VIII.

Aerosols

Size distribution
Formation and Processing
Composition
Aerosol phase chemistry
Importance of aerosols
human health
air quality, airborne pathogen transport
climate change
direct/indirect effects
aerosol optical properties, aerosol/cloud interactions
geochemical cycles
metals, nutrients, organics
acidification (sulfur, nitrogen)
Terminology
Aerosol a dispersion of solid and liquid particles suspended in gas (air).

note: aerosol is defined as the dispersion of both particles and gas, but in
common practice it is used to refer to the particles only!

Primary aerosol atmospheric particles that are emitted or injected
directly into the atmosphere.

Secondary aerosol atmospheric particles that are created by in situ
aggregation or nucleation from gas phase molecules (gas to particle
conversion).

Either type may be natural or anthropogenic or both


How much aerosol is there? typically ~10s of ug/m
3
(air density ~1kg/m
3
)

Global Particle Production (Table 2.19 from Seinfeld and Pandis)
Source Estimate Flux (Tg/yr) Particle Size Category
Primary
Soil dust (mineral aerosol) 1000-3000 Mainly coarse
Sea salt 1000-10000 Coarse
Volcanic dust 2-10000 Coarse
Biological debris 26-80 Coarse
Secondary
Sulfates from biogenic gases 80-150 Fine
Sulfates from volcanic SO2 5-60 Fine
Organic matter from biogenic VOC 40-200 Fine
Nitrates from NOx 15-50 Fine and coarse
Total Natural 2200-23500 Best estimate 3100
Anthropogenic
Primary
Industrial dust etc. (except soot) 40-130 Fine and coarse
Soot 5-20 Mainly fine
Secondary
Sulfates from SO2 170-250 Fine
Biomass burning 60-150 Fine
Nitrates from NOx 25-65 Mainly coarse
Organics from anthropogenic VOC 5-25 Fine
Total anthropogenic 300-650 Best estimate 450
Total 2500-24000 Best estimate 3600
Aerosol Size Distributions
Number distribution
n
n
(D
p
)=dN/dD
p



Surface area distribution
n
s
(D
p
)= dS/dD
p

S=tD
p
2



Volume distribution
n
v
(D
p
)=dV/dD
p

V=(t/6)*D
p
3


Log-normal distributions
Aitken mode
Accumulation mode
Coarse mode
Number distribution
n
n
(log D
p
)=dN/d log D
p



Surface area distribution
n
s
(log D
p
)= dS/d log D
p



Volume distribution
n
v
(log D
p
)=dV/d log D
p
Aitken mode 0.01-0.1 m
Accumulation mode 0.1-1 m
Coarse mode - >1 m

and sometimes, the elusive
nucleation mode <0.01 um
The Aerosol Modes
A process oriented view of
aerosol size distribution

hygroscopic aerosols
grow/shrink with RH
(with hysteresis!)


aerosol size strongly affects
light scattering cross-section
deliquescence
efflorescence
Humidity and aerosol size...
Removal mechanisms... gravitational settling
10 m particle 1000 cm hr
-1

1 m particle 10 cm hr
-1
coarse particles
fine particles
Diameter (m) Distance diffused in 1 s (cm)
.001 0.2
.01 0.02
.1 .002
1 .0004
10 .0001

You can estimate the distance a
particle will diffuse in a given
time from the equation:
where D is the diffusion
coefficient
Dt ) cm ( ce tan dis =
Diffusion/Coagulation
Why is there an accumulation mode?
impaction, settling
diffusion,
coagulation
So lifetimes are .
Aitken nuclei hours to days
(diffusion/coagulation)
Accumulation mode weeks
Coarse mode hours to days
(deposition)
Ultrafine minutes to hours
Secondary organic aerosol formation
VOC oxidized to less-volatile OC
Partitioning to aerosol phase depends on
vapor pressure
High equilibrium vapor pressure high
tendency to stay in gas phase
Low equilibrium vapor pressure partitions to
aerosol phase non-volatiles
Large organics (C> 6) tend form aerosols
while organics C<6 do not.
Oligomerization on/in acid aerosol
Aqueous Aerosol
Thermodynamic partitioning (A
g
A
aq
)
liquid water content (L=g of H
2
O/m
3
of
air)
L=0.1-0.3 in clouds
L=0.02-0.5 in fogs
Henrys law constant (H)
H
A
=[A] (M)/
A
(atm)

H
O2
=1.3x10
-3
M/atm
H
O3
=1.1x10
-2
M/atm
H
NH3
=62 M/atm
H
H2O2
=7x10
4
M/atm
H
H2CO
=2.5 M/atm

Exercise: Calculate the concentration
of ozone in pure water in equilibrium
with 10 ppbv ozone, assume ideal gas.

A few Henrys law constants
Formaldehyde
constant law s Henry' effective the is * H
6300 5 . 2 2530 * H
H 2530
] CO H [ 2530 ] C(OH) [H CO] [H
H*
2530 K 2.5 H
) OH ( C H CO H CO H
CO H
) aq ( 2
CO H
2 2 (aq) 2
eq A
2 2 ) aq ( 2 ) g ( 2
2 2
= =
=

+
=
= =

Acids
8
7
eq
*
HNO
*
3
eq
HNO 3 HNO 3 ) ( 3 3
HNO 3 HNO eq
3
2 3 ) ( 3
5
3 HNO ) ( 3 ) ( 3
5
3 HNO
10 5 . 1
10
4 . 15
1
] H [
1
] [
] H [
1 H ] [ ] [ ] [
] H [
H
] NO [
4 . 15
M/atm 2.1x10 H
M/atm) 2.1x10 (H soluble r very wate is acid Nitric
3
HNO
3
HNO
2
3
HNO
3
HNO
3
3
2
3
3 2
=
|
.
|

\
|
+ =
|
|
.
|

\
|
+ =
=
|
|
.
|

\
|
+ = + =
=
= +
=
=
+
+

H
M
M
H
K
H H
H HNO
K
NO HNO HNO
K
M K H NO HNO
HNO HNO
HNO
total
aq total
eq aq
aq g

Because K
eq2
/H
+
>>1 nearly all nitric acid will exist as nitrate.
The chemical perspective ... a chemical size
distribution
1. chemical size distributions
resemble mass, not number

2. sulfate and organics
dominate the accumulation
mode, but theres a
surprising amount of
seasalt

3. there are a lot of
unidentified organics

4. the coarse mode has the
expected mechanically
generated aerosols, but
also nitrate and sometimes
sulfate
M
a
s
s

(C. Leck)

Dust (mineral aerosols)
-diameter size: 2-300 m
-main material: sand, silt, clay
-includes essential trace metals such as Fe
-consists of insoluble and soluble fractions
Mineral Dust
brown carbon:
sugars
alcohols
aromatics
di/tri acids
ketoacids
hydroxyacids
soot elemental carbon
formed in flames
little spectral dependence
carbon-only
Organic aerosols - burning
Seasalt aerosols...
seasalt production via
bubble bursting...

film drops (many, small,
organics)
jet drops (fewer, larger)
wind bubbles spray

whitecap coverage W U
3+

The sulfur story (in brief) ...
emissions: fossil fuel SO
2
, volcanic SO
2
, oceanic DMS
DMS oxidation ... gas phase ... complex!
3 3
OH
CH
3
SCH
3
CH
3
SCH
3
2
.
CH
3
SCH
CH
3
SCH
O
O
CH
3
SCH
O
CH
3
SCH
O
3
OH
2
.
CH
3
SCH OO CH
3
S
CH
3
SOH
2
.
CH
3
SCH O
CH
3
SO SO SO
2
SO
3
SO
4
H
2
CH
3
SO
2
CH
3
SO
3
CH
3
SO
3
H
2
CH
3
SCH OOH
. .
dimethylsulfone
methanesulfonic acid
sulfuric acid
OH
OH
O
2
OH O
2
O
2
HO
2
NO
O
3
+ CH
3
.
+ CH
2
O
OH
HO
2
H
2
O
Atmospheric Reaction Pathways for Dimethylsulfide
M
O
2
H O
2
ONO
CH
3
SCH
3
2
NO
3
CH
2
O HO
2
,
NO
2
,
(mod. from Yin et al., 1990)
SO
2
oxidation in the gas phase is simple...
but most SO
2
oxidation occurs in the aqueous phase...

O H SO H O H 2 SO
SO HO O HOSO
HOSO OH SO
2 4 2 2 3
3 2
M
2 2
2
M
2
+ +
+ +
+
+
+
+ +
+ +

H SO O H HSO
H HSO O H SO
SO SO
2
3
8 ~ pK
2 3
3
4 ~ pK
2 2
) aq ( 2 ) g ( 2
2
1
heterogeneous oxidation of SO
2
in-cloud oxidation
weakly buffered, pH ~4
oxidation by H
2
O
2






seasalt aerosols
strongly buffered by carbonate system
rapid oxidation by O
3

slower oxidation by H
2
O
2
(also OH, halogen radicals...)
growth of existing particles, inhibits nucleation of new
particles
(Chameides and Stelson, 1992)