Heterogeneous Reactions of Alkylamines with Ammonium Sulfate and Ammonium Bisulfate

Qiu, Chong; Wang, Lin; Lal, Vinita; Khalizov, Alexei F.; Zhang, Renyi

doi:10.1021/es1043112

Cited by 119 publications

(175 citation statements)

References 44 publications

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“…Note that this acidity effect on aerosol sulfate formation (i.e., decreasing with increasing particle size) is analogous to the Kelvin (curvature) effect, which represents a major barrier in aerosol nucleation (36,37). In addition, neutralization of fine PM can be facilitated by amines, albeit at a lower atmospheric concentration than NH 3 (38,39). The exponential fit is y = 1.8 × 10 6 + 417exp (x/7.9) with R 2 = 0.97.…”

Section: Resultsmentioning

confidence: 90%

Persistent sulfate formation from London Fog to Chinese haze

Wang

Zhang

Gómez

et al. 2016

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

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1,163

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: 90%

Persistent sulfate formation from London Fog to Chinese haze

Wang

Zhang

Gómez

et al. 2016

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

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1,163

922

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“…53 As shown in Figure 5A-C, however, the uptake coefficients of TMA are clearly lower than those of DMA and MA on citric acid, humic acid, and (NH 4 ) 2 SO 4 . 16 This is contrary to the linear free energy relationship for the acid−base reaction, which means other factors should be important in the reaction kinetics.…”

Section: −1mentioning

confidence: 98%

Heterogeneous Uptake of Amines by Citric Acid and Humic Acid

2012

Environ. Sci. Technol.

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Heterogeneous uptake of methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA) onto citric acid and humic acid was investigated using a Knudsen cell reactor coupled to a quadrupole mass spectrometer at 298 K. Acid−base reactions between amines and carboxylic acids were confirmed. The observed uptake coefficients of MA, DMA, and TMA on citric acid at 298 K were measured to be 7.31 ± 1.13 × 10 −3 , 6.65 ± 0.49 × 10 −3 , and 5.82 ± 0.68 × 10, respectively, and showed independence of sample mass. The observed uptake coefficients of MA, DMA, and TMA on humic acid at 298 K increased linearly with sample mass, and the true uptake coefficients of MA, DMA, and TMA were measured to be 1.26 ± 0.07 × 10 −5 , 7.33 ± 0.40 × 10 , respectively. Citric acid, having stronger acidity, showed a higher reactivity than humic acid for a given amine; while the steric effect of amines was found to govern the reactivity between amines and citric acid or humic acid.

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“…16 On the other hand, although it has not been evaluated by modelers, heterogeneous uptake onto fine particles might also contribute to reduced nitrogen in particle phase due to the relative large uptake coefficients as reported previously. 22,53,66,67 Whatever the formation path is, once formed, organic nitrogen containing compounds including particulate amines nearly immediately begin the heterogeneous oxidation by oxidants in the lower atmosphere. 62 The lifetimes of alkylamines exposed to ozone in the gas phase usually vary from a few hours to several days.…”

Section: ■ Atmospheric Implicationsmentioning

confidence: 99%

Ozonolysis of Trimethylamine Exchanged with Typical Ammonium Salts in the Particle Phase

Chu

et al. 2016

Environ. Sci. Technol.

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Alkylamines contribute to both new particle formation and brown carbon. The toxicity of particle-phase amines is of great concern in the atmospheric chemistry community. Degradation of particulate amines may lead to secondary products in the particle phase, which are associated with changes in the adverse health impacts of aerosols. In this study, O 3 oxidation of particulate trimethylamine (TMA) formed via heterogeneous uptake of TMA by (NH 4 ) 2 SO 4 , NH 4 HSO 4 , NH 4 NO 3 and NH 4 Cl, was investigated with in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and proton transfer reaction mass spectrometry (PTR-MS). HCOOH, HCHO, CH 3 NCH 2 , (CH 3 ) 2 NCHO, CH 3 NO 2 , CH 3 N(OH)CHO, CH 3 NHOH and H 2 O were identified as products on all the substrates based upon IR (one-dimensional IR and two-dimensional correlation infrared spectroscopy), quantum chemical calculation and PTR-MS results. A reaction mechanism was proposed to explain the observed products. This work demonstrates that oxidation might be a degradation pathway of particulate amines in the atmosphere. This will aid in understanding the fate of particulate amines formed by nucleation and heterogeneous uptake and their potential health impacts during atmospheric aging.

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Heterogeneous Reactions of Alkylamines with Ammonium Sulfate and Ammonium Bisulfate

Cited by 119 publications

References 44 publications

Persistent sulfate formation from London Fog to Chinese haze

Persistent sulfate formation from London Fog to Chinese haze

Heterogeneous Uptake of Amines by Citric Acid and Humic Acid

Ozonolysis of Trimethylamine Exchanged with Typical Ammonium Salts in the Particle Phase

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