1

DAUREDiscriminación del origen de Aerosoles Urbanos y REgionales en el NE de la Península Ibérica

Identification of the origin of atmospheric aerosols in NE Iberian Peninsula

CSIC, 2nd March 2009 Xavier.querol@ija.csic.es

Querol X., Alastuey A., Pandolfi M., Pey J., Moreno T., Viana M., Amato F., Pérez N., Cusack M., Reche C., Moreno N.

1Instituto de Diagnóstico Ambiental y Estudios sobre Agua, IDÆA CSIC, Barcelona

Objectives• Origin of carbonaceous aerosols winter/summer• Exportation of urban aerosols• Origin of mineral dust

BARCELONABARCELONA

KERB SIDE SITE(T)

60

5045

URBAN BACKGROND (UB)

40

PM10

(µg/

m3 )

REGIONAL BACKGROUND (RB)

15

CONTINENTAL BACKGROOUND (CB)8

SITES

2

http://w3.bcn.es/fitxers/mobilitat/dadesbasiques2006.222.pdf

0

500

1000

1500

2000

2500

Lond

res 20

01

Roma 2

002

Madrid

2005

Berlín

2006

Milán 20

02

Munich

2005

Viena 2

004

Barcelo

na 20

06

Budap

est 20

05

Praga 2

004

Valenc

ia 200

6

Frank

furt 2

005

Estoco

lmo 200

6

Ámsterda

m 2006

Bolonia

2005

Helsink

i 200

4

Oslo 20

05

Copen

hagu

e 200

5

Turismos (x1000)

617

2379

139

1398

359

7971226

Very high density (cars/km2)

Cars (x1000)

0

1

2

3

4

5

6

7

Barcelo

na 20

06

Milán 20

02

Valenc

ia 200

6

Madrid

2005

Munich

2005

Copen

hagu

e 200

5

Viena 2

004

Lond

res 20

01

Roma 2

002

Berlín

2006

Bolonia

2005

Estoco

lmo 200

6

Frank

furt 2

005

Praga 2

004

Budap

est 20

05

Helsink

i 200

4

Ámsterda

m 2006

Oslo 20

05

Turismos/Km2 (x1000) 6.1

2.6 2.3

1.4

1.0 0.4

Cars/km2 (x1000)

160000 vehicles/day

100000 vehicles/day

From 20000 to 80000 veh/day

3

192 m

420 m

Llobregat Besos

Airport Port

Topography exaggerated x 10

NO3- (µg/m3) PM10Thermal instability of

NH4NO3 along the year

J F M A M J J A S O N D

Seasonal trend<11-22-33-44-5>5

NH4NO3 Major specie (excluding Canary Isl.)

NaNO3

Ca(NO3)2

EMEP

4

nmSO42- (µg/m3) PM10External origin

J F M A M J J A S O N D

Seasonal trend

2.5

<33-44-55-66-7

(NH4)2SO4 Major specie

Na2SO4

CaSO4

EMEP

OM+EC (µg/m3) PM10Maximal dispersion, Trade winds

No local C sources

J F M A M J J A S O N D

Seasonal trend

<33-55-77-1010-1515-18

5

Mineral matter (µg/m3) PM10

J F M A M J J A S O N D

Seasonal trend

African contribution

Low re-suspension

Influence from Traffic

Influence from Traffic

<33-55-77-1010-1515-18>18

unnacountedmetalsOC+ECmarinemineralNH4+NO3-nmSO42-

µg/m

3

PM10/PM2.5

Las Palmas48/18 µg/m3

Barcelona47/28 µg/m3

Llodio33/24 µg/m3

Bemantes19/14 µg/m3

Alcobendas29/17 µg/m3

Huelva36/19 µg/m3

Wien (4)53/38 µg/m3

Illmitz (4)24/20 µg/m3

Berlin (5)40/26 µg/m3

Berlin (5)29/22 µg/m3

Helsinki (1)25/12 µg/m3

Helsinki (1)14/8 µg/m3

Basel (9)28/- µg/m3

Kerbside station

Urban background

Rural background

Sweden(3)10 µg/m3

Krakow (2)100 µg/m3

22/14

25/20 30/20

UK (7) 25/16

UK (7) 35/24

Gent (8) 24/19

Milano (10)--/47

1. Pakkanen et al., (2001)2. Marelli et al., 2006; Putaud et al., 20063. EC, 20044. EC, 20045. Abraham et al., 20016. Visser et al., 20017. EC, 20048. Viana et al., 2006a9. Röösli et al., 200110. Rodriguez et al., 200711. Perrino and Allegrini, 200612. Querol et al., 2004

TheNetherlands

(6)

Spain(12)

Roma (11)

28/-

37/-

48/-

6

Obras

Salida Puerto

Ronda de Dalt

Ronda Litoral

Plaça Cerdá

Meridiana

3-9 mg/m2

10-20 mg/m2

21-40 mg/m2

41-80 mg/m2

>81 mg/m2

Masa PM10

3-9 mg/m2

10-20 mg/m2

21-40 mg/m2

41-80 mg/m2

>81 mg/m2

Masa PM10

Av. Diagonal

Centre City C4

0.01

0.10

1.00

10.00

100.00

OC EC

CO

3=A

l2O Ca K Fe P S

SON

O3-

NH

4+ Ti V Cr

Mn

Co

Ni

Cu Zn A

s

Rb

Sr Zr

Mo

C

d S

n S

b Ba Pb

Mas

s pe

rcen

t

PARTPARTÍÍCULAS RESUSPENSICULAS RESUSPENSIÓÓN FIRME N FIRME RODADURARODADURA

Fuente: Tesis doctoral F. AmatoCSIC-IJA

Obras

Salida Puerto

Ronda de Dalt

Ronda Litoral

Plaza Cerdà

Meridiana

Sb ( µg/g PM10)

Sb (µg/ g P M 10)

0

20

40

60

80

100

120

140

1

Av. Diagonal

Fuente: Tesis doctoral F. AmatoCSIC-IJA

7

AFRICAN DUST CONTRIBUTIONS: ANNUAL PMAFRICAN DUST CONTRIBUTIONS: ANNUAL PM1010 LEVELSLEVELS

Barcarrota

Campisábalos

OSaviñao

Peñausende

Zarra

Risco Llano

Niembro

Torms

Cabo de Creus

Tenerife (El Río, Arinaga, Buzanada, Sardina)

Níjar

Bellver

Valderejo

Sierra Norte

Montseny

Monagrega

Izki

Morella

MundakaPagoeta

OloLamas de

Alcoutim

Monfragüe

Barcarrota

Campisábalos

OSaviñao

Peñausende

Zarra

Risco Llano

Niembro

Torms

Cabo de Creus

Tenerife (El Río, , Buzanada, Sardina)

Níjar

Bellver

Valderejo

Sierra Norte

Montseny

Monagrega

Izki

Morella

MundakaPagoeta

OloLamas de

Alcoutim

Monfragüe

7-6 µg/m3 PM10 on an annual basis6-5 µg/m3 PM10 on an annual basis5-4 µg/m3 PM10 on an annual basis4-3 µg/m3 PM10 on an annual basis3-2 µg/m3 PM10 on an annual basis2-1 µg/m3 PM10 on an annual basis

Víznar

Arinaga

Marine aerosol (µg/m3) PM10

Na+

Cl-J F M A M J J A S O N D

Seasonal trend

Constant inputs and insolation

<11-22-33-55-1010-12

8

Fuel oil, 1.5, 3%Marino, 3.5, 8%

Industrial, 1.0, 2% Intrusión

Sahariana, 1.5, 3% Motores, 9.0,

20%

Sulfatos, 7.9, 18%

Nitratos , 4.9, 11%

Road dust, 6.7, 15%

Mineral, 8.8, 20%

PM10

Mineral, 2.9, 10%

Road dust, 2.2, 8%

Nitratos , 4.3, 15%

Sulfatos, 7.8, 27%

Motores, 8.0, 27%

Intrusión Sahariana, 0.9,

3%

Industrial, 0.9, 3%

Marino, 0.9, 3%

Fuel oil, 1.3, 4%

PM2.5

Fuel oil, 0.9, 5%

Marino, 0.1, 1%

Industrial, 0.5, 3% Intrusión

Sahariana, 0.3, 2%

Motores, 6.3, 35%

Sulfatos, 6.1, 34%

Nitratos , 3.0, 17%

Road dust, 0.3, 2%Mineral, 0.2, 1%

PM1

Traffic: 43%

Traffic: 46% Traffic: 50%

Max.Shipping: 3%

Max.Shipping: 5%

Max.Shipping: 4%

Demolition-resuspension (reg.): 10% Demolition-resuspension (reg.):

Dem.-res. (reg.): 20%

Fuente: Tesis doctoralF. Amato CSIC-IJA

ME2: Source apportionment in Barcelona

Barcelona

Montseny

PM10, PM2.5 and PM1

Mean daily cycles

1015202530354045505560

0 1 2 3 4 5 6 7 8 9 1011121314151617181920212223Hora (GMT)

Winter

8

13

18

23

0 1 2 3 4 5 6 7 8 9 1011121314151617181920212223Hora (GMT)

Summer

8101214161820222426

0 1 2 3 4 5 6 7 8 9 1011121314151617181920212223Hora (GMT)

PM10 PM2.5 PM1

µg/m

3

µg/m

3µg

/m3

9

0

10

20

30

40

50

60

70

80

90

100

01 04 07 10 01 04 07 10 01 04 07 10 01 04 07 10 01 04 07 10 01 04 07 10 01 04 07 10

PM

(µg/

m3 )

NAF PM10 PM2.5 PM1

2003 2004 2005 2006 20072002 2008

0

5

10

15

20

25

30

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

µg/m

3

PM1 PM1-2.5 PM2.5-10

THr, P

HWinter Episodes

MNY

BCN

THr, P

MNY

BCN

H

PM1

PM1

0

20

40

60

80

100

01/02 02/02 03/02 04/02 05/02 06/02 07/02 08/02 09/02 10/02 11/02 12/02 13/02 14/02 15/02 16/02

PM10 PM2.5 PM1

AA

Anticyclonic situation

µg/m

3

10

PM10 16.2 µg/m3

Crustal; 4,1; 24%

OM; 3,4; 21%

NH4+; 0,9; 6%

NO3-; 1,7; 11%

SO42-; 2,6; 16%

Unaccounted; 2,9; 18%

EC; 0,2; 1%Sea Spray; 0,5; 3%

PM2.5 13.6 µg/m3

Crustal; 1,3; 9%

OM; 3,5; 27%

EC; 0,2; 1%

Sea Spray; 0,2; 2%

Unaccounted; 3,4; 25%

SO42-; 2,8; 20%

NO3-; 1,2; 8%

NH4+; 1,2; 8%

0

2

4

6

8

10

12

14

16

03/2

002

05/2

002

07/2

002

09/2

002

11/2

002

01/2

003

03/2

003

05/2

003

07/2

003

09/2

003

11/2

003

01/2

004

03/2

004

05/2

004

07/2

004

09/2

004

11/2

004

01/2

005

03/2

005

05/2

005

07/2

005

09/2

005

11/2

005

01/2

006

03/2

006

05/2

006

07/2

006

09/2

006

11/2

006

01/2

007

03/2

007

05/2

007

07/2

007

09/2

007

11/2

007

µg/m

3

SO42- NO3-

PM2.5

K%

0

10

20

30

40

50

60

03/2

002

05/2

002

07/2

002

09/2

002

11/2

002

01/2

003

03/2

003

05/2

003

07/2

003

09/2

003

11/2

003

01/2

004

03/2

004

05/2

004

07/2

004

09/2

004

11/2

004

01/2

005

03/2

005

05/2

005

07/2

005

09/2

005

11/2

005

01/2

006

03/2

006

05/2

006

07/2

006

09/2

006

11/2

006

01/2

007

03/2

007

05/2

007

07/2

007

09/2

007

11/2

007

% K

/ cr

usta

l mas

s

K%

PM2.5

0

1

2

3

4

5

6

7

8

03/2

002

05/2

002

07/2

002

09/2

002

11/2

002

01/2

003

03/2

003

05/2

003

07/2

003

09/2

003

11/2

003

01/2

004

03/2

004

05/2

004

07/2

004

09/2

004

11/2

004

01/2

005

03/2

005

05/2

005

07/2

005

09/2

005

11/2

005

01/2

006

03/2

006

05/2

006

07/2

006

09/2

006

11/2

006

01/2

007

03/2

007

05/2

007

07/2

007

09/2

007

11/2

007

µg/m

3

OC+EC NH4+ Sea spray

PM2.5

0

1

2

3

03/2

002

05/2

002

07/2

002

09/2

002

11/2

002

01/2

003

03/2

003

05/2

003

07/2

003

09/2

003

11/2

003

01/2

004

03/2

004

05/2

004

07/2

004

09/2

004

11/2

004

01/2

005

03/2

005

05/2

005

07/2

005

09/2

005

11/2

005

01/2

006

03/2

006

05/2

006

07/2

006

09/2

006

11/2

006

01/2

007

03/2

007

05/2

007

07/2

007

09/2

007

11/2

007

µg/m

3

Al2O3 Ca Fe

PM2.5

0

10

20

30

40

50

60

70

03/2

002

05/2

002

07/2

002

09/2

002

11/2

002

01/2

003

03/2

003

05/2

003

07/2

003

09/2

003

11/2

003

01/2

004

03/2

004

05/2

004

07/2

004

09/2

004

11/2

004

01/2

005

03/2

005

05/2

005

07/2

005

09/2

005

11/2

005

01/2

006

03/2

006

05/2

006

07/2

006

09/2

006

11/2

006

01/2

007

03/2

007

05/2

007

07/2

007

09/2

007

11/2

007

ng/m

3

Ti P

PM2.5

02468

101214

1618

03/2

002

05/2

002

07/2

002

09/2

002

11/2

002

01/2

003

03/2

003

05/2

003

07/2

003

09/2

003

11/2

003

01/2

004

03/2

004

05/2

004

07/2

004

09/2

004

11/2

004

01/2

005

03/2

005

05/2

005

07/2

005

09/2

005

11/2

005

01/2

006

03/2

006

05/2

006

07/2

006

09/2

006

11/2

006

01/2

007

03/2

007

05/2

007

07/2

007

09/2

007

11/2

007

ng/m

3

Pb V

PM2.5

11

0

20

40

60

80

PM10

(µg/

m3 )

PM10 Moving average PM10 ATL NAF MED EU REG ANTPM10 PM10

Montseny 2004

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

Very important to repeat measurements in summer: totally different conditions

Instrumentation: MSY-1

Optical counter PM10, PM2.5, PM1 (hourly)

Hivol PM10, PM2.5, PM1 (12-h, 9-21 and 21-9 GMT)

Low vol PM2.5 for additional OC and EC (24-h)

SMPS

MAAP: AC

O3, SO2, CO, NOx

Meteorology

12

Instrumentation: BCN-1

Optical counter PM10, PM2.5, PM1 (hourly)

Hivol PM10, PM2.5, PM1 (12-h, 9-21 and 21-9 GMT)

Low vol PM2.5 for additional OC and EC (24-h)

CPC

MAAP: AC

O3, SO2, CO, Nox (Department of the Environment)

Meteorology (Faculty of Physics, J. Lorente)

Glories

Av. Diag

onal

Av. Meridiana

010

2030

4050

600 15 30

45

60

75

90

105

120

135

150165

180195210225

240

255

270

285

300

315330

345

WashWash out out ofof pavementpavement toto abate abate roadroad dustdust

c/ V

alen

cia

13

Leaching

IC:

NO3-, Cl-, SO4

2-

Selective electr.

NH4+

HF:HNO3:HClO4digestion

ICP-AES:Al, Ca, K, Na, Mg, Fe, Ti, P

ICP-MS:Li, Ti, V, Cr, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Y, Zr, Cd, Sn, Cs, Ba, La, Ce, Pr, Nd, Hf, Tl, Pb, Bi, Th, U

OC+EC

Suma de componentes: 75-85% PM

Chemical analysis

Thermo-Optical, alsowith Partisol

(denuder+back filter)

ICP-AES

Ca2+, K+, Na+

Mg2+, Fe2+,Mn2+

Modified from Schauer et al. (2006)

ChemicalMass

Balance

Receptor modelsXt = Λ ft + et

p x 1 p x k k x 1 p x 1

Little Complete

MultivariateModels

Knowledge required about pollution sourcesprior to receptor modelling

Exploratory Factor Analysis Models

UNMIX

Regression Models

BayesianModels

Measurement Error Models

Confirmatory Factor Analysis Models

PMFPCACMB

COPREMME

Receptor modelling

14

Enjoy nature more.xavier.querol@ija.csic.es

Thanks:

Department of the Environment, Ministry of Science and Innovation