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