Reactive uptake and hydration experiments on amorphous carbon treated with NO2, SO2, O3, HNO3, and H2SO4

Rogaski, C. A.; Golden, David M.; Williams, Leah R.

doi:10.1029/97gl00093

Cited by 155 publications

(172 citation statements)

References 24 publications

(20 reference statements)

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“…With the strong seasonal variation. As indicated in Figure 18, in December, heterogeneous uptake of CH20 into sulfate aerosols, the HO x the rate of heterogeneous reaction of CH20 decreases due to the Northern Hemisphere during winter, producing a 90% decrease in [1995] and Rogaski et al [1997] have shown that the uptake CH20 and a 10% decrease in HO 2 in northern middle and high coefficient for ozone on black carbon particles occurs with an latitudes (see Figure 19). With a lower uptake coefficient for uptake coefficient of the order of 2x10 -4 to 3.3x10 -3.…”

Section: Reaction Of Ho2 On Sulfate Aerosolsmentioning

confidence: 99%

Effects of aerosols on tropospheric oxidants: A global model study

Tie¹,

Brasseur²,

Emmons³

et al. 2001

J. Geophys. Res.

193

183

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with an uptake coefficient of 0.2. However, this uptake coefficient could be overestimated, and the results should be regard as an upper limit estimation. (3) The N20 5 reaction on the surface of sulfate aerosols leads to an 80% reduction of NOx at middle to high latitudes during winter. Because ozone production efficiency is low in winter, ozone decreases by only 10% as a result of this reaction. However, during summer the N20 5 reaction reduces NOx by 15% and 03 by 8-10% at middle to high latitudes. (4) The heterogeneous reaction of CH20 on sulfate aerosols with an upper limit uptake coefficient (5'-0.01) leads to an 80 to 90% decrease in CH20 and 8 to 10% reduction of HO 2 at middle to high latitudes during winter. Many uncertainties remain in our understanding of heterogeneous chemical processes and in the estimate of kinetic parameters. This model study should therefore be regarded as exploratory and subject to further improvements before final conclusions can be made.

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Section: Reaction Of Ho2 On Sulfate Aerosolsmentioning

confidence: 99%

Effects of aerosols on tropospheric oxidants: A global model study

Tie¹,

Brasseur²,

Emmons³

et al. 2001

J. Geophys. Res.

193

183

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“…The temporal evolution of the gas-phase O 3 concentration is shown for a base scenario with no heterogeneous chemistry and for the constant uptake scenarios A const , B const , C const . Scenarios A const , B const , C const use constant uptake coefficients of γ O 3 =1×10 −3 (Stephens et al, 1986;Pöschl et al, 2001), γ NO 2 =0.14 (Gerecke et al, 1998;Ammann and Pöschl, 2007), and γ H 2 O =0.4×10 −3 (Rogaski et al, 1997;Pöschl et al, 2001) but are otherwise equivalent to scenarios A, B, and C as defined in Table 1. surfaces that are older than six hours is not significant. After one hour of simulation time, the uptake coefficients fall by one to two orders of magnitude, depending on the scenario.…”

Section: Feedback On the Gas-phase O 3 Concentration With Differing Umentioning

confidence: 99%

“…To study the gas-phase feedback from a heterogeneous modeling approach employing constant uptake coefficients, we implement the experimentally determined constant uptake coefficients of γ O 3 =1×10 −3 for O 3 uptake , γ NO 2 =0.14 for NO 2 uptake (Gerecke et al, 1998), and γ H 2 O =0.4×10 −3 for the uptake of water vapor (Rogaski et al, 1997) into the non-emission scenarios A, B, and C. These γ X i -values represent initial uptake coefficients that were previously implemented in our model as accommodation coefficients. The gas-phase loss is computed according to Eq.…”

Section: Gas-phase O 3 Feedback For Constant Uptake Parameterizationsmentioning

confidence: 99%

“…Since freshly emitted discharge soot particles are known to be hydrophobic, physisorption of water vapor on soot was suggested as mechanism for adsorption, supported by the water vapor's small desorption lifetime . The H 2 O specific parameters α s,0,H 2 O and τ d,H 2 O are adapted from Rogaski et al (1997) and Pöschl et al (2001), and σ H 2 O is taken from Nishino (2001).…”

Section: Surface Reactionsmentioning

confidence: 99%

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Detailed heterogeneous chemistry in an urban plume box model: reversible co-adsorption of O3, NO2, and H2O on soot coated with benzo[a]pyrene

2009

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Abstract. This study assesses in detail the effects of heterogeneous chemistry on the particle surface and gas-phase composition by modeling the reversible co-adsorption of O 3 , NO 2 , and H 2 O on soot coated with benzo[a]pyrene (BaP) for an urban plume scenario over a period of five days. By coupling the Pöschl-Rudich-Ammann (PRA) kinetic framework for aerosols ) to a box model version of the gas phase mechanism RADM2, we are able to track individual concentrations of gas-phase and surface species over the course of several days. The flux-based PRA formulation takes into account changes in the uptake kinetics due to changes in the chemical gas-phase and particle surface compositions. This dynamic uptake coefficient approach is employed for the first time in a broader atmospheric context of an urban plume scenario. Our model scenarios include one to three adsorbents and three to five coupled surface reactions. The results show a variation of the O 3 and NO 2 uptake coefficients of more than five orders of magnitude over the course of the simulation time and a decrease in the uptake coefficients in the various scenarios by more than three orders of magnitude within the first six hours. Thereafter, periodic peaks of the uptake coefficients follow the diurnal cycle of gas-phase O 3 -NO x reactions. Physisorption of water vapor reduces the half-life of the coating substance BaP by up to a factor of seven by permanently occupying ∼75% of the soot surface. Soot emissions modeled by replenishing reactive surface sites lead to maximum gas-phase O 3 depletions Correspondence to: D. A. Knopf (daniel.knopf@stonybrook.edu) of 41 ppbv and 7.8 ppbv for an hourly and six-hourly replenishment cycle, respectively. This conceptual study highlights the interdependence of co-adsorbing species and their nonlinear gas-phase feedback. It yields further insight into the atmospheric importance of the chemical oxidation of particles and emphasizes the necessity to implement detailed heterogeneous kinetics in future modeling studies.

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“…These studies where mainly done in Knudsen cells or in aerosol flow reactors and resulted in sometimes very high uptake coefficients of e.g. NO 2 of the order of 10 −2 on soot surfaces (Rogaski et al, 1997;Gerecke et al, 1998). Other studies found uptake rates that were several orders of magnitude lower (Kalberer et al, 1996;Ammann et al, 1998;Longfellow et al, 1999;Al-Abadleh and Grassian, 2000;Kirchner et al, 2000), surface saturation effects that result in a time dependence of the uptake (Ammann et al, 1998;Longfellow et al, 1999;Al-Abadleh and Grassian, 2000;Kirchner et al, 2000) and also a strong dependency on the type of soot used (Kalberer et al, 1996;Kirchner et al, 2000).…”

Section: Chemistry In the Plumementioning

confidence: 99%

Modeling the chemical effects of ship exhaust in the cloud-free marine boundary layer

Glasow

Lawrence²,

Sander³

et al. 2003

Atmos. Chem. Phys.

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Abstract. The chemical evolution of the exhaust plumes of ocean-going ships in the cloud-free marine boundary layer is examined with a box model. Dilution of the ship plume via entrainment of background air was treated as in studies of aircraft emissions and was found to be a very important process that significantly alters model results. We estimated the chemical lifetime (defined as the time when differences between plume and background air are reduced to 5% or less) of the exhaust plume of a single ship to be 2 days. Increased concentrations of NO x (= NO + NO 2 ) in the plume air lead to higher catalytical photochemical production rates of O 3 and also of OH. Due to increased OH concentrations in the plume, the lifetime of many species (especially NO x ) is significantly reduced in plume air. The chemistry on background aerosols has a significant effect on gas phase chemistry in the ship plume, while partly soluble shipproduced aerosols are computed to only have a very small effect. Soot particles emitted by ships showed no effect on gas phase chemistry. Halogen species that are released from sea salt aerosols are slightly increased in plume air. In the early plume stages, however, the mixing ratio of BrO is decreased because it reacts rapidly with NO. To study the global effects of ship emissions we used a simple upscaling approach which suggested that the parameterization of ship emissions in global chemistry models as a constant source at the sea surface leads to an overestimation of the effects of ship emissions on O 3 of about 50% and on OH of roughly a factor of 2. The differences are mainly caused by a strongly reduced lifetime (compared to background air) of NO x in the early stages of a ship plume.

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Reactive uptake and hydration experiments on amorphous carbon treated with NO₂, SO₂, O₃, HNO₃, and H₂SO₄

Cited by 155 publications

References 24 publications

Effects of aerosols on tropospheric oxidants: A global model study

Effects of aerosols on tropospheric oxidants: A global model study

Detailed heterogeneous chemistry in an urban plume box model: reversible co-adsorption of O<sub>3</sub>, NO<sub>2</sub>, and H<sub>2</sub>O on soot coated with benzo[a]pyrene

Modeling the chemical effects of ship exhaust in the cloud-free marine boundary layer

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Reactive uptake and hydration experiments on amorphous carbon treated with NO2, SO2, O3, HNO3, and H2SO4

Cited by 155 publications

References 24 publications

Effects of aerosols on tropospheric oxidants: A global model study

Effects of aerosols on tropospheric oxidants: A global model study

Detailed heterogeneous chemistry in an urban plume box model: reversible co-adsorption of O&lt;sub&gt;3&lt;/sub&gt;, NO&lt;sub&gt;2&lt;/sub&gt;, and H&lt;sub&gt;2&lt;/sub&gt;O on soot coated with benzo[a]pyrene

Modeling the chemical effects of ship exhaust in the cloud-free marine boundary layer

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Reactive uptake and hydration experiments on amorphous carbon treated with NO₂, SO₂, O₃, HNO₃, and H₂SO₄

Detailed heterogeneous chemistry in an urban plume box model: reversible co-adsorption of O<sub>3</sub>, NO<sub>2</sub>, and H<sub>2</sub>O on soot coated with benzo[a]pyrene