Perturbaciones antropogénicas de la quimiosfera orgánica: Implicaciones a
escala global.
Jordi DachsDepartamento de Química Ambiental,
Instituto de Investigaciones Químicas y Ambientales de BarcelonaConsejo Superior de Investigaciones Científicas (CSIC)
Objetivos
- Perturbaciones antropogénicas de la quimiosfera
- ¿Es posible cuantificar y caracterizar las perturbaciones químicas por compuestos sintéticos?
- Transporte y sumideros de contaminantes orgánicos a escala global.
- Evaluación de riesgo de las familias de compuestos químicos antropogénicos.
- Cambio climático y la quimiosfera tóxica
Anthropogenic perturbations of the chemosphere
- Emissions from fossil fuels (CO2, CO, NO, hydrocarbons….).
- Emissions from combustion processes (Dioxins and Furans, PAHs, …)
- Sinthetic chemicals used in industry and consumer products.
- Emission of anthropogenic aerosols.
- Changes in atmospheric chemistry and composition produced by all the above perturbations.
Emissions from Gasoline Combustion
Schauer et al. Environ. Sci. Technol. 40, 1169-1180, 2002.
0
20000
40000
60000
Bra
nch
ed a
lkan
es
Alk
an
es
UC
M 1
n-A
lke
nes
Sat
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ted
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clo
alk
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Bra
nch
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Un
satu
rate
d c
yclo
alk
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Alk
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Mo
no
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mat
ic h
ydro
ca
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ns
Eth
ers
Alip
ha
tic
ald
eh
yd
es (
>c8
)
Alip
ha
tic
ald
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yd
es (
c3-7
)
Ace
tald
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de
2-3
rin
g P
AH
s
Aro
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tic
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Ole
fin
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UC
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Tri
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Alip
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tic
Ket
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es
Aro
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tic
ket
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es
n-A
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no
ic a
cid
s
Fo
rma
lde
hyd
e
Aro
ma
tic
aci
ds
Oth
ers
Oth
er
PA
Hs
Dic
arb
on
yls
Em
issi
on
(m
g k
g-1
)
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
Bra
nc
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d a
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s
Alk
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n-A
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Sa
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Bra
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Un
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Alk
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Mo
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Eth
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Ali
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>c
8)
Ali
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c3
-7)
Ac
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Aro
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Ole
fin
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Aro
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tic
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n-A
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no
ic a
cid
s
Fo
rma
lde
hy
de
Aro
ma
tic
ac
ids
Oth
ers
Oth
er
PA
Hs
Dic
arb
on
yls
Air
-wat
er f
lux
(% o
f to
tal O
C f
lux)
1.E-07
1.E-05
1.E-03
1.E-01
1.E+01B
ran
ch
ed
alk
an
es
Alk
an
es
UC
M 1
n-A
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ne
s
Sa
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Bra
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Un
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dro
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ns
Eth
ers
Ali
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lde
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de
s (
>c
8)
Ali
ph
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c a
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c3
-7)
Ac
eta
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2-3
rin
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AH
s
Aro
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tic
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Ole
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Aro
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s
Fo
rma
lde
hy
de
Aro
ma
tic
ac
ids
Oth
ers
Oth
er
PA
Hs
Dic
arb
on
yls
H' (
dim
ensi
on
less
)
FAbs=k CGas / H’
H’=CGas / CWater
Gas absorption
(Schauer et al. ES&T 2002)
More than 95% of anthropogenic emissions of OC are as gas phase compounds
Semivolatile Compounds Dominate Air to Water Fluxes of OC
Emissions
Emissions from Gasoline Combustion
Shauer et al. Environ. Sci. Technol. 40, 1169-1180, 2002.
Semi-Volatile Aliphatic Hydrocarbons in Petroleum(Quantified by GC-MS)
Cn = CnH2n+2
CPI = Odd Cn/Even Cn = 1
RT: 4.00 - 48.00
5 10 15 20 25 30 35 40 45
Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
NL:4.11E7
TIC MS alcanos tirso
Pristano
C13
C11
C14
C12 C33
C17
C34
C35
C36
C32
C30
C31
C29
C23
C24
C25
C26
C27
C28
C21
C20
C22
C16
C18
C19
Fitano
C15
C10
RT: 4.00 - 48.00
5 10 15 20 25 30 35 40 45
Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
NL:4.11E7
TIC MS alcanos tirso
Pristano
C13
C11
C14
C12 C33
C17
C34
C35
C36
C32
C30
C31
C29
C23
C24
C25
C26
C27
C28
C21
C20
C22
C16
C18
C19
Fitano
C15
C10 UCM
The UCM has a toxic effect in marine organisms (Rowland et al. ES&T 2001, Donkin et al. 2003…)
RT: 0.00 - 47.44
0 5 10 15 20 25 30 35 40 45
Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
NL:7.92E7
TIC MS BG_COCA 245G FI
Pristano
C33
C17
C34C35
C36
C32
C30
C31C29C23
C24
C25C26
C27
C28
C21
C20
C22
C16
C18
C19
Fitano
C15
C12 C13
C14
C11
C10
RT: 0.00 - 47.44
0 5 10 15 20 25 30 35 40 45
Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
NL:7.92E7
TIC MS BG_COCA 245G FI
Pristano
C33
C17
C34C35
C36
C32
C30
C31C29C23
C24
C25C26
C27
C28
C21
C20
C22
C16
C18
C19
Fitano
C15
C12 C13
C14
C11
C10
RT: 4.00 - 48.00
5 10 15 20 25 30 35 40 45
Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lativ
e A
bu
nd
an
ce
NL:2.25E7
TIC MS BG_COCA 245A FI 40uL IS
C31
Pristano
C33
C17
C34
C35
C36
C32
C30
C29
C23
C24
C25
C26
C27
C28
C21C20 C22
C16
C18
C19
FitanoC15
RT: 4.00 - 48.00
5 10 15 20 25 30 35 40 45
Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lativ
e A
bu
nd
an
ce
NL:2.25E7
TIC MS BG_COCA 245A FI 40uL IS
C31
Pristano
C33
C17
C34
C35
C36
C32
C30
C29
C23
C24
C25
C26
C27
C28
C21C20 C22
C16
C18
C19
FitanoC15
Aliphatic Hydrocarbons in the NE Atlantic atmosphere
UCM
UCM
Gas Phase --- 312 nmol m-3
CPI =1.2
Aerosol Phase --- 40 nmol m-3
(6% of total AOC)
CPI =1.9
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 CO
X1018 [molecules cm-2]
The anthropogenic chemosphere(from non-combustion sources)
- There are more than 8 millions substances available…
-There are over 200.000 substances registered and in use, most of them in low volume production (less than 1 ton/year).
-The world production of synthetic chemicals is of 3 108 tons y-1 (1993).
The anthropogenic chemosphere(except from combustion sources)
- New chemicals are produced every year
The anthropogenic chemosphere(not including combustion sources)
-About 30.000 chemicals are commercially available and have a production higher than 1 ton/year.
-10000 chemicals have a production higher than 4.5 tons y-1.
- 4000 chemicals have a production higher than 1000 tons y-1.
Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.
The anthropogenic chemosphere, last 30 years(not including combustion sources)
Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.
Risk criteria to identify priority chemicals (PBT chemicals)
- Production volume
- Use profile
- Physical-chemical characteristics: - Persistent- Bioaccumulative- Toxicity- Potential for long range transport.
¿Qué contaminantes orgánicos estudiar?
(Hermens, J.L.M. En Toxicology, Niesink R.J.M. (Editor) CRC Press, New York, 1996)
log KOW
Polychlorinated Dibenzo Dioxins and Furans
(PCDD/Fs)
Cln Clm
O
O
Cln Clm
O
Polychlorinated Biphenyls (PCBs)
Cln Clm
Persistent Organic Pollutants (POPs)
- Used in capacitors and transformers. Other uses in paints, plasticizers, etc.
- Carcinogens. Neurological, reproductive and immune effects.
- By-product of combustion (plastics..)
- Carcinogens.
• Nonylphenols
• Polycyclic Aromatics Hydrocarbons (PAH)
Other POPs ….
- Degradation product of alkylphenol polyethoxylates (industrial surfactants).
- Endocrine disrupter.
- Produced during the incomplete combustion of organic matter (fossil fuels, vegetation ….).
- Some are carcinogens.
Global Distribution of POPs in the atmosphere
Pozo et al. Environ. Sci. Technol. 2006.
PCBs PBDEs
CG
CWCP
CAAir-WaterExchange
Water-Particle Partitioning
Gas-Particle Partitioning
Dry Deposition
Wet Deposition
Vertical Fluxes
Advection
Bioaccumulation
Continental Inputs
Atmospheric Transport
Degradation
Environmental fate of organic pollutants
Major Permanent sinks:
- Ocean interior (sediments, deep waters)
- Atmospheric OH degradation
Persistent Organic Pollutants (POPs)
Multimedia Partitioning of POPs
air
water octanol
eq iA,
eq iO,OA
C C K
eq iw,
eq iO,ow
CC K
eq iw,
eq iA,AW
CC K H=
Off-shore Banyuls sur Mer
Off-shore Barcelona
SW Mediterranean
Sampling Locations Western Mediterranean Sea
Air-Water Exchange and Dry Aerosol Deposition of Nonylphenols to the Western Mediterranean Sea
-30000
-20000
-10000
0
10000
20000
30000
40000
Sep
tem
ber
, 200
1
Mar
ch, 2
002
Jun
e, 2
002
Sep
tem
ber
, 200
1
Mar
ch, 2
002
July
, 200
2
Jun
e, 2
001
Flu
x (
ng
d-1
m-2
)
A-W Exchange Dry Deposition
Of-shore Barcelona
Of-shore Banyuls sur Mer
SW Mediterranean
n.a. n.a.
1/Temp (K-1)
0.0033 0.0034 0.0035 0.0036
-1
0
1
2
Sandy Hook - ENPs
Jun Jul Aug Sep Oct Nov Dec Jan
0
10
20
30
40
Gas Phase
Aerosol Phase
Con
cen
trat
ion
(n
g m
-3)
Log
CG (
ng
m-3)
( Dachs, J., D.A. Van Ry, S.J. Eisenreich. Environ. Sci. Technol., 1999 and 2000.)
Atlantic Ocean
Sandy Hook
Liberty ScienceCenter
Lower Hudson River
Estuary
New York CityJersey City
PA
Paterson
Elizabeth
Newark
30 km
NJ
Long Island
New Brunswick
Atlantic Ocean
Sandy Hook
Liberty ScienceCenter
Lower Hudson River
Estuary
New York CityJersey City
PA
Paterson
Elizabeth
Newark
30 km
NJ
Long Island
Atlantic Ocean
Sandy Hook
Liberty ScienceCenter
Lower Hudson River
Estuary
New York CityJersey City
PA
Paterson
Elizabeth
Newark
30 km
NJ
Long Island
New Brunswick
Atmospheric Occurrence of Nonylphenols Driven by Air-Water Exchange
1/Temp (K-1)
0.0033 0.0034 0.0035 0.0036
-1
0
1
2
Sandy Hook -ENPs
Jun Jul Aug Sep Oct Nov Dec Jan
0
10
20
30
40
Gas Phase
Aerosol Phase
Con
cent
rati
on(n
gm
-3)
Log
CG
( ng
m-3
)
1/Temp (K-1)
0.0033 0.0034 0.0035 0.0036
-1
0
1
2
Sandy Hook -ENPs
Jun Jul Aug Sep Oct Nov Dec Jan
0
10
20
30
40
Gas Phase
Aerosol Phase
Con
cent
rati
on(n
gm
-3)
1/Temp (K-1)
0.0033 0.0034 0.0035 0.0036
-1
0
1
2
Sandy Hook -ENPs
Jun Jul Aug Sep Oct Nov Dec Jan
0
10
20
30
40
Gas Phase
Aerosol Phase
Con
cent
rati
on(n
gm
-3)
Log
CG
( ng
m-3
) Nonylphenols
PCBs
Log Cg = -9135/T + 31.7R2 = 0.88
Atmospheric occurrence of Persistent Organic Pollutants (POPs)
Global distillation of semivolatile organic compounds
(Wania, F. and Mackay, D. , Environ. Sci. Technol. 30, 390A-396A, 1996)
Selective Sequestration of Atmospheric POPs in Sediments from High Mountain
Lakes
(Grimalt et al. Environ. Sci. Technol. 2001)
Inventories in sediments vs. Temperature
Controls on the Sequestration of atmospheric POPs in Sediments from
High Mountain Lakes(Lake Redo, Pyrenees Mountains)
(Meijer, S. et al. J. Geophys. Res.. On revision 2007)
Meltwater input
CWCP
Dry Deposition
Sinking
Ca(gas)Ca(part)
Resuspension
Air-WaterExchange
Diffusion
Wet Deposition (snow / rain)
CS
Burial
Cpore
Uptake
Depuration
Meltwater input
CWCP
Dry Deposition
Sinking
Ca(gas)Ca(part)
Resuspension
Air-WaterExchange
Diffusion
Wet Deposition (snow / rain)
CS
Burial
Cpore
Uptake
Depuration
k’W-Sed/k’W-Air = 2.5
Fluxes in mg y-1
k’W-Sed/k’W-Air = 0.5
Dissolved Phase
[PC
B]
(pg
/L)
0
20
40
60
80
Gaseous Phase
[PC
B]
(pg
/m3)
0
10
20
30
SPM Phase
[PC
B]
(pg
/L)
0
20
40
60
80
Phytoplankton Phase
18
16
+3
23
12
82
24
54
65
2+
43
49
47
+4
84
43
7+
42
41
+7
16
44
07
47
0+
76
66
+9
59
15
6+
60
+8
99
2+
84
10
19
98
39
78
7+
81
85
+1
36
11
0+
77
82
15
11
35
+1
44
+1
47
+1
24
14
9+
12
3+
10
71
18
14
61
53
+1
32
10
51
41
+1
79
16
3+
13
81
58
17
8+
12
91
87
+1
82
18
31
85
17
41
77
20
2+
17
1+
15
61
80
19
91
70
+1
90
20
12
03
+1
96
19
5+
20
81
94
20
6
[PC
B]
(pg
/L)
0
20
40
60
80
Aerosol Phase
[PC
B]
(pg
/m3)
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 PCBsNW Atlantic Ocean
(Yan, et al. Environ. Pollut. 2007)
To which extend atmospheric inputs control water concentrations of POPs?
CWT [ng m-3]
B PCB 180
dept
h [m
]
CWT [ng m-3]
A PCB 28
dept
h [m
]
CWT [ng m-3]
B PCB 180
dept
h [m
]
CWT [ng m-3]
A PCB 28
dept
h [m
]
[ng m-2 s-1]
FSINK PCB 180dept
h [m]
precipitation
* 10-5[ng m-2 s-1]
FSINK PCB 180dept
h [m]
precipitation
* 10-5
PCB 28
(Jurado et al. 2007, Mar. Pollut. Bull 54, 441-451)
Influence of turbulence on water column concentrations and variability
(Example: Adriatic Sea)
Acumulación de contaminantes orgánicosen la vegetación
4
5
6
7
8
9
6 7 8 9 10 11 12 13
log KOA
log
CV/C
G
Maiz
(Böhme et al. Environ. Sci. Technol. 33, 1805-1813, 1999)
PCBsPCDDsPCDFs
La vegetación como filtro de contaminantes
Flujo de deposición en la vegetaciónFlujo de deposición en el suelo
________________________________
F=
(Mclachlan M.S. y M. Horstmann, Environ. Sci. Technol. 32, 413-420, 1998)
Global distribution of PCBs in Soils
Meijer et al. Environ. Sci. Technol. 2003.
Potential Environmental Reservoirs of POPs
(Dalla valle, M., Dachs, J., Sweetman, A.J., Jones, K.C. Global Biogeochem. Cycles 2004.
Dalla valle, M., Jurado, E., Dachs, J., Sweetman, A.J., Jones, K.C. Environ. Pollut. 2005.)
180ºW 135ºW 90ºW 45ºW 0º 45ºE 90ºE 135ºE 180ºE
90ºN
60ºN
30ºN
0º
30ºS
60ºS
90ºS
0 20 40 60 80 100 120 140 160 180 200
Inventory in soil or ocean mixed layer / Inventory in atm boundary layer
PCB 101
0
20000
40000
60000
80000
100000
120000 -9
0-6
0-3
00
30
60
90
La
titu
de
Soil conc (pg/g dry wt)020000
40000
60000
80000
100000
120000
Total PCB usage (tonnes)
Soil Conc (pg g-1)
PCB usage (tn)
(January 2001)
ATSR, ERS-2 (ESA) SeaWIFS (NASA)
[K] [mg m-3]
SST [chl a]
(January 2001)
ATSR, ERS-2 (ESA) SeaWIFS (NASA)
[K] [mg m-3]
(January 2001)
ATSR, ERS-2 (ESA) SeaWIFS (NASA)
[K] [mg m-3]
SST [chl a]
Potential Drivers of Oceanic Sink of POPs
>> cruise data>> cruise data
RRS Bransfield Oct-Dec 1998, Rainer Lohmann PCDD/Fs
RV PELAGIA Jan-Feb 2001Foday Jaward PCBs
GAS: Cg
[fg m-3]0 10 20 30 40 50 60
90ºN
60ºN
30ºN
0º
30ºS
60ºS
90ºS
AEROSOL: Cp
[fg m-3]0 10 20 30 40
90ºN
60ºN
30ºN
0º
30ºS
60ºS
90ºS
(Lohmann et al. EST 2001, Jaward et al. EST 2004)
ClCl55DD atmospheric concentration DD atmospheric concentration
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
90S
180W 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
Climatological and Remote Sensing Data
Pu
GdWWPWP C
kkk
CkF
Water-Phytoplankton Fluxes
uWP kMLDBiomassk
0
0.4
0.8
1.2
1.6
2
22 52 95 99 110 187 174
FS
ink
(ng
m-2
d-1
)
Measured
Predicted
0
2
4
6
8
10
28 52 44 70 101 118 153 138 187 180 170
FS
ink
(ng
m-2
d-1
)
MeasuredPredicted
0
1
2
3
4
28 52 101 118 153 138 180
FS
ink
(ng
m-2
d-1
)
Measured
Predicted
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
360
180W 90W 0 90E 180E
90N
60N
30N
0
30S
60S
90S
ng m-2 d-1
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
360
180W 90W 0 90E 180E
90N
60N
30N
0
30S
60S
90S
ng m-2 d-1
PCB 180
Comparison of Measured and Predicted PCB Sinking FluxesNorth Atlantic Ocean
(Gustafsson et al 1997)
Mediterranean Sea
(Dachs et al 1996)
Arabian Sea
(Dachs et al 1999)
(Dachs et al. Environ Sci. Technol, 2002)
AEROSOLS
DRY DEPOSITIONOF PARTICLES
contaminants associated with particles
VOLATILIZATION
gaseous contaminants
ABSORPTION OF GASES
WATER DROPLETS
WASHOUT OF GASES
WASHOUT OF PARTICLES
Atmospheric Depositional Processes of POPs
0
5
10
15
20
25
30
Cl4DF Cl5DF Cl6DF Cl7DF OCDF Cl4DD Cl5DD Cl6DD Cl7DD OCDD
pg
m-2
d-1
0
100
200
300
400
500
600
PCB28 PCB52 PCB101 PCB118 PCB138 PCB153 PCB180
pg m
-2 d
-1
Wet depositionNet air-water exchange
Dry aerosol deposition
A
B
0
5
10
15
20
25
30
Cl4DF Cl5DF Cl6DF Cl7DF OCDF Cl4DD Cl5DD Cl6DD Cl7DD OCDD
pg
m-2
d-1
0
100
200
300
400
500
600
PCB28 PCB52 PCB101 PCB118 PCB138 PCB153 PCB180
pg m
-2 d
-1
Wet depositionNet air-water exchange
Dry aerosol deposition
A
B
Comparison of Atmospheric Depositional Processes for PCBs and PCDD/Fs
(Atlantic Ocean)
(Jurado et al. Environ. Sci. Technol. 2005)
* In brakets when referred to all the PCBs congeners
3600(1530)(29N, 95WGalveston Bay,
TexasPark et al. 2001
706735 (28N,16E)Izaña, Tenerife,
NE AtlanticVan Drooge 2001
107(820)(35N, 25E)Crete island,
eastern Mediterranean
Mandalakis et al. 2004
130268 (39N, 74WTuckerton, USVan Ry 2002
modelled FWD PCBs[ng m-2 y-1]
measured FWD PCBs[ng m-2 y-1]
(Latitude, Longitude)
LocationName
Source
3600(1530)(29N, 95WGalveston Bay,
TexasPark et al. 2001
706735 (28N,16E)Izaña, Tenerife,
NE AtlanticVan Drooge 2001
107(820)(35N, 25E)Crete island,
eastern Mediterranean
Mandalakis et al. 2004
130268 (39N, 74WTuckerton, USVan Ry 2002
modelled FWD PCBs[ng m-2 y-1]
measured FWD PCBs[ng m-2 y-1]
(Latitude, Longitude)
LocationName
Source
Comparison of Predictions and Measurements of Wet Deposition of POPs
(Lohmann R., Jurado E. Dachs J., Lohmann U. Jones K.C 2006. J. Geophys. Res. DOI 10.1029/2005JD006923)
Global Sinks for atmospheric PCDD/Fs
PCB Cycling Over the Open Atlantic Ocean
Occurrence of Gas Phase PCBs
(Jaward, F. et al. Evidence for dynamic air-water coupling and cycling of POPs over the Atlantic ocean Environ. Sci. Technol. 2004)
POP air-water coupling and cycling in the Open Atlantic Ocean
CGday/CGnight = 0.3kAW + 0.88
R2 = 0.76
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0 1 2 3 4 5
kAW (m d-1)C
Gd
ay/C
Gn
igh
t
Air-water exchange controls the diurnal cycle
Are Atmospheric Diurnal Cycles of PCBs Driven by the Marine Organic Carbon Cycle?
Air-water mass transfer coefficient
0
4
8
12
16
20
-0.7
-3.5
-6.6
-9.6
-12.
6
-15.
5
-18.
2
-20.
8
-26.
4
-30.
5
-32.
0
Latitude
CG
(pg
m-3
)
0.00
5.00
10.00
15.00
20.00
25.00
30.00
PCB 28 PCB 52 PCB 138 Series3
D
D
D
D
D
D
DD
DD
D
N
NNNN
N
NNN N
SST
Diurnal Cycling of Gas Phase PCBs
Persistent Organic Pollutants (POPs)
Sampling Cruise in the NE Atlantic (Off-shore Sahara, May-June 2003)
-26 -24 -22 -20 -18 -16 -14 16
18
20
22
24
26
28
PAHs Along Two East-West Transects
(NE Atlantic)
-26 -24 -22 -20 -18 -16 -14 16
18
20
22
24
26
28
0.00
0.02
0.04
0.06
0.08
1315171921232527
Longitude (W)
CA (
ng
m-3
)
0
2
4
6
8
CG (
ng
m-3
)
Aerosol Phase Gas Phase
0.00
0.03
0.06
0.09
0.12
1315171921232527
Longitude (W)
CA (
ng
m-3
)
0
1
2
3
4
CG (
ng
m-3
)
Aerosol Phase Gas Phase
Phenanthrene
Pyrene
(Del Vento & Dachs ES&T, 2007)
0.00
0.02
0.04
0.06
0.08
1315171921232527
Longitude (W)
CA (
ng
m-3
)
0
2
4
6
8
CG (
ng
m-3
)
Aerosol Phase Gas Phase
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
00.511.522.530.00
0.10
0.20
0.30
0.40
Aerosol
BghiP - North Transect (21ºN)
CG = 8.0481e-0.4055 t
R2 = 0.6716
CA = 0.0617e-0.8683 t
R2 = 0.8617
0
2
4
6
8
00.511.522.53Time (d)
CG (
ng
/m3)
0.00
0.02
0.04
0.06
0.08
0.10
CA (
ng
/m3) Gas
Aerosol
Phenantrene - North Transect (21ºN)
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
00.511.522.530.00
0.10
0.20
0.30
0.40
Aerosol
BghiP - North Transect (21ºN)
CG = 8.0481e-0.4055 t
R2 = 0.6716
CA = 0.0617e-0.8683 t
R2 = 0.8617
0
2
4
6
8
00.511.522.53Time (d)
CG (
ng
/m3)
0.00
0.02
0.04
0.06
0.08
0.10
CA (
ng
/m3) Gas
Aerosol
Phenantrene - North Transect (21ºN)
Atmospheric Residence times of PAHs
The observed atmospheric residence times are 3.5 and 3.7 days for gas and aerosol
phase PAHs
Atmospheric residence time over the ocean(atm. dep + reaction with OH radical)
CA
CWCP
CAPAir-WaterExchange
Dry Deposition
Wet Deposition
ML
D
Sinking Fluxes
CA
CWCP
CAPAir-WaterExchange
Dry Deposition
Wet DepositionDry
Deposition
Wet Deposition
ML
D
Sinking Fluxes
Air-deep water mass transfer coefficient (kADW)
kADW = kAT kSink / (kAT + kSink)
kAT= kAW + k’DD+ k’WD
Then
FAtm-Ocean = kADW CG/H’
Atmospheric Residence Time of POPs
τ = inventory/net output = 1 / (rdeg + rADW)
PCB 180 as example
Role of the Biological Pump and Temp.(air-deep water mass transfer coef.)
CA
CWCP
CAPAir-WaterExchange
Dry Deposition
Wet Deposition
ML
D
Sinking Fluxes
CA
CWCP
CAPAir-WaterExchange
Dry Deposition
Wet DepositionDry
Deposition
Wet Deposition
ML
D
Sinking Fluxes
Role of precipitation intensity
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
Atmospheric Residence times
(Jurado 2006)
How pollutants reach the Arctic and Antarctica?
Wania & Mackay 1996
How pollutants reach the Arctic and Antarctica?
Atmospheric Concentrations of PCBs(june-july 2005)
(Gioia et al. 2008)
How pollutants reach the Arctic and Antarctica?
Air-water gradient of PCB fugacity
(Gioia et al. 2008)
Is the Formation of Deep Oceanic Water a Sink of POPs
Formation of Deep Oceanic Water as a Sink of POPs
Lohmann R., Jurado E. Pilson M. , Dachs, J. 2006. Geophys. Res. Lett. DOI 10.1029/2006GL025953.
Clobal Change and POPs in the Arctic
(MacDonald et al. Sci. Total Environ. 2005)
Case Study: POPs in the Arctic
- MacDonald and coworkers have published the first comprehensive study on the implications of climate change on POP cycling and impact. This will modify:
- Atmospheric inputs of POPs/pesticides - Atmosphere-ocean gas exchange and delivery of ice-cover content
of POPs- Riverine inputs- Chemical partitioning and degradation of POPs.
- These changes are also linked to:- Altered food web structure- Food deprivation or shifts in diet- Altered migration pathways and invading species
-The literature suggests that there is a dynamic link between organochlorine compounds and disease and epidemics in wildlife arctic populations.
The anthropogenic chemosphere, last 30 years(except from combustion sources)
Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.
Persistent Organic Pollutants
Production and occurrence of Legacy POPs
Lohmann, R., Breivik, K., Dachs, J., Muir, D. 2007, Environ. Pollut. In press.
Production and Occurrence of Emerging POPs
Potential POPs
Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.
The anthropogenic chemosphere, last 30 years(except from combustion sources)
Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.
Potential POPs
Bioaccumulative and Persistent
Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.
Potential POPs: Bioaccumulative and Persistent and with long-range transport potential
Muir & Howard. Environ. Sci. Technol. 40, 7157-7166, 2006.
POPs in the global environment
- The potential for sintetic compounds to become global pollutants is a function of their physical chemical properties and toxicity.
-Carbon cycle and temperature are important variables controlling global distribution of POPs
-Atmospheric transport is important for legacy POPs while oceanic transport is important for many emerging POPs.
- Only the environmental fate and impact of few pollutants is know. Difficult to get the key information from other chemicals.
-The organic fraction of the chemosphere is largely uncharacterized.
- Since the different vectors of global change (climatic, biodiversity, hydrologic cycle…) will modify the ecosystem functioning, the fate and impact fo POPs will also be modified under a global change scenario…
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