Rate constant for the reaction of nitrogen dioxide with sulfur(IV) over the pH range 5.3-13

Clifton, Carol L.; Altstein, N.; Huie, Robert E.

doi:10.1021/es00170a018

Cited by 131 publications

(149 citation statements)

References 11 publications

(13 reference statements)

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“…2A). Hence, SO 4 2− and NO 3 − in fine PM are completely neutralized, because of the presence of high levels of gaseous ammonia (17)(18)(19)(20)(21)(22)(23) , and Cl − ) is also near unity (Fig. 2B and SI Appendix, Fig.…”

Section: Resultsmentioning

confidence: 99%

“…This reaction is also dependent on pH, which not only governs the solubility but also the aqueous reaction rate. For example, when the pH value is varied from 6 to 4, the effective Henry's constant of SO 2 decreases by more than two orders of magnitude (1-3), leading to a decreased oxidation rate of approximately two orders of magnitude (17)(18)(19). In addition, the solubility is dependent of temperature, i.e., increasing with decreasing temperature (32)(33)(34).…”

Section: Resultsmentioning

confidence: 99%

“…The aqueous pathways of SO 2 oxidation may occur much faster, including reactions with dissolved ozone, hydrogen peroxide, organic peroxides, OH, and NO 2 via catalytic or noncatalytic pathways involving mineral oxides (15)(16)(17)(18)(19)(20). Most recently, an interfacial SO 2 oxidation mechanism involving O 2 on acidic microdroplets has been suggested (16).…”

mentioning

confidence: 99%

“…Several earlier experimental studies, in which gaseous NO 2 was exposed to bulk solutions containing sulfite (SO 3 2− ) and hydrogen sulfite (HSO 3 − ) ions prepared from Na 2 SO 3 , investigated the aqueous sulfur oxidation by NO 2 ; the measured rate constants differed by 1-2 orders of magnitude (17)(18)(19). Typically, this aqueous oxidation has been neglected in atmospheric models because of limited water solubility of NO 2 (1,13,20).…”

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confidence: 99%

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Persistent sulfate formation from London Fog to Chinese haze

Wang

Zhang

Gómez

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

1,161

922

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Sulfate aerosols exert profound impacts on human and ecosystem health, weather, and climate, but their formation mechanism remains uncertain. Atmospheric models consistently underpredict sulfate levels under diverse environmental conditions. From atmospheric measurements in two Chinese megacities and complementary laboratory experiments, we show that the aqueous oxidation of SO 2 by NO 2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH 3 neutralization or under cloud conditions. Under polluted environments, this SO 2 oxidation process leads to large sulfate production rates and promotes formation of nitrate and organic matter on aqueous particles, exacerbating severe haze development. Effective haze mitigation is achievable by intervening in the sulfate formation process with enforced NH 3 and NO 2 control measures. In addition to explaining the polluted episodes currently occurring in China and during the 1952 London Fog, this sulfate production mechanism is widespread, and our results suggest a way to tackle this growing problem in China and much of the developing world.sulfate aerosol | severe haze | pollution | human health | climate

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Persistent sulfate formation from London Fog to Chinese haze

Wang

Zhang

Gómez

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

1,161

922

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“…Beijing haze, while Cheng et al(2016) suggested that S(IV) oxidation by NO 2 (Lee and Schwartz, 1982;Clifton et al, 1988) 59 in aerosol water could be important due to the high RH and NO 2 concentrations during severe haze in NCP. Due to the 60 strong pH-dependence of these two pathways and the large variability of model calculated aerosol pH in Beijing haze 61 (Cheng et al, 2016;Wang et al, 2016;Liu et al, 2017), the relative importance of these two pathways is difficult to constrain.…”

Section: Introduction 39mentioning

confidence: 99%

Isotopic constraints on heterogeneous sulphate production in Beijing haze

He¹,

Alexander²,

Geng³

et al. 2017

Preprint

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Abstract. Discerning mechanisms of sulfate formation during fine-particle pollution (referred to as haze hereafter)in Beijing 16 is important for understanding the rapid evolution of haze and for developing cost-effective air pollution mitigation strategies. 17Here we present the first observations of the oxygen-17 excess of PM 2.5 sulfate (Δ 17 O(SO 4 2-)) collected in Beijing haze from 18October 2014 to January 2015, to constrain possible sulfate formation pathways. Throughout the sampling campaign, the 19 12h-averaged PM 2.5 concentrations ranged from 16 to 323 μg m -3 with a mean of (141±88 (1σ)

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The heterogeneous formation of N2O in the presence of acidic solutions: Experiments and modeling

Pires¹,

Rossi²

1997

Int. J. Chem. Kinet.

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We investigated the heterogeneous processes that contribute towards the formation of N 2 O in an environment that comes as closely as possible to exhaust conditions containing NO and SO 2 among other constituents. The simultaneous presence of NO, SO 2 , O 2 , and condensed phase water in the liquid state has been confirmed to be necessary for the production of significant levels of N 2 O. The maximum rate of N 2 O formation occurred at the beginning of the reaction and scales with the surface area of the condensed phase and is independent of its volume. The replacement of NO by either NO 2 or HONO significantly increases the rate constant for N 2 O formation. The measured reaction orders in the rate law change depending upon the choice of the nitrogen reactant used and were fractional in some cases. The rate constants of N 2 O formation for the three different nitrogen reactants reveal the following series of increasing reactivity:indicating the probable se-NO Ͻ NO Ͻ HONO, 2 quential involvement of those species in the elementary reactions. Furthermore, we observed a complex dependence of the rate constant on the acidity of the liquid phase where both the initial rate as well as the yield of N 2 O are largest at of a H 2 SO 4 /H 2 O solution. The pH ϭ 0 results suggest that HONO is the major reacting N(III) species over a wide range of acidities studied. The N 2 O formation in synthetic flue gas may be simulated using a relatively simple mechanism based on the model of Lyon and Cole. The first step of the complex overall reaction corresponds to NO oxidation by O 2 to NO 2 mainly in the gas phase, with the presence of both H 2 O and active surfaces significantly accelerating NO 2 production. Subsequently, NO 2 reacts with excess NO to obtain HONO which reacts with S(IV) to result in N 2 O and H 2 SO 4 through a complex reaction sequence probably involving nitroxyl (HON) and its dimer, hyponitrous acid.

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Rate constant for the reaction of nitrogen dioxide with sulfur(IV) over the pH range 5.3-13

Cited by 131 publications

References 11 publications

Persistent sulfate formation from London Fog to Chinese haze

Persistent sulfate formation from London Fog to Chinese haze

Isotopic constraints on heterogeneous sulphate production in Beijing haze

The heterogeneous formation of N2O in the presence of acidic solutions: Experiments and modeling

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