perturbaciones antropogénicas de la quimiosfera orgánica: implicaciones a escala global

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

ura

ted

cy

clo

alk

anes

Bra

nch

ed a

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es

Un

satu

rate

d c

yclo

alk

enes

Alk

yn

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Mo

no

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ic h

ydro

ca

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ns

Eth

ers

Alip

ha

tic

ald

eh

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es (

>c8

)

Alip

ha

tic

ald

eh

yd

es (

c3-7

)

Ace

tald

ehy

de

2-3

rin

g P

AH

s

Aro

ma

tic

ald

eh

yd

es

Ole

fin

ic a

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s

UC

M 2

Tri

cyc

lic

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es

Alip

ha

tic

Ket

on

es

Aro

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tic

ket

on

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

he

d a

lka

ne

s

Alk

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UC

M 1

n-A

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s

Sa

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Alk

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ca

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ns

Eth

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Ali

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c a

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s (

>c

8)

Ali

ph

ati

c a

lde

hy

de

s (

c3

-7)

Ac

eta

lde

hy

de

2-3

rin

g P

AH

s

Aro

ma

tic

ald

eh

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es

Ole

fin

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hy

de

s

UC

M 2

Tri

cy

cli

c t

erp

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Ali

ph

ati

c K

eto

ne

s

Aro

ma

tic

ke

ton

es

n-A

lka

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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s

Sa

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Bra

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Eth

ers

Ali

ph

ati

c a

lde

hy

de

s (

>c

8)

Ali

ph

ati

c a

lde

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de

s (

c3

-7)

Ac

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lde

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de

2-3

rin

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AH

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Ole

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Ali

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ic a

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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

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40

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60

65

70

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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

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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)


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


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


Lower Hudson River

Estuary


PA

Paterson

Elizabeth

Newark

30 km

NJ

Long Island

Atlantic Ocean

Sandy Hook


Lower Hudson River

Estuary


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


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


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


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)


[K] [mg m-3]

(January 2001)


[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

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

)


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

)


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


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


Dry Deposition

Wet Deposition

ML

D

Sinking Fluxes

CA

CWCP


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


Atmospheric Concentrations of PCBs(june-july 2005)

(Gioia et al. 2008)


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)


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


The anthropogenic chemosphere, last 30 years(except from combustion sources)


Potential POPs

Bioaccumulative and Persistent


Potential POPs: Bioaccumulative and Persistent and with long-range transport potential


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…

perturbaciones antropogénicas de la quimiosfera orgánica: implicaciones a escala global

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