Life cycle of atmospheric aerosol

Atmospheric transport

1 nm 10 nm 100nm 1 μm 10 μm
gas condensation coagulation cloud cycling
molecular clusters
(nucleation)
condensation from gases

H2 SO4 oxygenated HNO3 NH3 direct emission

deposition
sulfuric acid VOCs nitric acid ammonia
organic particles soil dust
atmospheric oxidation black carbon sea salt

SO2 VOCs NOx

wind
combustion

combustion
combustion

agriculture
coal

vegetation

vehicles
Industry
 Chemical composition of particles
• Atmospheric particles have a multitude of sources, primary
and secondary or natural and anthropogenic, and their
chemical composition in any given region of the world is the
result of not only the type and strength of the sources
affecting the area but also of the physical and chemical
atmospheric processes undergone by the aerosol and its
precursors.
• In fact, aerosol particles are strictly coupled with the
atmospheric gas phase and the liquid phase of clouds, and
understanding the properties and effects of the
atmospheric aerosol requires that gas, aerosol, and cloud
phases are treated as single system.
• Atmospheric aerosol particles exhibit a wide range of sizes,
from nanometers to micrometers, and a wide range of
shapes. Their chemical composition usually differs among
the different size ranges and even among particles within a
given size range.
Chemical composition of particles
Note on secondary aerosol:
Chances of chemical species to
undergo from gas to aerosol phase
depends on the vapour pressure.
Lower or no vapour pressure
results in aerosol formation. Adding
molecular weight to existing
molecules has high tendency to
form aerosol particles while
Evaporation or fragmentation of
molecule can results aerosol back
to gaseous state due to high vapour
pressure
Chemical composition drives the aerosol properties

• The chemical composition affects aerosol properties like

• radiative effects,
• hygroscopic growth,
• reactivity,
• ability to form cloud droplets,
• consequently, their effects on the environment, from visibility impairment to effects on
human health and from effects on the biosphere to material deterioration and to climate
change.
Chemical composition varies by emission source
Chemical composition varies by region
Aerosol aging – How aerosol composition changes during its interaction in the
atmosphere via different chemical reactions and results into differential effects
with respect to its origin (characteristic of primary emission source)
Which size range particles will undergo more aging?

• Particle size with high

residence time in
atmosphere
• Accumulation range
Multiphase Reactions
• In atmospheric chemistry, the term multiphase reactions is used to
describe reactions occurring inside or at the surface of a droplet or uptake
into a droplet.
 PM2.5 composition

Two components dominate PM2.5 mass under almost all conditions:

• Sulfate-nitrate-ammonium (SNA)
• Organic carbon (OC)
Inorganic species- Sulfate via SO2 oxidation
Sulfate originates from atmospheric oxidation of SO2
Global SO2 emission trends

Klimont et al., 2013

Long-term trends in US SO2 emissions

Scrubbers on coal power plants, transition to natural gas

EPA National Emission Inventory

Removal of SO2 via scrubber technology in industry
 Ammonia in the atmosphere

Global ammonia emissions (kg N ha-1 a-1) IASI satellite observations of ammonia

Paulot et al. [2014]

Van Damme et al. [2014]

Agriculture (manure, fertilizer) is 75% of global source

Ammonia is a weak base:

NH3 ( g )  NH3 (aq )
NH3 (aq )  H +  NH 4+ K1  7  109 M 1

It partitions into the aerosol if the aerosol is sufficiently acidic

 Inorganic chemistry: Formation of sulfate-nitrate-
ammonium (SNA) aerosol
High RH (aqueous aerosol)
Low RH (dry aerosol)
H2O
H2SO4(g)
SO2 oxidation H SO (aq) HSO4- SO42- NH4HSO4
2 4
(NH4)2SO4
NH3 NH3(aq) NH4+ NH4NO3
HNO3 HNO3(aq) NO3-

oxidation
NOx

EMISSION
SO2: coal combustion
NH3: agriculture
NOx: fuel combustion
• Sulfuric acid produced from SO2 oxidation is ~100% incorporated into the aerosol
• Ammonium and nitrate are incorporated as determined by acid-base titration