes. The atmospheric cycle of the terpenoids is discussed, and it is concluded that inadequate information currently precludes quantitative assessments of the relative impact of terpenoids on local, regional, and global atmospheric processes.

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Section: Rate Constants For Birnolecular Reactionsmentioning

confidence: 92%

Terpenoids in the atmosphere

Graedel¹

1979

Reviews of Geophysics

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139

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“…0094-8276/79/049L-0388501.00 tions for H2S, DMS, and SO2 are well established and rate constant information is available in the literature. For H2S the subsequent steps also appear to be satisfactorily determined [Graedel, 1977[Graedel, ,1978. The products of the HO.-CH3SCH 3 reaction chain have not been established, and Kurylo [1978] points out that the laboratory data can be interpreted either as HO.…”

Section: The H•s Concentrations Measured By S!att Et Al [1978] Inmentioning

confidence: 94%

Reduced sulfur emission from the open oceans

Graedel¹

1979

Geophysical Research Letters

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The reduced sulfur compounds H2S and CH3SCH3 have been included in a diurnal kinetic photochemical model of the natural marine atmosphere. The self‐consistent solution provides the oceanic emission fluxes necessary to balance atmospheric chemical removal. These fluxes imply global values of 30 Tg S yr−1, near the lower limit prescribed by current global sulfur cycle assessments. The conversion of reduced sulfur gases to SO2 does not result in SO2 concentrations as high as are measured; either a natural or transport source of SO2 is present or additional reduced sulfur compounds are involved in oceanic SO2 production. The calculated upper limit for sulfate formation as a result of oxidation chemistry from the H2S and CH3SCH3 precursors is of order 25 Tg S yr−1, with an additional 29 Tg S yr−1 resulting from oxidation of SO2 generated from sources other than H2S and CH3SCH3.

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“…Until adequate thermodynamic and kinetic data are available for these sulfur-containing radicals and their hydrates, theoretical considerations dealing with the role of sulfur oxidation in atmospheric chemistry are dependent on inferences of mechanisms and rates from the limited observations currently available. Under normal atmospheric conditions the hydroxyl radical has been suggested by Graedel [1977b] and $ze and Ko [1980], but rates for this reaction sequence are not available in the kinetic literature. Leu and Smith [1982] also proposed the reaction…”

Section: Introductionmentioning

confidence: 97%

On the chemistry of stratospheric SO₂ from volcanic eruptions

McKeen¹,

Liu²,

Kiang³

1984

J. Geophys. Res.

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The April 4, 1982, eruption of El Chich6n in southern Mexico introduced several megatons of gaseous sulfur into the stratosphere, mostly as SO: or H:S. Available kinetic information indicates that H:S is converted to SO: much faster than SO: is oxidized to sulfate by homogeneous gas phase reactions. The process by which SO: is chemically converted to sulfate is not precisely known, and various reaction mechanisms have been proposed. The rate-limiting step of SO: oxidation is believed to be reaction with the OH radical to form the HOSO: radical. Depending on the fate of HOSO:, odd hydrogen may or may not be regenerated in the overall oxidation sequence. A decrease in OH due to volcanic SO: should be observable through the gaseous species that depend on OH, and in particular SO: itself. One-and two-dimensional model results are presented that estimate the photochemical effects of the SO: from the E1 Chich6n volcano under various assumptions of HOSO: to sulfate conversion. It is found that the chemical lifetime for the volcanic SO: would be greater than 100 days for a large portion of the cloud if HOSO: does not regenerate odd hydrogen during conversion to sulfate and if heterogeneous losses of SO: are not competitive. However, observations of sulfate particle formation and SO: imply a chemical lifetime of 30-40 days, which is consistent with HOSO: conversion regenerating odd hydrogen. The implications of this finding for the problem of sulfate formation in the polluted troposphere is briefly reviewed. INTRODUCTIONThe optical and climatic importance of stratospheric sulfur injections by volcanic eruptions [e.g., Whitten, 1982] has drawn worldwide attention to the recent eruption of E1 Chich6n in southeastern Mexico on April 4, 1982. Large volcanic eruptions may also cause some interesting changes in stratospheric chemistry [Turco et al., 1982; Capone et al., 1983; Crutzen and Schmailzl, 1983]. It is generally accepted that the primary sulfur-bearing species injected into the stratosphere by volcanic eruptions is SO2 [Lazrus et al., 1979] and H2S [Hobbs et al., 1982]. Suggestions that COS or CS2 could also be injected by E1 Chich6n have not been substantiated by observations [Leifer et al., 1982; Vedder et al., 1982].One of the many interesting photochemical problems related to atmospheric chemistry is the mechanism of SO2 oxidation to sulfate. Experimental evidence supports the assertion that SO2 oxidation by the OH addition reaction is the ratecontrolling step in sulfate formation [Calvert et al., 1978; Davis et al., 1979]. The reaction paths of the HOSO2 conversion to sulfate are uncertain, and several investigators have proposed a variety of homogeneous and heterogeneous processes I-Cox, 1975; Calvert and McQuigg, 1975; Benson, 1978; Davis et al., 1979; Friend et al., 1980; Calvert and Stockwell, 1983]. Large stratospheric injections of SO2 have the potential for depleting the OH radical [Cadle, 1980], which in turn increases the chemical lifetime of SO2 and affects the abundance of several chemical species. Howe...

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The oxidation of ammonia, hydrogen sulfide, and methane in nonurban tropospheres

Cited by 22 publications

References 33 publications

Terpenoids in the atmosphere

Terpenoids in the atmosphere

Reduced sulfur emission from the open oceans

On the chemistry of stratospheric SO₂ from volcanic eruptions

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The oxidation of ammonia, hydrogen sulfide, and methane in nonurban tropospheres

Cited by 22 publications

References 33 publications

Terpenoids in the atmosphere

Terpenoids in the atmosphere

Reduced sulfur emission from the open oceans

On the chemistry of stratospheric SO2 from volcanic eruptions

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Product

Resources

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On the chemistry of stratospheric SO₂ from volcanic eruptions