CHAPTER 8: ATMOSPHERIC AEROSOLS

Homework: 8-1
二次有機氣膠
原本放出來的氣體經過化學變化產生固體
 ORIGIN OF THE ATMOSPHERIC AEROSOL
Aerosol: dispersed condensed phases suspended in a gas
Size range: 0.001 mm (molecular cluster) to 100 mm (small raindrop)

Soil dust
Sea salt

Environmental importance: health (respiration), visibility, climate,

cloud formation, heterogeneous reactions, long-range transport of nutrients…
 Nucleation
FINE PARTICLE Burst
GROWTH on 10/6/01
AT BLODGETT FOREST
“Banana Plot”
4

100
D p (nm)

2 核化

10

2 7 9 .0 2 7 9 .2 2 7 9 .4 2 7 9 .6 2 7 9 .8 2 8 0 .0

Day
-3
dN/dlog(D p ) (cm )

0 2000 4000 6000 8000

[Lunden et al., 2006]

EPA REGIONAL HAZE RULE: WILDERNESS AREAS MUST
ACHIEVE NATURAL VISIBILITY CONDITIONS BY 2064
Visibility degradation by aerosols at Glacier National Park, Montana

7.6 µgm-3
12.0 µgm-3
Glacier
National
Park

21.7 µgm-3 65.3 µgm-3

(previous) U.S. air quality standard

Natural aerosol concentrations are typically less than 2 mg m-3

TYPICAL AEROSOL SIZE DISTRIBUTION

dN
ultrafine n(D p ) 
fine coarse dDp
accumulation PM PM10 N=number
2.5
concentration
(particles/cm3)

N   n(D p )dD p
surface area 0

dS
n s (D p ) 
dDp
  D p 2 n(D p )

volumn
dV
n v (D p ) 
dD p

 D p 3n(D p )
6
 WHY SIZE MATTERS

(1) Toxicity (2) Light Scattering (3) Particle Lifetime

=550 nm

[Seinfeld & Pandis]

[Finlayson-Pitts & Pitts]

[NARSTO, 2003]

(4) Surface Reactions: smaller particles have greater relative surface area
 2013 高雄氣膠粒徑譜的逐時變化
source 產生
1.primary dust/海鹽/元素炭
直接排放

2.secondary 硫酸=>硫酸根
間接排放

(火山、燃煤、藻類DMS)
SO2氧化變硫酸

NO2+OH+M=>HNO3(g)
HNO3(g)+H2O=>HNO3(aq)
=>H+ + NO3-

排泄物施肥
NH3(aq)+H2O=>NH4+OH-

(植物、工廠揮發性有機物質)
氧化變低揮發性有機物

NaCl+HNO3=>NaNO3+HCl

小粒子早上核化 By 徐嘉鴻
FINE AEROSOL COMPOSITION IN NORTH AMERICA
Annual mean PM2.5 concentrations (NARSTO, 2004)
Average PM10 Composition in Taiwan

Chou et al.
DUST: MOST IMPORTANT(?) NATURALLY EMITTED AEROSOL

Sources: arid / semi-arid regions

Emission in both fine and coarse

mode, depends on surface
properties and wind speed.

Resulting lifetime ~weeks

Dust Emissions (2001)

g m-2 y-1
Fairlie et al. [2007]

[Husar et al., 2002]

 WILDFIRES: A GROWING AEROSOL SOURCE
S. California fire plumes, Total carbonaceous (TC) aerosol
Oct. 25 2004 averaged over U.S. IMPROVE sites

Interannual variability is driven

by wildfires
 SECONDARY ORGANIC AEROSOL PRODUCTION FROM
BIOGENIC VOC EMISSIONS

Biogenic
Nucleation
VOC Oxidation Growth
(oxidation products)
Emissions Reactions
(OH, O3,NO3)

Condensation
on pre-existing
aerosol

Over 500 reactions to describe the formation of SOA precursors, ozone, and other
photochemical pollutants [Griffin et al., 2002; Griffin et al., 2005; Chen and Griffin, 2005]
 BIOGENIC HYDROCARBONS

Isoprene (C5H8) 不容易凝結去競爭氧化物核化

Monoterpenes(C10H16)

Sesquiterpenes (C15H24)

Anthropogenic SOA-precursors =
aromatics (emissions are 10x smaller)
人類工業產生

"Trees cause more pollution than automobiles do.“

要產生O3還要NOx NOx是人為很多
 Nucleation
FINE PARTICLE Burst
GROWTH on 10/6/01
AT BLODGETT FOREST
“Banana Plot”
4

100
D p (nm)

10

2 7 9 .0 2 7 9 .2 2 7 9 .4 2 7 9 .6 2 7 9 .8 2 8 0 .0

Day
-3
dN/dlog(D p ) (cm )

0 2000 4000 6000 8000

[Lunden et al., 2006]

 PRIMARY BIOLOGICAL AEROSOL PARTICLES (PBAP)

BACTERIA VIRUSES

POLLEN
FUNGUS

PLANT ALGAE
DEBRIS

Very large and likely short-lived

These particles have not traditionally been considered part of the OA budget, but
this has been revised in recent years.
Not much is known about emissions, processing, climate effects.
 STRATOSPHERIC AEROSOL

PSCs (nitric acid /

Injection of water vapor)
volcanic ash
TROPOPAUSE
(SiO2, Al2O3, Fe2O3)
as well as gases
(H2S, SO2, HCl) Transport of
long-lived S
gases (eg. COS)

Aerosols in the stratosphere are long-lived due to absence of precipitation

and “layered” transport (due to stability)
 GLOBAL SULFUR BUDGET [Chin et al., 1996]
(flux terms in Tg S yr-1)

DMS: CH3-S-CH3

cloud
42 SO42-
SO2 OH t  3.9d
t  1.3d 8 H2SO4(g)
4 18

NO3 OH

(CH3)2S 64
DMS 10 dep dep
t  1.0d 27 dry 6 dry
20 wet 44 wet

22

Phytoplankton Volcanoes Combustion

Smelters
HOW COMPOSITION AND SIZE FIT TOGETHER…

Image from: C. Leck

 RAOULT’S LAW

P o
H 2 O , SAT PH 2O , SAT  xH 2O PHo 2O , SAT

water saturation vapor pressure water saturation vapor pressure

over pure liquid water surface over aqueous solution of water
mixing ratio xH2O

An atmosphere of relative humidity RH can contain at equilibrium

aqueous solution particles of water mixing ratio
 HOWEVER, AEROSOL PARTICLES MUST ALSO
SATISFY SOLUBILITY EQUILIBRIA

Consider an aqueous sea salt (NaCl) particle: it must satisfy

xNa  xCl   K s (solubility equilibrium)

xNa   xCl  (electroneutrality)
xNa   xCl   xH 2O  1 (closure)

This requires:
1
RH  100(1  2 K s ) "deliquescence RH"
2

At lower RH, the particle is solid at equilibrium, though it can

also remain in metastable aqueous state
UPTAKE OF WATER BY AEROSOLS
 RELATIVE HUMIDITIES FOR
DELIQUESCENCE/CRYSTALLIZATION OF AEROSOLS
AEROSOL CLIMATE FORCING

IPCC [2007]
SCATTERING OF
By scattering
RADIATION solar radiation,
BY AEROSOLS: aerosols
“DIRECT EFFECT” increase the
Earth’s albedo

Scattering efficiency is
maximum when
particle radius = 
particles in 0.1-1 mm
size range are efficient
scatterers of solar
radiation
ANNUAL MEAN PM2.5 CONCENTRATIONS (2002)
derived from MODIS satellite instrument data

0.47 mm
0.65 mm
2.13 mm

AEROSOL

SURFACE
 EVIDENCE OF AEROSOL EFFECTS ON CLIMATE:
Temperature decrease following large volcanic eruptions
+0.2

Observations
NASA/GISS general
0

circulation model
Temperature
Change (oC)
-0.6 -0.4 -0.2

1991 1992 1993 1994

Mt. Pinatubo eruption

 SCATTERING vs. ABSORBING AEROSOLS

Scattering sulfate and organic aerosol Partly absorbing dust aerosol

over Massachusetts downwind of Sahara

Absorbing aerosols (black carbon, dust) warm the climate by absorbing solar
radiation
 AEROSOL “INDIRECT EFFECT” FROM CLOUD CHANGES

Clouds form by condensation on pre-existing aerosol particles (“cloud

condensation nuclei”) when RH>100%

clean cloud (few particles): polluted cloud (many particles):

large cloud droplets small cloud droplets
• low albedo • high albedo (1st indirect)
• efficient precipitation • suppressed precipitation (2nd indirect)
 EVIDENCE OF INDIRECT EFFECT: SHIP TRACKS

N ~ 40 cm-3 N ~ 100 cm-3

W ~ 0.30 g m-3 W ~ 0.75 g m-3
re ~ 11.2 µm re ~ 10.5 µm

from D. Rosenfeld

 Particles emitted by ships increase concentration of cloud condensation nuclei (CCN)

 Increased CCN increase concentration of cloud droplets and reduce their avg. size
 Increased concentration and smaller particles reduce production of drizzle
 Liquid water content increases because loss of drizzle particles is suppressed
 Clouds are optically thicker and brighter along ship track
 SATELLITE IMAGES OF SHIP TRACKS

NASA, 2002
Atlantic, France, Spain

AVHRR, 27. Sept. 1987, 22:45 GMT

US-west coast
OTHER EVIDENCE OF CLOUD FORCING:
CONTRAILS AND “AIRCRAFT CIRRUS”

Aircraft condensation trails (contrails) over France, photographed from the Space Shuttle (©NASA).