Heterogeneous Chemical Processing of <sup>13</sup>NO<sub>2</sub> by Monodisperse Carbon Aerosols at Very Low Concentrations

Kalberer, Markus; Tabor, Kevin D.; Ammann, Markus; Parrat, Y.; Weingärtner, E.; Piguet, D.; Rössler, E.; Jost, D.T.; Türler, Α.; Gäggeler, H. W.; Baltensperger, Urs

doi:10.1021/jp9606974

Cited by 60 publications

(50 citation statements)

References 22 publications

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“…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). Recent papers by Kamm et al (1999) and Saathoff et al (2001) show results from a very large aerosol chamber (AIDA, 84 m 3 volume) where spark discharge produced soot particles were used.…”

Section: Chemistry In the Plumementioning

confidence: 94%

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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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Section: Chemistry In the Plumementioning

confidence: 94%

“…by converting NO 2 in a heterogeneous reaction to HONO (Kalberer et al, 1996;Ammann et al, 1998). HONO rapidly photolyzes, thereby producing OH and NO.…”

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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“…To carry out experiments with only one 13 NO y species in the gas phase, a series of selective gas traps were used to scrub all but one species from the gas phase, where possible. The traps, which were designed as cylindrical denuders, were coated with Na 2 CO 3 for absorbing HONO or PAN, a mixture of NDA and KOH (1/1) for NO 2 , NaCl for HNO 3 and Co 2 O 3 for NO (see Kalberer et al, 1996Kalberer et al, , 1999. Those denuders, in combination with γ -detectors and the chemiluminescence NO y analyzer, were also used to identify and quantify the various 13 NO y species (Ammann, 2001).…”

Section: Methodsmentioning

confidence: 99%

The adsorption of nitrogen oxides on crystalline ice

et al. 2002

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Abstract. The partitioning of nitrogen oxides between ice and air is important to the ozone budget in the upper troposphere. In the present study, the adsorption of nitrogen oxides on ice was investigated at atmospheric pressure using a chromatographic technique with low concentrations of radioactively labelled nitrogen oxides. The measured retentions solely depended on molecular adsorption and were not influenced by dimerisation, formation of encapsulated hydrates on the ice surface, dissociation of the acids, nor by migration into a quasi-liquid layer or grain boundaries. Based on the chromatographic retention and the model of thermochromatography, the adsorption enthalpies of −20 kJ mol −1 for NO, −22 kJ mol −1 for NO 2 , −30 kJ mol −1 for peroxyacetyl nitrate, −32 kJ mol −1 for HONO and −44 kJ mol −1 for HNO 3 were calculated. To assess the adsorption enthalpies, standard adsorption entropies were calculated based on statistical thermodynamics. In this work, the use of two different standard states was demonstrated. Consequently different values of the standard adsorption entropy, of either between −39 J (K mol) −1 and −45 J (K mol) −1 , or −164 J (K mol) −1 and −169 J (K mol) −1 for each nitrogen oxide were deduced. The adsorption enthalpy derived from the measurements, was independent of the choice of standard state. A brief outlook on environmental implications of our findings indicates that adsorption on ice might be an important removal process of HNO 3 . In addition, it might be of some importance for HONO and peroxyacetyl nitrate and irrelevant for NO and NO 2 .

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“…To each trap (the coatings and filter) a separate CsI scintillator crystal with integrated PIN diode was attached (Carroll and Ramsey, USA) which detects the gamma quanta emitted after decay of the 13 N atoms. The detector signal is converted to the flux of the gaseous species into the trap using the inversion procedure reported elsewhere (Guimbaud et al, 2002;Kalberer et al, 1996;Rogak et al, 1991). This flux is proportional to the concentration of the species in the gas phase.…”

Section: Detection Systemmentioning

confidence: 99%

Effect of humidity on nitric acid uptake to mineral dust aerosol particles

et al. 2006

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Abstract. This study presents the first laboratory observation of HNO 3 uptake by airborne mineral dust particles. The model aerosols were generated by dry dispersion of Arizona Test Dust (ATD), SiO 2 , and by nebulizing a saturated solution of calcium carbonate. The uptake of 13 N-labeled gaseous nitric acid was observed in a flow reactor on the 0.2-2 s reaction time scale at room temperature and atmospheric pressure. The amount of nitric acid appearing in the aerosol phase at the end of the flow tube was found to be a linear function of the aerosol surface area. SiO 2 particles did not show any significant uptake, while the CaCO 3 aerosol was found to be more reactive than ATD. Due to the smaller uncertainty associated with the reactive surface area in the case of suspended particles as compared to bulk powder samples, we believe that we provide an improved estimate of the rate of uptake of HNO 3 to mineral dust. The fact that the rate of uptake was smaller at a concentration of 10 12 than at 10 11 was indicative of a complex uptake mechanism. The uptake coefficient averaged over the first 2s of reaction time at a concentration of 10 12 molecules cm −3 was found to increase with increasing relative humidity, from 0.022±0.007 at 12% RH to 0.113±0.017 at 73% RH , which was attributed to an increasing degree of solvation of the more basic minerals. The extended processing of the dust by higher concentrations of HNO 3 at 85% RH led to a water soluble coating on the particles and enhanced their hygroscopicity.

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Heterogeneous Chemical Processing of ¹³NO₂ by Monodisperse Carbon Aerosols at Very Low Concentrations

Cited by 60 publications

References 22 publications

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

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

The adsorption of nitrogen oxides on crystalline ice

Effect of humidity on nitric acid uptake to mineral dust aerosol particles

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Heterogeneous Chemical Processing of 13NO2 by Monodisperse Carbon Aerosols at Very Low Concentrations

Cited by 60 publications

References 22 publications

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

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

The adsorption of nitrogen oxides on crystalline ice

Effect of humidity on nitric acid uptake to mineral dust aerosol particles

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Product

Resources

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Heterogeneous Chemical Processing of ¹³NO₂ by Monodisperse Carbon Aerosols at Very Low Concentrations