The iron catalyzed oxidation of sulfur: Reconciliation of the literature rates

Martin, Leigh R.; Hill, Michael W.

doi:10.1016/0004-6981(67)90100-x

Cited by 87 publications

(37 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For O 3 , the rate constant is positively related to I . For TMI + O 2 [here, only Fe(III) and Mn(II) are considered as effective catalyzing TMIs ( 58 , 59 )], the rate constant decreases significantly with increasing I , even without considering the sulfate inhabitation effect (referring to the effect that the formation of the sulfate-TMI complex would reduce catalytically active TMI concentrations) ( 55 , 60 ). …”

Section: Methodsmentioning

confidence: 99%

Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China

et al. 2016

View full text Add to dashboard Cite

show abstract

Section: Methodsmentioning

confidence: 99%

Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Due to the large decrease in the aqueous-phase reaction rate constant for TMI-initiated S(IV) oxidation by O 2 with increasing I s (Martin and Hill, 1967) and the high I s of aerosols (Table S4), combined with the fact that the rate constant for the S(IV) + O 2 mechanism on acidic microdroplets proposed by Hung and Hoffman (2015) likely includes the effect of TMIs, we do not directly consider TMI-initiated S(IV) oxidation by O 2 in aerosol water. R S(IV) + oxi was calculated as described in Table S3.…”

Section: Estimate Of Sulfate Production Rate In Aerosol Watermentioning

confidence: 99%

Isotopic constraints on heterogeneous sulfate production in Beijing haze

et al. 2018

View full text Add to dashboard Cite

Abstract. Discerning mechanisms of sulfate formation during fine-particle pollution (referred to as haze hereafter) in Beijing is important for understanding the rapid evolution of haze and for developing cost-effective air pollution mitigation strategies. Here we present observations of the oxygen-17 excess of PM 2.5 sulfate ( 17 O(SO 2− 4 )) collected in Beijing haze from October 2014 to January 2015 to constrain possible sulfate formation pathways. Throughout the sampling campaign, the 12-hourly averaged PM 2.5 concentrations ranged from 16 to 323 µg m −3 with a mean of (141 ± 88 (1σ )) µg m −3 , with SO Our estimate suggested that in-cloud reactions dominated sulfate production on polluted days (PDs, PM 2.5 ≥ 75 µg m −3 ) of Case II in October 2014 due to the relatively high cloud liquid water content, with a fractional contribution of up to 68 %. During PDs of Cases I and III-V, heterogeneous sulfate production (P het ) was estimated to contribute 41-54 % to total sulfate formation with a mean of (48 ± 5) %. For the specific mechanisms of heterogeneous oxidation of SO 2 , chemical reaction kinetics calculations suggested S(IV) (= SO 2 q H 2 O + HSO − 3 + SO 2− 3 ) oxidation by H 2 O 2 in aerosol water accounted for 5-13 % of P het . The relative importance of heterogeneous sulfate production by other mechanisms was constrained by our observed 17 O(SO 2− 4 ). Heterogeneous sulfate production via S(IV) oxidation by O 3 was estimated to contribute 21-22 % of P het on average. Heterogeneous sulfate production pathways that result in zero-17 O(SO 2− 4 ), such as S(IV) oxidation by NO 2 in aerosol water and/or by O 2 via a radical chain mechanism, contributed the remaining 66-73 % of P het . The assumption about the thermodynamic state of aerosols (stable or metastable) was found to significantly influence the calculated aerosol pH (7.6 ± 0.1 or 4.7 ± 1.1, respectively), and thus influence the relative importance of heterogeneous sulfate production via S(IV) oxidation by NO 2 and by O 2 . Our local atmospheric conditions-based calculations suggest sulfate formation via NO 2 oxidation can be the dominant pathway in aerosols at high-pH conditions calculated assuming stable state while S(IV) oxidation by O 2 can be the dominant pathway providing that highly acidic aerosols (pH ≤ 3) exist. Our local atmospheric-conditions-based calculations illustrate the utility of 17 O(SO 2− 4 ) for quantifying sulfate forPublished by Copernicus Publications on behalf of the European Geosciences Union. 5516 P. He et al.: Isotopic constraints on heterogeneous sulfate production in Beijing haze mation pathways, but this estimate may be further improved with future regional modeling work.

show abstract

“…Large uncertainty exists in the reaction rates of Fe(III)‐ and Mn(II)‐catalyzed S(IV) + O 2 [ Hoffmann and Jacob , 1984; Martin and Hill , 1987a], and the reaction is thought to be inhibited by increasing ionic strength, the sulfate ion, various organics, and self‐inhibited [ Kotronarou and Sigg , 1993; Martin and Hill , 1987a, 1987b; Podkrajsek et al , 2006; Tursic et al , 2003; Zuo and Zhan , 2005]. The presence of both Fe(III) and Mn(II) enhances the reaction rate synergistically, so that the overall reaction rate is greater than the sum of the individual rates [ Berglund et al , 1993; Chughtai et al , 1993; Coichev et al , 1992; Grgic et al , 1992; Martin , 1984].…”

Section: Atmospheric Iron (Fe) and Manganese (Mn)mentioning

confidence: 99%

Transition metal‐catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

et al. 2009

View full text Add to dashboard Cite

[1] We use observations of the oxygen-17 excess (D 17 O) of sulfate in the Arctic to quantify the sulfate source from aqueous SO 2 (S(IV)) oxidation by O 2 catalyzed by transition metals. Due to the lack of photochemically produced OH and H 2 O 2 in high latitudes during winter, combined with high anthropogenic SO 2 emissions in the Northern Hemisphere, oxidation by O 3 is predicted to dominate sulfate formation during winter in this region. However, D 17 O measurements of sulfate aerosol collected in Alert, Canada, are not consistent with O 3 as the dominant oxidant and indicate that a S(IV) oxidant with near-zero D 17 O values (O 2 ) is important during winter. We use a global chemical transport model to interpret quantitatively the Alert observations and assess the global importance of sulfate production by Fe(III)-and Mn(II)-catalyzed oxidation of S(IV) by O 2 . We scale anthropogenic and natural atmospheric metal concentrations to primary anthropogenic sulfate and dust concentrations, respectively. The solubility and oxidation state of these metals is determined by cloud liquid water content, source, and sunlight. By including metal-catalyzed S(IV) oxidation, the model is consistent with the D 17 O magnitudes in the Alert data during winter. Globally, we find that this mechanism contributes 9-17% to sulfate production. The inclusion of metal-catalyzed oxidation does not resolve model discrepancies with surface SO 2 and sulfate observations in Europe. Oxygen isotope measurements of sulfate aerosols collected near anthropogenic and dust sources of metals would help to verify the importance of this sulfur oxidation pathway.

show abstract

The iron catalyzed oxidation of sulfur: Reconciliation of the literature rates

Cited by 87 publications

References 2 publications

Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China

Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China

Isotopic constraints on heterogeneous sulfate production in Beijing haze

Transition metal‐catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

Contact Info

Product

Resources

About