Transporte y deposición atmosférica de contaminantes...
Transcript of Transporte y deposición atmosférica de contaminantes...
Transporte y deposición atmosférica de contaminantes orgánicos
Jordi DachsDepartamento de Química Ambiental,
Instituto de Diagnóstico Ambiental y Estudios del Agua de BarcelonaConsejo Superior de Investigaciones Científicas (CSIC)
Transporte y deposición atmosférica de contaminantes orgánicos
- Mecanismos advectivos de transporte
- Transporte atmosférico- Transporte marino- Ríos…- Biota- Actividades antropogénicas (desguace, vertidos…)
- Mecanismos Difusivos de transporte
- Difusión molecular – importante a escalas pequeñas(interfases)- Difusión Turbulenta – importante a escalas medianas
Pag 52 of jacob
ANAN EXAMPLE OF TRANSPACIFIC TRANSPORT OF EXAMPLE OF TRANSPACIFIC TRANSPORT OF ASIAN AEROSOL POLLUTION AS SEEN BY MODISASIAN AEROSOL POLLUTION AS SEEN BY MODIS
Detectable sulfate pollution signal correlated with MOPITT COX1018 [molecules cm-2]
Pag 70 of jacob
CG
CWCP
CAIntercambioAire-Agua
Sorción-desorción
Sorción-desorción
DeposiciónSeca
DeposiciónHúmeda
Flujosverticales
Procesos físico-químicos y biogeoquímicosEcosistemas acuáticos
Advección y difusión turbulenta
Bioacumulación
Aportescontinentales
Transporteatmosférico
Slope = -6300R2 = 0.61
-23
-22
-21
-20
-19
-18
-17
0.0032 0.0033 0.0034 0.0035 0.0036 0.0037 0.0038
1/T (K)
ln P
o L (P
a)
PCBs
New Brunswick
Temperature Dependence of AtmosphericConcentrations of POPs
- P.A. Brunciak, J. Dachs, C.L. Gigliotti, E.D. Nelson andS. J. Eisenreich. Atmos. Environ. 35, 3325-3339, 2001.
Sedimentos4.900 kg
Columna de agua10.000 kg
???143 kg/a
Ríos110 kg/a
Deposición atmosférica
Seca32 kg/a
Húmeda125 kg/a
Intercambioaire-agua
680 kg/a440 kg/a
Ríos60 kg/a
Sedimentación110 kg/a
(Hornbuckle et al. Environ. Sci. Technol. 28, 1491-1501, 1994)(Hornbuckle et al. Environ. Sci. Technol. 29, 869-877, 1995)
Balance de masas de PCBs en el Lago Superior
FLUJOS AIRE-AGUA DE PCBS EN ZONAS COSTERAS
Chicago y Lago Michigan
(Green et al. Environ. Sci. Technol. 34, edición web, 2000)(Zhang et al. Environ. Sci. Technol. 33, 2129-2137, 1999)
CG
Figure 5.
Fluo
rene
Phena
nthr
ene
MePhe
nsFl
uora
nthe
nePyr
ene
Benzo
[b]fl
uor
Chrys
ene
Benzo
[a]p
yren
e
% o
f T
otal
A
tmos
pher
ic D
epos
itio
nal F
lux
0
20
40
60
80
100Dry Deposition Wet Deposition GasAbsorption
288 1930 2050 480 250 16 58Total Flux (ng/ m2 day)
22
Relative importance of air-water exchange for PAHs
(Gigliotti et al. 2001, Submitted)
AEROSOLS
DRY DEPOSITION
OF PARTICLES
Chemicalsassociatedwithparticles
VOLATILIZATION
Gas phaseOrganicCompounds
ABSORPTION OF GASES
WATER DROPLETS
WASHOUT OF GASES
WASHOUT OF PARTICLES
Atmospheric Depositional Processes of Organic Compounds
INTERCAMBIO AIRE-AGUA
Interfase Aire-AguaTransferencia de fase
0.1 mm
1 mmCapa límite
del aire
Capa límitedel agua
Difusión
Difusión
Mezcla TurbulentaAire Turbulento
Mezcla TurbulentaAgua Turbulenta
AIR-WATER FLUX (FA-W)
RS
RTH
Η´ VapVap ..lnΔ
+Δ
−=
61.0
,
,,,
2
2 ⎟⎟⎠
⎞⎜⎜⎝
⎛=
AirOH
AirPOPAirOHAirPOP D
Dkk
´111,, Hkkk AirPOPWPOPAW
+=
⎟⎠⎞
⎜⎝⎛ −= Water
AirAWAW C
HCkF
´
CAir
CWater
Cwater, Int.
CAir, Int.
5.0
,2
2
−
⎟⎟⎠
⎞⎜⎜⎝
⎛=
CO
POPCOWPOP Sc
Sckk
Air
Water
Influence of wind speed on kWCO2
0
40
80
120
160
200
0 2 4 6 8 10 12 14 16 18 20
Wind Speed (m s-1)
k W
CO
2
LM86 W92 W99 N00
LM 86
N00
W92
W99
W99: KWCO2=0.0283U103 (Wanninkhof & McGillis 1999)
NOO: KWCO2=0.24U102+0.061U10 (Nightingale et al. 2000)
Coeficiente de transferencia de masa
(Schwarzenbach et al. EnvironmentalOrganic Chemistry, John Wiley & Sons, New York 1993)
0
5
10
15
20
25
30
24-7
-01
25-7
-01
26-7
-01
27-7
-01
28-7
-01
Tem
pera
ture
(C),
win
d sp
eed
(m s
-1)
Temperature
Wind speed
SE SW W NW E S W SE NE SW W NE SW W NE
Atmosphere Water ColumnInfluence of sea breeze onair-water exchange
PAH occurrence and Met data
(Pérez et al. ES&T 2003, 37, 3794-3802)
Influence of sea breeze on air-water exchange of PAHsMasnou Harbor (NW Mediterranean Sea)
0
200
400
600
800
1000
120024
-7-0
1
25-7
-01
26-7
-01
27-7
-01
28-7
-01
Net
Vol
atili
zatio
n Fl
ux (u
g m
-2 d
-1)
0
5
10
15
20
25
30
35
40
Win
d sp
eed
(m s
-1)
⎟⎠⎞
⎜⎝⎛ −= Water
AirAWAW C
HCkF
´
Role of sea breeze on air-water exchangeInfluence of parameterizations using instantaneous wind speeds
0
20
40
60
80
100
Fluo
rene
Phen
anth
rene
met
ylph
enan
thre
nes
dim
etyl
phen
anth
rene
s
Ant
hrac
ene
Dib
enzo
thio
phen
e
met
yldi
benz
othi
ophe
ne
Fluo
rant
hene
Pyre
ne
Ben
z[a]
anth
race
ne
Chr
ysen
e
Ben
zo[b
]fluo
rant
hene
Ben
zo[k
]fluo
rant
hene
Net
vol
atili
zatio
n flu
x (u
g m
-2 d
-1)
What would happen if an average wind speed is used?
W99: KWCO2=0.0283U103
NOO: KWCO2=0.24U102+0.061U10
Role of sea breeze on air-water exchangeComparison of fluxes using average and instantaneous wind speeds
0
20
40
60
80
100
Fluo
rene
Phen
anth
rene
met
hylp
hena
nthr
enes
dim
ethy
lphe
nant
hren
es
Ant
hrac
ene
Dib
enzo
thio
phen
e
met
hyld
iben
zoth
ioph
ene
Fluo
rant
hene
Pyre
ne
Ben
z[a]
anth
race
ne
Chr
ysen
e
Ben
zo[b
]fluo
rant
hene
Ben
zo[k
]fluo
rant
hene
Net
vol
atili
zatio
n flu
x (u
g m
-2 d
-1)
Using 12-hour average wind speeds underestimate the flux by a factor of two
W99: KWCO2=0.0283U103
Instantaneous wind speed
Average wind speed
0
2000
4000
6000
8000
10000
25-6
-01
- 6 p
m
26-6
-01
- 12
am
- 6 a
m
- 12
pm
- 6 p
m
27-6
-01
- 12
am
- 6 a
m
- 12
pm
- 6 p
m
28-6
-01
- 6 a
m
pg m
-3
Gas Phase
Aerosol Phase
SW Mediterranean SeaRV Pelagia, May 2001
0
4
8
12
16
20
25-5
-01
26-5
-01
27-5
-01
28-5
-01
Win
d Sp
eed
(m s
-1)
PAHs
-5000
-4000
-3000
-2000
-1000
0
25-5
-01
26-5
-01
27-5
-01
28-5
-01
Net
Air
-Wat
er F
lux
(ng
m-2
d-1
)
PAHs
Air-water exchange of PAHs in the SW Mediterranean SeaMay, 2001
Comparison of fluxes using averaged and instantaneous wind speedsSW Mediterranean Sea, May 2001
Increase of fluxes using instantaneous wind speeddepends on POP physical chemical properties
0
10
20
30
40
50
0 5 10 15 20 25 30
H298(Pa m3 mol-1)
Flux
Incr
emen
t whe
n us
ing
inst
anta
neou
s U
10 (%
)
PAH
PCB
NP
W99: KWCO2=0.0283U103
NOO: KWCO2=0.24U102+0.061U10
Two Film Air-Water Exchange model
Phase transfer
0.1 mm
1 mm
Diffusion
Diffusion
Two Film Air-Water Exchange model
Phase transfer
0.1 mm
1 mm
Diffusion
Diffusion
( )ξ
ηυ⎟⎟⎠
⎞⎜⎜⎝
⎛−
= evFWeibull distribution:
Wind speed variability and air-water exchange
Scale parameter: ηShape parameter: ξ
Weibull corrected kWCO2 :
Shape parameter
Reference N00 (quadratic)
% increment
W99 (cubic) % increment
Sea Breeze (coastal NW Mediterranean) Open SW Mediterranean
1.8
2.4
This study This study
31%
16%
105%
45%
Global Oceans 2 Conradsen et al. 1984
30%
98%
Alpine lakes
1
Livingston&Imboden 1993
49%
380%
Pyrenees lakes
1.4 This study 46% 204%
102 061.02124.0
2UkwCO +⎟⎟
⎠
⎞⎜⎜⎝
⎛+Γ=ξ
η
⎟⎟⎠
⎞⎜⎜⎝
⎛+Γ=ξ
η 310283.0 32wCOk
AEROSOLS
DRY DEPOSITION
OF PARTICLES
Chemicalsassociatedwithparticles
VOLATILIZATION
Gas phaseOrganicCompounds
ABSORPTION OF GASES
WATER DROPLETS
WASHOUT OF GASES
WASHOUT OF PARTICLES
Atmospheric Depositional Processes of Organic Compounds
Page 148 of jacob
Atmospheric cycling of aerosols
Aerosol size distribution
Aerosol size distribution
Aerosol size distribution
Aerosol size distribution
Number
Surface
Volume
Number
Surface
Volume
Aerosol size distribution
Number
Surface
Volume
Aerosol size distribution
Number
Surface
Volume
Aerosol size distribution
Number
Surface
Volume
Aerosol size distribution
Vertical profiles of aerosols
Aerosol size distribution and composition
Page 147 of jacob
Composition of aerosols
Aerosol Size Distributions of Aerosols
ACE-Asia aircraft observations over Japan (spring 2001)
• implies large secondary production of OC in free troposphere missing from present models;• OC dominates aerosol loading in free troposphere
Colette Heald and Daniel JacobHarvard University
Elevated OC aerosol is observed in free tropospheric Asian Outflow
Observed (Huebert)GEOS-Chem
Observed (Russell)
OC/sulfate ratio
Observed (Huebert)GEOS-ChemObserved (Huebert)GEOS-Chem
Observed (Russell)
OC/sulfate ratio
AEROSOLS
DRY DEPOSITION
OF PARTICLES
Chemicalsassociatedwithparticles
VOLATILIZATION
Gas phaseOrganicCompounds
ABSORPTION OF GASES
WATER DROPLETS
WASHOUT OF GASES
WASHOUT OF PARTICLES
Atmospheric Depositional Processes of Organic Compounds
10-3 10-2 10-1 100 101 10210-3
10-2
10-1
100
101
102
20 m s-1
10 m s-1
2 m s-1
v D[c
m s-1
]
Dp [μm]
10-3 10-2 10-1 100 101 10210-3
10-2
10-1
100
101
102
20 m s-1
10 m s-1
2 m s-1
v D[c
m s-1
]
Dp [μm]pDDD Cv F ×=
Dry Deposition of Aerosols
Influence of surface microlayer on Atmospheric deposition ofaerosols and pollutants
180ºW 135ºW 90ºW 45ºW 0º 45ºE 90ºE 135ºE 180ºE
90ºN
60ºN
30ºN
0º
30ºS
60ºS
90ºS
0 0.5 1 1.5 2
>> >> drydry depositiondeposition > > aerosol aerosol sizesize fromfrom MODISMODIS
EffectiveEffective RadiusRadius
MODIS (TERRA, NASA) November 2002-2003http://modis.gsfc.nasa.gov
[μm]
10-1 100 1010
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Dp: 2-3 μm
Dp: 1-2 μm
Dp: 3-5 μm
DDpp: : ParticleParticle DiameterDiameter [[μμm]m]
wwii
+ Standard deviation effective radius
VolumetricVolumetric ffractionraction ofofparticlesparticles ((wwii))
parameters lognormal distributionnumber concentration of aerosols
10-3
10-2
10-1
100
101
102
10-3
10-2
10-1
100
101
102
20 m s-1
10 m s-1
2 m s-1
v D[c
m s-1
]
Dp [μm]
10-3
10-2
10-1
100
101
102
10-3
10-2
10-1
100
101
102
20 m s-1
10 m s-1
2 m s-1
v D[c
m s-1
]
Dp [μm]
Dry Aerosol Deposition
(Adapted from Ondov et al 1997)
pDDD Cv F ×=
Dry deposition fluxes MODISInformation on aerosol concentration and size distribution
[μg m-3]
>> >> organicorganic andand blackblack carboncarbon aerosol aerosol fractionsfractions
Baseline backgroundaerosol
Continentallyinfluenced
Sea-salt
Urban and suburban, industrial emissions
Biomass burning
Dust plumes
Baseline backgroundaerosol
Continentallyinfluenced
Sea-salt
Urban and suburban, industrial emissions
Biomass burning
Dust plumes
Cavalli et al. 20040.14Sea-salt
submicron aerosol6.337
supermicron aerosol0.94.3Brasseur et al. 2003
submicron aerosol1.918.5Backgroundaerosol
supermicron aerosol0.53.2Brasseur et al. 2003
submicron aerosol1.213.7Continentallyinfluenced
Kinne et al. 20030.53.5Dust
Brasseur et al. 2003supermicron aerosol1.431.9
Industrial emissions
supermicron aerosol0.63.8Brasseur et al. 2003
submicron aerosol15.319.1BiomassBurning
ref.fBC (%)fOC (%)Aerosol type
Cavalli et al. 20040.14Sea-salt
submicron aerosol6.337
supermicron aerosol0.94.3Brasseur et al. 2003
submicron aerosol1.918.5Backgroundaerosol
supermicron aerosol0.53.2Brasseur et al. 2003
submicron aerosol1.213.7Continentallyinfluenced
Kinne et al. 20030.53.5Dust
Brasseur et al. 2003supermicron aerosol1.431.9
Industrial emissions
supermicron aerosol0.63.8Brasseur et al. 2003
submicron aerosol15.319.1BiomassBurning
ref.fBC (%)fOC (%)Aerosol type
>> d>> dryry deposition of OC aerosoldeposition of OC aerosol
[mg C m-2 d-1]Nov. 2002-2003
TOTAL: 20 Tg C yr-1
10.5
FDD_OC
( ) ( )( ) p0PG0rainWD CpW1WpCF ×
φ×φ+φ−=×=
WP: particle washout ratio ----cteWG: gas washout ratio ---- equilibriumφ: fraction of contaminant bound to particles in
the atmosphere
[mm month-1]
SSM/I (NOAA) http://www.noaa.gov/November 1998
p0: p0: precipitationprecipitation intensityintensity
180ºW 135ºW 90ºW 45ºW 0º 45ºE 90ºE 135ºE 180ºE
90ºN
60ºN
30ºN
0º
30ºS
60ºS
90ºS
0 50 100 150 200 250 300 350 400 450 500
Wet Deposition
DRY DEPOSITION
ATMOSPHERIC DEPOSITIONAL PROCESSES
AIR-WATER EXCHANGE
WET DEPOSITION
FDD=vDCAER FAW =kAW(CG/H’-Cw) FWD=(WPCAER+WGCG)p0
WG = 2000·KiA·Λ+RT/HWP = 2 · 105
>> >> wetwet deposition of OC aerosoldeposition of OC aerosol
Wet deposition to global oceans: 77 Tg C yr-1
2.5[mg C m-2 d-1]Nov. 2002-2003
FWD_p_OC
(90 Tg C yr-1 , Willey et al 2000)
>> latitudinal >> latitudinal profilesprofiles toto thethe AtlanticAtlantic
0 5 10 15 20 25
90ºN
60ºN
30ºN
0º
30ºS
60ºS
90ºS
Dry deposition flux
Wet deposition flux
Net air-waterexchange flux
ClCl55DDDD
(Jurado et al. EsT, 38, 5505-5513. 2004)
(Jurado et al. EsT, 39, 2426-2435. 2005)
[pg m-2 d-1]
>> >> validationvalidation
Without brakets when referred to PCB 28, 52, 101, 118, 138, 153, 180In brakets when referred to all the PCB congeners
3600(1530)(29N, 95W)Galveston Bay, TexasPark et al. 2001
706735 (1300)(28N, 16E)Izaña,
Tenerife, NE Atlantic
Van Drooge 2001
130268 (310)(39N, 74W)Tuckerton, USVan Ry 2002
107(820)(35N, 25E)Crete island,
eastern Mediterranean
Mandalakis et al. 2004
estimatedFWD ΣPCBs[ng m-2 yr-1]
measured FWD ΣPCBs[ng m-2 yr-1]
(Latitude, Longitude)
LocationName
Source
(Jurado et al. EsT, 39, 2426-2435. 2005)
Factor 1-2
0
100
200
300
400
500
600
PCB28 PCB52 PCB101 PCB118 PCB138 PCB153 PCB180
pg m
-2 d
1
0
5
10
15
20
25
30
Cl4DF Cl5DF Cl6DF Cl7DF OCDF Cl4DD Cl5DD Cl6DD Cl7DD OCDD
pg m
-2 d
-1
>> mean >> mean depositionaldepositional fluxesfluxes toto thethe AtlanticAtlantic
Net Air-water exchange
DryDeposition
PCBs: FAW >> FDD, FWD !!
Wet Deposition
- volatile+ volatile
Figure 5.
Fluo
rene
Phena
nthr
ene
MePhe
nsFl
uora
nthe
nePyr
ene
Benzo
[b]fl
uor
Chrys
ene
Benzo
[a]p
yren
e
% o
f T
otal
A
tmos
pher
ic D
epos
itio
nal F
lux
0
20
40
60
80
100Dry Deposition Wet Deposition GasAbsorption
288 1930 2050 480 250 16 58Total Flux (ng/ m2 day)
22
Relative importance of air-water exchange for PAHs
(Gigliotti et al. 2001, Submitted)
D is s o lv e d P h a s e
[PC
B]
(pg/
L)
0
2 0
4 0
6 0
8 0
G a s e o u s P h a s e
[PC
B]
(pg/
m3 )
0
1 0
2 0
3 0
S P M P h a s e
[PC
B]
(pg/
L)
0
2 0
4 0
6 0
8 0
P h y to p la n k to n P h a s e
1816
+32 31 28 22 45 46
52+4
3 4947
+48 44
37+4
241
+71 64 40 74
70+7
666
+95 91
+60+
8992
+84
101 99 83 97
87+8
185
+136
10+7
7 82 151
47+1
2423
+107 118
146
53+1
32 105
41+1
7963
+138 158
78+1
2987
+182 183
185
174
177
71+1
56 180
199
70+1
90 201
03+1
9695
+208 194
206
[PC
B]
(pg/
L)
0
2 0
4 0
6 0
8 0
A e ro s o l P h a s e[P
CB
] (p
g/m
3 )
0 .0
.1
.2
.3
Correlated: R2 = 0.90
un-correlated
Correlated: R2 = 0.96
Correlated: R2 = 0.70
Evidence for Gas-Phase Driven Phytoplankton accumulation of PCBs
Air-Water-Phytoplankton Exchange of POPs
Air-water exchange
Water-phytoplankton exchange
CA
MLD CW CP
FWP
FAW⎟⎠⎞
⎜⎝⎛ −= WA
AWAW CHCkF
'
⎟⎟⎠
⎞⎜⎜⎝
⎛ +−= P
u
GdWWPWP Ck
kkCkF
-J. Dachs, S.J. Eisenreich, J.E. Baker, F.C. Ko, J.D. Jeremiason. Environ. Sci. Technol. 33, 3653-3660, 1999.
Vertical Flux
P
u
GdSinkSink C
kkkkF +
=FSink
0 20 40 60 80 100
CP
(pg
g-1)
0
500
1000
1500
2000
2500
3000
June July August
Lake 227
1994
0 20 40 60 80 100
CP
(pg
g-1)
0
500
1000
1500
2000
2500
3000
June July August
Lake 227
1994
Observed
Model
Air-Water Exchange Controls Aquatic Concentrations of POPs(Experimental Lakes Area)
Phytoplankton concentrations of PCB 52
Proceso de destilación global
Global Atmospheric Depositional Processes
270 275 280 285 290 295 300 305
180 360 540 720
60
120
180
240
300
360
90N
60N
30N
0
30S
60S
90S180W 90W 0 90E 180E
273 275 280 285 290 295 300 305T (K)
Temperature
-90
-60
-30
0
30
60
90
0.000 0.004 0.008 0.012
H'
Latit
ud
Henry’s Law ConstantPCB 52
Air-Water Exchange
⎟⎠⎞
⎜⎝⎛ −= W
AAWAW C
HCkF
'L
atitu
de
¿Qué explica la distribución global de loscontaminantes Orgánicos?
Temperatura Productividad primaria
(NASA Goddard Space Flight Center; www.gsfc.nasa.gov)
270 275 280 285 290 295 300 305
180 360 540 720
60
120
180
240
300
360
90N
60N
30N
0
30S
60S
90S
0 5 10 15
180 360 540 720
60
120
180
240
300
360
90N
60N
30N
0
30S
60S
90S180W 90W 0 90E 180E 180W 90W 0 90E 180E
273 275 280 285 290 295 300 305T (K)
0 5 10 15U10 ( m s-1)
Temperature Wind Speed
Remote Sensing MeasurementsOctober-December 1998
0 0.5 1 1.5 2 2.5 3 3.5
180 360 540 720
60
120
180
240
300
360
180W 90W 0 90E 180E
90N
60N
30N
0
30S
60S
90S
0 0.5 1 1.5 2 2.5 3 3.5 kAW (m d-1)
-90
-75
-60
-45
-30
-15
0
15
30
45
60
75
90
0 1 2 3
kAW (m d-1)
Latit
ude
Global Variability of kAWPCB 52
Air-Water Exchange
⎟⎠⎞
⎜⎝⎛ −= W
AAWAW C
HCkF
'
Air-Water Fluxes
Air-Water-Phytoplankton Exchange of POPs
Air-water exchange
Water-phytoplankton exchange
CA
MLD CW CP
FWP
FAW⎟⎠⎞
⎜⎝⎛ −= WA
AWAW CHCkF
'
⎟⎟⎠
⎞⎜⎜⎝
⎛ +−= P
u
GdWWPWP Ck
kkCkF
-J. Dachs, S.J. Eisenreich, J.E. Baker, F.C. Ko, J.D. Jeremiason. Environ. Sci. Technol. 33, 3653-3660, 1999.
k WP = Biomass ku MLDVertical Flux
P
u
GdSinkSink C
kkkkF +
=FSink
Gd
uOMSink kkkFk+
=
0 100 200 300 400 500 600 700 800 900
180 360 540 720
60
120
180
240
300
360
90N
60N
30N
0
30S
60S
90S180W 90W 0 90E 180E
0 100 200 300 400 500 600 700 800 900MLD (m)
Mixed Layer Depth
0 0.5 1 1.5 2 2.5 3 3.5 4
180 360 540 720
60
120
180
240
300
360
90N
60N
30N
0
30S
60S
90S
180W 90W 0 90E 180E
0 1 2 3 4Chlorophyll ( mg m-3)
Chlorophyll
Remote Sensing Measurements
⎟⎟⎠
⎞⎜⎜⎝
⎛ +−= P
u
GdWWPWP C
kkkCkF
Water-Phytoplankton Fluxes
uWP kMLDBiomassk ⋅⋅=
0 1 2 3 4 5 6 7 8 9 10
180 360 540 720
60
120
180
240
300
360180W 90W 0 90E 180E
90N
60N
30N
0
30S
60S
90S
0 2 4 6 8 10kWP (m d-1)
Global Variability of kWPPCB 52
-90
-75
-60
-45
-30
-15
0
15
30
45
60
75
90
0 5 10 15
kWP (m d-1)
Latit
ude
Water-Phytoplankton Exchange
⎟⎟⎠
⎞⎜⎜⎝
⎛ +−= P
u
GdWWPWP C
kkkCkF
Water-Phytoplankton Fluxes
Air-Water-Phytoplankton Exchange of POPs
Air-water exchange
Water-phytoplankton exchange
MLD
⎟⎠⎞
⎜⎝⎛ −= WA
AWAW CHCkF
'
⎟⎟⎠
⎞⎜⎜⎝
⎛−= P
u
dWWPWP CkkCkF
-J. Dachs, S.J. Eisenreich, J.E. Baker, F.C. Ko, J.D. Jeremiason. Environ. Sci. Technol. 33, 3653-3660, 1999.
k WP = Biomass ku MLDVertical Flux
P
u
dSinkSink C
kkkF =
CA
CW CP
FWP
FAW
FSink
d
uOMSink kkFk =
(Lohmann, R., Ockenden, W.A., Shears, J., Jones, K.C. Environ. Sci. Technol. 2001)
Atmospheric Concentrations of PCBs, Dioxins and FuransAtlantic Ocean Transect (52N-74S)
-90
-75
-60
-45
-30
-15
0
15
30
45
60
75
90
0 30 60 90 120 150
CA (pg m-3)
Latit
ude
-90
-75
-60
-45
-30
-15
0
15
30
45
60
75
90
0 5 10 15
CA (pg m-3)
Latit
ude
-90
-75
-60
-45
-30
-15
0
15
30
45
60
75
90
0 50 100 150
CA (pg m-3)
Latit
ude
PCB 52 PCB 180 Cl4DD
North
South
Latit
ude
Latit
ude
Latit
ude
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
180 360 540 720
60
120
180
240
300
360180W 90W 0 90E 180E
90N
60N
30N
0
30S
60S
90S
ng m-2 d-1
Predicted Air-Water and Sinking Fluxes of PCBs, Dioxins and Furans
PCB 52
-90
-75
-60
-45
-30
-15
0
15
30
45
60
75
90
0 0.4 0.8 1.2 1.6 2
Flux (ng m-2d-1)
Latit
ude
Measured by Gustafsson, Gschwend and Buesseler, Environ. Sci. Technol. 31, 3544-3550, 1997
-90
-75
-60
-45
-30
-15
0
15
30
45
60
75
90
0 1 2 3
kAW, kSink (m d-1)
Latit
ude
-90
-75
-60
-45
-30
-15
0
15
30
45
60
75
90
0 1 2 3 4
kAW, kSink (m d-1)
Latit
ude
-90
-75
-60
-45
-30
-15
0
15
30
45
60
75
90
0 4 8 12 16 20
fA/fW
Latit
ude
PCB52
PCB180
PCB180PCB52
Latitudinal Variability of Air to Water Fugacity RatiosAtlantic Ocean
kAW
kAW
kSink
kSink
0
10
20
30
40
Apr
il
May
Jun
e
Jul
y
Aug
ust
Sep
t
Oct
Nov
Dec Ja
n
Febr
Mar
ch
Apr
il
May
250m1440m2850m
ΣBenzofluoranthene Flux
ngm
-2d-
1m
gm
-2d-
1
0
100
200
300 Mass Flux
ngm
-2d-
1
Biogeochemical Coupling of Atmospheric Deposition and Settling Fluxes
0
20
40
60
Settling Flux
Atmospheric Dep.
Atm. Dep.
Sed. Traps
L. Méjanelle, UPMC
PBDE and PAH atmospheric deposition
0
100
200
300
Aug
08-
Sep
03
Sep
03-
15S
ep 1
5-29
Sep
29-
Oct
15
Oct
15-
Nov
05
Nov
05
-12
Nov
12-
20N
ov 2
0-D
ec 0
3D
ec 0
3-12
Dec
12-
Jan
02Ja
n 02
-15
Jan
15-F
eb 0
2Fe
b 02
-18
Feb
18-M
ar 0
6M
ar 0
6- A
pr 0
2A
pr 0
2-15
Apr
15-
May
01
May
01-
Jun
02Ju
n 02
-17
Jun
17-J
ul 2
2Ju
l 22-
Aug
04
Aug
04-
23A
ug 2
3-31
Aug
31-
Sep
15
Sep
15-
Oct
02
Oct
02-
13O
ct 1
3-N
ov 0
4N
ov 0
4-10
Nov
12-
25N
ov 2
5-D
ec 0
9D
ec 0
9-Ja
n 02
Jan
02-2
0Ja
n 20
-Feb
21
Feb
21-A
pr 0
6A
pr 0
6-M
ay 0
5M
ay 0
5- J
un
BDE 47BDE 100BDE 99BDE 153BDE 183BDE 209SUM PAH Flux
pg m-2 d-1
ng m-2 d-1
2001 2002 2003
Atmospheric Deposition of Polybrominated BiphenylEthers and Polycyclic Aromatic Hydrocabons
L. Méjanelle, UPMC
Persistent Organic Pollutants (POPs)
Lohmann, R., K. Breivik, J. Dachs, D. Muir. Environ. Poll. 2007
Legacy POPs Emerging POPs
0
150
300
450
600
750
T3 T9 T11 T13 T15 T16 R6 R14 R18
Conc
entra
ció
(ng/
L)
Antiinflammatories Lipid regulators AntidepressantsAntihistaminics Antibiotics B-blockers
T12
R14
R17
T16
T15
T9R1T3
R18
T8
R4R6T7
T13
T11T10
T5
T2
TORTOSA
LLEIDAZARAGOZA
HUESCAMONZÓN
SABIÑÁNIGO
PAMPLONA
LOGROÑO
VITORIA
TUDELA
T12
R14
R17
T16
T15
T9R1T3
R18
T8
R4R6T7
T13
T11T10
T5
T2
TORTOSA
LLEIDAZARAGOZA
HUESCAMONZÓN
SABIÑÁNIGO
PAMPLONA
LOGROÑO
VITORIA
TUDELA
T12
R14
R17
T16
T15
T9R1T3
R18
T8
R4R6T7
T13
T11T10
T5
T2
TORTOSA
LLEIDAZARAGOZA
HUESCAMONZÓN
SABIÑÁNIGO
PAMPLONA
LOGROÑO
VITORIA
TUDELA
Emerging (non-regulated) POPs: Pharmaceuticals in theEbro River
Atenolol
Sotalol
Metoprolol
Propranolol
Erythromycin
Azithromycin
Sulfamethaxole
Trimethoprim
Ofloxacin
Lansoprazole
Loratadine
Famotidine
Ranitidine
Carbamazepine
Fluoxetine
Paroxetine
Clofibric acid
Gemfibrozil
Bezafibrate
Pravastatin
Mevastatin
Ibuprofen
Naproxen
Ketoprofen
Indomethacine
Diclofenac
Acetaminophen
Mefenamic acid
Propyphenazone
b-blokersAntibioticsAntiulceragents
Psychiatricdrugs
Lipid regulatorand cholesterollowering statin
drugs
Analgesics and antiinflammatories
Atenolol
Sotalol
Metoprolol
Propranolol
Erythromycin
Azithromycin
Sulfamethaxole
Trimethoprim
Ofloxacin
Lansoprazole
Loratadine
Famotidine
Ranitidine
Carbamazepine
Fluoxetine
Paroxetine
Clofibric acid
Gemfibrozil
Bezafibrate
Pravastatin
Mevastatin
Ibuprofen
Naproxen
Ketoprofen
Indomethacine
Diclofenac
Acetaminophen
Mefenamic acid
Propyphenazone
b-blokersAntibioticsAntiulceragents
Psychiatricdrugs
Lipid regulatorand cholesterollowering statin
drugs
Analgesics and antiinflammatories
Barceló et al. Personal comunication
Perfluoroalkyl substances are globally distributed, anthropogenic contaminants.
Perfluoroalkyl acids (PFAs) are synthetic, perfluorinated, straight- or branched-chain organic acids characterized by a carboxylate or sulfonate moiety.
Surface treatment applications to provide soil, oil and water resistance to personal apparel and home furnishings (e.g. carpet cleaner and Goretex®). on paper products to provide grease, water, and oil resistance to plates, food containers, bags, and wrap (Teflon ®)aqueous film-forming foams (AFFF) for fire-fighting,
To which extend atmospheric inputs control water concentrations of POPs?
CWT [ng m-3]
A PCB 28
dept
h [m
]
CWT [ng m-3]
A PCB 28
dept
h [m
]precipitationprecipitation
PCB 28(Jurado et al. 2007, Mar. Pollut. Bull 54, 441-451)
Influence of turbulence on water column concentrations and variability
(Example: Adriatic Sea)
CWT [ng m-3]
A PCB 28
dept
h [m
]
CWT [ng m-3]
A PCB 28
dept
h [m
]
precipitationprecipitation
(Jurado et al. 2007, Mar. Pollut. Bull 54, 441-451Dachs & Méjanelle 2010)
Water column mixing in shallow waters: Importance of sediments
as a source of POPs