effects of degraded air-quality on precipitation and
TRANSCRIPT
MGWA Simcik 04.12.06
Effects of degraded air-quality on precipitation and recharge
quality
Matt F SimcikDivision of Environmental Health Sciences
School of Public HealthUniversity of Minnesota
MGWA Simcik 04.12.06
MGWA Simcik 04.12.06
USGS website
MGWA Simcik 04.12.06
Percolation• Volatilization
– Henry’s Law• Adsorption
– Kd• Absorption
– fOM
– KOW
• Biodegradation
sw
l
x
x
Cp
CPH
0
≈=Low H
water
soild C
CK =Low Kd
omomneutw
omomOC fK
CfCK ⋅=
⋅=
,
14.0log82.0log +≅ owom KKLow fOM
Low KOW
Recalcitrant
MGWA Simcik 04.12.06
Precipitation/Deposition
• Precipitation– Solubility– Particulate– Surface adsorption
• Dry Deposition– Particle size distribution– Gas-Particle Partioning
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Wet Deposition
C
C
C
C
C
CHenry’s
Law
Air-icepartitioning
or
Absorptioninto organic film
impaction
Browniandiffusion
interceptionimpaction
interceptionfiltration
Brownian diffusion
aq
p s,rain
g s
org
Simcik, 2001 In: Persistent Organic Pollutants: Environmental Behavior and Pathways of Human Exposure
MGWA Simcik 04.12.06
Washout of Air Pollutants
( )φφ −+= 1GPT WWWAir
ecipT C
CW Pr= ( )
( )
3
3
mng
mng
air of volumeair in SOC of mass
rain of volumerain in SOC of mass
gasAir,
gas Precip,
C
CWG =
particle Air,
particle Precip,
C
CWP =
MGWA Simcik 04.12.06
Gas ScavengingHenry’s Law Partitioning• partitioning to bulk dissolved phase• equilibrium is reached in 10m fall of raindrop• equilibrium described by Henry’s Law:
wCP
H =
RTH
H ='Dimensionless HLC:
',
, HC
C gAdR =
Partitioning to surface
gas Air,
surface water
CC
K ia =
( )( )air of volume
air in SOC of mass waterof area surface
surface on SOC of mass
2
3
mm
K ia =
Kia is inversely proportional to pL
0 just as K from gas-particle partitioning
MGWA Simcik 04.12.06
Gas ScavengingHenry’s Law Partitioning Partitioning to surface
( )'bulk , H
WG
φ−=
1 ( )φ−= 16000
dKW iaG surface ,
( )φ−
+= 1
60001d
KH
W iaG 'Partitioning to surface becomes important only for compounds with high Kia values and low enough F
MGWA Simcik 04.12.06
Particle Scavenging• Particle washout ratio not so easily calculated from theory• Dependent on both particle size and raindrop size, but more so particle size• Generally 104 – 106, but often operationally defined
MGWA Simcik 04.12.06
Dry Deposition
•Particle phase pollutants depositing on terrestrial aquatic surfaces•Gravitational settling•Molecular diffusion
Turbulence
Boundary layer = no turbulence
Well-mixed Bulk Air
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Transfer Depends on:
• Meterology– T, atmospheric stability, relative humidity,
wind speed, pollutant concentration• Particles
– Size, electrostatic effects, density, shape• Surface
– Type (terr vs. aquatic), canopy structure, pH effects, roughness
MGWA Simcik 04.12.06
Removal Rate = Flux, F
F = Vd Ca,p Vd – Deposition velocityCa,p – Air particle concentration of
pollutant
0.0001
0.001
0.01
0.1
1
10
100
Vd (cm sec )
0.001 0.01 0.1 1 10 100Particle Diameter ( m)µ
BrownianDiffusion
GravitySedimentationInertial forces
-1
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Physi-chemicalsorptionAd
sorptioninto Liquid-like MatrixAb
Surfaces:MineralElemental CarbonIce
Liquid-like Matrices: Organic Carbon Water
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What determines whether a HAP will be a gas, particle or both?
Vapor Pressure = partial pressure of a compound above the pure substance at STP
p0 < 10-7 Pa
10-7 < p0 < 10Pa
p0 > 10 Pa
particles
both
gas
Metals and some large organics
SOCs
Hg0, radon, VOCs
MGWA Simcik 04.12.06
Precipitation/Deposition
• Precipitation– Solubility High Solubility/Low H– Particulate Particulate– Surface adsorption air-water afinity
• Dry Deposition– Particle size distribution larger/smaller– Gas-Particle Partioning low volatility
MGWA Simcik 04.12.06
Atmospheric transport
• Gas-Particle– Gases transport farther– Particles greater potential for deposition
• Reactions– Reactive compounds won’t make it very far– Reaction products may – Gas-particle partitioning
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Physical Chemical Properties• Low H• Low Kd• Low Kow• Recalcitrant• Low vapor pressure
• Non-Reactive• High aqueous
solubility
Large sources are necessary to be significant
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Candidate Chemicals
• BTEX• Ammonia• Metals• Pesticides• Perfluorochemicals
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BTEX
• High H• Low solubility• Moderate Kd• High vapor pressure
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Ammonia
• Gas/particle– Relative humidity
• Large sources• Present in precipitation• Biodegradation?• Adsorption?
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Metals (Se, Al, Zn etc.)
• Low H• Low vapor pressure• Low Kow• Kd?• Solubility?
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Pesticides
• Long-range transport• Low H• High solubility• Moderate Kow• Kd?• Reactive?
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PerfluorochemicalsPFOS
PFOA
F3C
F2C
COOH
n
Other perfluorinated acids
n = 4-10
F3C
F2C
CCF2
F2C
CF2
F2C
CF2
COOH
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Perfluorochemicals
• Surface active molecules• Stain protectant• Non-stick surfaces• AFFF – Aqueous Film Forming Foam• Residual by-products
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Physical/Chemical Properties
• Extremely low H• Low Kd• Kow?• Extremely recalcitrant & non-reactive• Low vapor pressure• Relatively high aqueous solubility (mg/L)
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Transport
• Global distribution– Biota– Water
• Atmospheric transport– Precursors
• Direct discharge– WWTP– Landfill leaching
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MGWA Simcik 04.12.06
PFCPlant
MajorMidwestern
River
High PFCContamination
In Groundwater