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Dispersion of
Pollutants Introduced
into the Atmosphere
as Determined by
Residence Times
(Husar and Patterson, 1980)
Washout by rain:
Crain
WT
Wg (1 ) W p
Cair
Washout consists of capture of gas and particle phases
Gases equilibrate with rain via Henrys Law
(reversible air-water exchange)
Particles are irreversibly captured
For PCBs: Wg ~ 200-400, Wp ~ 104 105
For PAHs: Wg ~ 10-500, Wp ~ 103 106
Atmospheric reactions
Many (most?) organic species are reactive in the
atmosphere via direct or indirect photolysis
Half-lives of PAHs:
Gas phase = minutes-hours
Particle phase = hours-days
How does this contradict figure 1?
Health effects:
Particles can deposit in lungs.
What role does chemical makeup of these particles play?
Chemicals properties
(liquid VP, Koa)
2.
particle characteristics:
size distribution,
carbon content,
composition
3.
Atmospheric
conditions: T, RH
Denuder
under laminar
flow, gases
diffuse faster, so
adsorb to
surface
best for hi conc
and lo MW
gases (NOx, etc)
Impactor
MOUDI
micro-orifice
uniform deposit
impactor
nozzle size and thus
air velocity changes
in each chamber
8-10 stages
0.2 0.3 um cutoff
filter gets the rest
Cyclone
sampling artifacts?
Sorption of gases to filters or particles during
sampling
Volatile losses from filter, particles, impactor stages
especially at high T, high flow (I.e. large pressure
drop
Effect on partition coefficient?
N S aTSP T e ( Ql Qv ) / RT
CP
KP
CGTSP
1600 p Lo
f om 760 RT
CP
KP
o
6
CGTSP MWom om p L 10
K P f om
MWoct oct
K oa
12
MWom om oct 10
Temperature dependence
Yamasaki (1982)
Cg
A
log
B
C p / TSP
T
semi-volatile
compounds have
significant conc in
both the gas and
particle phases
Kp alone often
gives slopes of -1
normalizing Kp to
om, OC, or EC
improves R2, but
slopes still -1
accounting for OC
and EC usually
gives best R2,
slopes still -1
difference between PAHs and PCBs in same air mass sampled twice
July 22-23, 1994
1
Chicago PAH
LM PAH
Chicago PCB
LM PCB
log KP (m /g)
0
-1
Slopes:
Chicago
PAH = -0.734
-2
PCB = -0.517
-3
LM
-4
PAH = -0.811
-5
PCB = -0.634
-6
-6
-5
-4
-3
-2
-1