Crustal

Regional(SIC)

TrafficMarine

Not det.

Industrial

Burgos

Las Palmas

Urban background and traffic hotspots•High traffic: 30-48%•High crustal (mixture of sources!!!!!!)•High marine aerosol (Canary Isl.)•High proportion also of regional-industrial

Madrid

Alcobendas

Badajoz

Palma

Huelva

Urban-industrial Background•High industrial load (30% in most 15-44)•High crustal (mixture of sources!!!!!!)•Low regional due to mixing with local

Puertollano

Barcelona

Carta. Bast.

L’Hospitalet

Tarragona

Llodio

Carta. S. A.

Los Barrios

Algeciras

PM10

Regional Background•High undetermined (H2O) in remote sites•High crustal in E & S•Problem of origin of regional (SIC)

Montseny

Izaña

BemantesMonagrega

unnacountedmetalsOC+ECmarinemineralNH4+NO3-nmSO42- 10

20

30

40

50

60

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

Wien53/38 µg/m3

Illmitz24/20 µg/m3

Berlin40/26 µg/m3

Berlin29/22 µg/m3

Helsinki25/12 µg/m3

Helsinki14/8 µg/m3

Basel28/- µg/m3

Kerbside station

Urban background

Rural background

)

Wien: Schneider (2002)Berlin: Abraham (2001)Helsinki: Pakkanen et al., (2001)Basel: Röösli et al. (2001)

Diferenciación climática: El mismo volumen de emisión puede tenerun mayor efecto, sobretodo en resuspensión productos abrasión tráfico

JJ FD M A M J A S O N D2004

J FN MM J J A S OA D20052004

0

10

20

µg/m

3

Mineral dust Mineral dustMineral dust

African dust events

African dustevents

JJ F M A J A S O N D2004

MD

0

25

50

75

100

µg/m

3

SO 4=+ NO 3

- +NH 4+SO 4

=+ NO 3- +NH 4

+SO 4=+ NO 3

- +NH 4+

0

50

100

150

µg/m

3

BARCELONA LONDONMILANPM2.5PM2.5PM2.5

0

25

50

75

µg/m

3

OM + BCOM + BC OM + BC

0

1

2

3

4

5µg

/m3

Sea saltSea saltSea salt

0.0

0.2

0.4

0.6

µg/m

3

Cr+Cu+Pb+V+Zn+Co+As+CdCr+Cu+Pb+V+Zn+Co+As+CdCr+Cu+Pb+V+Zn+Co+As+Cd

Rodríguez S., Van Dingenen R., Putaud J.P., Dell’Acqua A., Querol X., Alastuey A., Pey J. Chenery S., Harrison R.M., Ho Kin Fai1, Institute of Earth Science “Jaume Almera”, CSIC, Barcelona, Spain.

2, Joint Research Centre of the European Commission, Ispra, Italy.

3, Natural Environmental Research Council (NERC), Keyworth-Nottingham, UK.

4, University of Birmingham

(In preparation)

PM2.5

ng/m 3 Fondo rural Fondo urbano Acero Acero

inoxidableMetalurgia del cobre Petroquím ica Cerám ica

m in m ax m in m ax m edia m edia M edia m in m ax m in m ax

Li 0.1 0.3 0.2 0.7 0.4 0.6 0.2 0.2 1.0 0.6 1.3 Be 0.01 0.02 0.02 0.05 0.06 0.03 0.07 0.01 0.07 0.02 0.05 Sc 0.1 0.1 0.1 0.3 0.1 0.2 0.1 0.1 0.3 0.3 0.5 T i 7 22 18 83 24 36 60 23 62 33 57 V 2 5 2 15 8 28 7 7 25 4 5 Cr 1 2 2 8 25 24 2 2 6 3 8 Mn 5 5 4 23 87 17 11 8 11 6 8 Co 0.1 0.1 0.2 0.5 0.5 0.6 0.4 0.2 0.8 0.4 0.7 N i 2 3 2 7 33 20 3 3 11 3 5 Cu 4 8 7 81 33 11 70 23 33 4 10 Zn 16 30 14 106 417 73 51 35 54 45 183 Ga 0.1 0.2 0.1 0.3 0.4 0.2 0.3 0.2 0.4 0.2 0.3 Ge 0.1 0.3 0.04 0.3 0.2 0.3 0.1 0.1 0.2 0.03 0.1 As 0.3 0.4 0.3 1.5 1.8 0.9 5 0.5 1.9 1.7 5 Se 0.3 0.5 0.3 1.1 3 0.8 1.5 0.5 0.6 1.0 3 Rb 0.5 0.6 0.5 1.8 1.1 0.8 1.5 0.6 1.6 1.2 2.4 S r 1 5 3 10 3 6 4 4 5 3 5 Y 0.1 0.1 0.1 0.4 0.1 0.3 0.3 0.1 0.3 0.2 0.3 Zr 4 4 2 10 2 5 2 2 6 10 20 Nb 0.04 0.1 0.05 0.4 0.1 0.2 0.2 0.1 0.3 0.2 0.3 Mo 2 3 2 5 15 15 2 2 7 1 2 Cd 0.2 0.2 0.1 0.7 1.2 0.3 0.8 0.1 0.8 0.6 1.5 Sn 1 2 1 6 38 1 2 2 2 1 1 Sb 0.6 0.6 1 11 4 1 3 1 7 1 6 Cs 0.01 0.04 0.03 0.13 0.1 0.1 0.1 0.04 0.2 0.1 0.3 Ba 5 11 4 41 14 15 16 12 16 12 16 La 0.1 0.2 0.2 0.6 0.3 0.6 0.5 0.3 0.9 0.3 0.6 Ce 0.2 0.4 0.4 1.3 0.4 0.7 0.9 0.5 1.2 0.7 1.9 P r 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.1 0.2 Hf 0.1 0.2 0.1 0.3 0.1 0.2 0.2 0.1 0.2 0.2 0.4 W 0.01 0.03 0.05 0.6 0.7 0.2 0.06 0.04 0.2 0.10 0.3 T l 0.1 0.1 0.05 0.4 0.3 0.0 0.2 0.03 0.3 0.5 2.8 Pb 5 10 7 57 102 13 37 8 37 35 103 Bi 0.1 0.1 0.1 1.0 0.5 0.1 1.6 0.1 0.2 0.4 1.5 Th 0.1 0.2 0.1 0.3 0.1 0.1 0.4 0.1 0.4 0.1 0.2 U 0.1 0.2 0.1 0.3 0.3 0.1 0.3 0.1 0.3 0.1 0.1

Niveles medios anuales

elementos trazaen PM10

28 emplazamientos en España1999-2005

(ng/m3)Valores objetivo

As 6 ng/m3

Cd 5 ng/m3

Ni 20 ng/m3

Valor límitePb 500 ng/m3

Valores guia OMSMn 150 ng/m3 anualV 1000 ng/m3 diario

Li Cd W La Nd Co Nb Y Tl U Ga Th Sc Hf Pr Cs Be

Zn Ti Cu Pb Ba Mn V Sb Cr Ni Sr Sn Zr Mo Rb As Ce Se Bi

1

10

100

1000

ng/m

3

0.01

0.1

1

10

ng/m

3

0.01

0.1

0.001Li Cd W La Nd Co Nb Y Tl U Ga Th Sc Hf Pr Cs Be

Zn Ti Cu Pb Ba Mn V Sb Cr Ni Sr Sn Zr Mo Rb As Ce Se Bi

1

10

100

1000

0.01

0.1

1

10

0.01

0.1

0.001Li Cd W La Nd Co Nb Y Tl U Ga Th Sc Hf Pr Cs Be

Zn Ti Cu Pb Ba Mn V Sb Cr Ni Sr Sn Zr Mo Rb As Ce Se Bi

1

10

100

1000

ng/m

3

0.01

0.1

1

10

ng/m

3

0.01

0.1

0.001Li Cd W La Nd Co Nb Y Tl U Ga Th Sc Hf Pr Cs Be

Zn Ti Cu Pb Ba Mn V Sb Cr Ni Sr Sn Zr Mo Rb As Ce Se Bi

1

10

100

1000

0.01

0.1

1

10

0.01

0.1

0.001

Fondo rural Fondo urbano

Fondo rural Fondo urbano

Rango en áreas de fondo urbano España

Metalurgia: La Línea 2004-2005Acerías: Llodio 2001

1

10

100

1000

Zn Ti Cu Pb Ba Mn V Sb Cr Ni Sr Sn Zr Mo Rb As Ce Se Bing

/m3

1

10

Li Cd W La Nd Co Nb Y Tl U Ga Th Sc Hf Pr Cs Be

ng/m

3

Zn Pb MnCr Ni Sn

Mo

Se

V

CdGa

0.01

0.1

0.001

0.01

0.1

As

Metalurgia-Cu: Huelva 2001Metalurgia-Zn: Cartagena 2004

7. No se prevén problemas de incumplimientos de los valores límite y objetivo de metales, excepto en zonas industriales muy concretas.

6. Es importante controlar las emisiones de NH3 (agropecauarias principalmente) para disminuir la fracción SIC de PM.

5. Fuera de estos núcleos las actuaciones (tecnológicas y no tecnológicas) sobre tráfico rodado son clave para la mejora de calidad del aire, aunque las reducciones de los volúmenes de emisión a escala global sean menos relevantes que las de otros sectores.

4. Existen hotspots industriales aislados con mucha carga industrial (hasta 45% PM10).

3. Mayoría de ambientes urbanos: Contribuciones directas del tráfico: 30-48% de PM10 (sin incluir SIA del tráfico). Industrial 15-30%. Aerosol marino natural: 3-5% (z. continentales), 5-10% (costeras), hasta 30-35% (Canarias).

CONCLUSIONES

2. El valor límite diario de PM10 se incumple con mucha frecuencia, incluso en zonas que cumplen en valor límite anual. El valor límite diario es mucho más estricto, y de muy difícil cumplimiento en estaciones hotspot.

1. Se registran incumplimientos de los valores límite y objetivo de PM10 y PM2.5, sobretodo en estaciones de tráfico, aunque existen zonas de fondo industrial que también registran superaciones.

8. Se dispone de listados de rangos de concentración de elementos traza para diferentes tipos de ambientes rurales, urbanos e industriales. Ello es una herramienta clave para definir valores objetivo de elementos de importancia ambiental (Cu, Zn, Se, Mo, V, ..) no legislados.

9. Se ha propuesto, y consensuado con las CCAA, un método para detectar y descontar contribuciones naturales. Se alerta desde Febrero de 2004 y se realizan informes anuales desde 2001

Natural episodesNatural episodes

1999/30/EC, Article 2: 15. ‘natural events' shall mean volcanic eruptions, seismic activities, geothermal activities, wild-land fires, high-wind events or the atmospheric resuspension or transport of natural particles from dry regions;

Draft New CAFE Directive, Article 2: (15) "contributions from natural sources" shall mean emissions of pollutants not caused directly or indirectly by human activities, including natural events such asvolcanic eruptions, seismic activities, geothermal activities, wild-land fires, high-wind events, sea sprays or the atmospheric resuspensionor transport of natural particles from dry regions;

EMEP station with gravimetric measurements

Barcarrota

Campisábalos

OSaviñao

Peñausende

EMEP stations with real time measurements

Zarra

M adeira

Canarias

NW

W

NNE

SESW

BalearesCentro

Levante

M adeira

Canarias

NW

W

NNE

SESW

BalearesCentro

Levante

Riscollano

Niembro

Torms

Cabo de Creus

Viznar

Other than EMEP

Tenerife (El Río, Arinaga)

Nijar

Bellver

Valderejo

Huelva Alcornocales

Sierra Norte

MontsenyMonagrega

Los Tojos Izki

Morella

MundakaPagoeta

Olo

(Quinta da Magnolia)Madeira

Regional background stations from Portugal with real-time measurements

Lamas de

Fundão

Chamusca

Alcoutim

Zones and monitoring networkZones and monitoring network

List of episodesList of episodes

Risco Llano EMEP

0

10

20

30

40

50

60

70

80

90

100

01/0

1

03/0

1

05/0

1

07/0

1

09/0

1

11/0

1

01/0

2

03/0

2

05/0

2

07/0

2

09/0

2

11/0

2

01/0

3

03/0

3

05/0

3

07/0

3

09/0

3

11/0

3

µg/m

3 PM

10

Atlantic advection Mobile m ean for ATL Mobile 30 percentile African episodes

0

5

10

15

20

25

30

35

40

45

01/01

/0802

/01/08

03/01

/0804

/01/08

05/01

/0806

/01/08

07/01

/0808

/01/08

09/01

/0810

/01/08

11/01

/0812

/01/08

13/01

/0814

/01/08

15/01

/0816

/01/08

PM10

µg/

m3

,

background before and after10 µg/m3

daily values during thedust outbreak

41 µg/m3

'net dust load'31 µg/m3

PM10 levels in Regional background stations SW Spain, and S Portugal Net dust contributions to be subtractedEspaña FR España EMEP España FR Portugal FR Sierra Norte Barcarrota Doñana Alcoutim

Sierra Norte Barcarrota Doñana Alcoutim01/03/2005 7 6 6 602/03/2005 9 9 12 1403/03/2005 9 8 16 1004/03/2005 7 9 9 1405/03/2005 12 10 8 1106/03/2005 11 8 7 1007/03/2005 11 9 8 1508/03/2005 14 16 1709/03/2005 14 18 15 1810/03/2005 16 18 2111/03/2005 17 22 34 41 6 12 25 3112/03/2005 59 54 56 15 48 44 45 513/03/2005 31 13 22 9 2114/03/2005 11 10 20 21 015/03/2005 25 27 24 56 14 17 11 4216/03/2005 34 48 40 44 23 38 25 3017/03/2005 32 47 31 52 21 37 15 3818/03/2005 36 55 38 73 24 45 23 5819/03/2005 86 181 60 128 75 171 45 11320/03/2005 114 96 86 32 103 76 71 1821/03/2005 96 21 21 15 85 11 5 022/03/2005 11 11 923/03/2005 12 724/03/2005 8 1025/03/2005 12 1026/03/2005 11 1727/03/2005 13 1428/03/2005 14 10 1229/03/2005 13 11 18 1530/03/2005 9 5 12 2131/03/2005 11 11 16 23

EXAMPLE FOR S Portugal and Spain

España EMEP España FRViznar Níjar

58

8 124

8 97 105 9

13 1114 1217 1823 2165 1923 3946 4144 3639 2736 2843 30

191 35147 5681 10110 3711 2810 207 226 33

10 2511 238 30

15 1822 16

España EMEP España FRViznar Níjar Viznar Níjar

58

8 124

8 97 105 9

13 1114 1217 1823 21 15 1165 19 56 823 39 13 2746 41 36 2944 36 34 2039 27 29 936 28 26 1143 30 33 13

191 35 180 17147 56 136 3881 101 69 8310 3711 2810 207 226 33

10 2511 238 30

15 1822 16

Net dust contributions to be subtractedSierra Norte Barcarrota Doñana Alcoutim

6 12 25 3148 44 45 521

014 17 11 4223 38 25 3021 37 15 3824 45 23 5875 171 45 113

103 76 71 1885 11 5 0

S. Norte Barcarrota Huelva Alcotium Viznar Nijar S. Norte Barcarrota Huelva Alcotium Viznar Nijar

Net dust contribution for each area

Days with African dust outbreaks

Net dust contribution may also be ‘0’If dust outbreak is weak at surface levels

Barcarrota

NijarHuelva

Sierra NorteAlcoutim Viznar

0

5

10

15

20

25

30

35

40

45

01/01

/0802

/01/08

03/01

/0804

/01/08

05/01

/0806

/01/08

07/01

/0808

/01/08

09/01

/0810

/01/08

11/01

/0812

/01/08

13/01

/0814

/01/08

15/01

/0816

/01/08

PM10

µg/

m3

,

background before and after10 µg/m 3

'net dust load'31 µg/m 3daily values during the

dust outbreak41 µg/m 3

PM10

(µg/

m3 )

Dust outbreak increases the regionalBackground to 31 µg/m3 PM10 (‘net dust load’)

Attributed to African dust inputs60-31 µg/m3 =29 µg/m3 <50 µg/m3

100 µg/m3 PM10 traffic

Not attributed to African dust inputs100-31 µg/m3 =69 µg/m3 >50 µg/m3

60 µg/m3 PM10 urban

EXAMPLE

Crustal; 10,97; 30%

M arine; 1,75; 5%

EC+OM ; 13,67; 38%

SIC; 9,79; 27%

PM10

Barcelona10-10-2005 to 08-01-2006n=22

Crustal; 3,65; 14%

M arine; 0,51; 2%

SIC; 7,80; 31%

EC+OM ; 13,50; 53%

PM2.5

Barcelona10-10-2005 to 08-01-2006

n=22

41 µg/m3 30 µg/m3

PMPM1010/PM/PM2.52.5/PM/PM11 crustal loadcrustal load

EC+OM ; 11,21; 63%

SIC; 5,83; 32%

M arine; 0,18; 1%

Crustal; 0,80; 4%PM1

Barcelona10-10-2005 to 08-01-2006

n=2221 µg/m3

undetermined: 5,2; 13%

undetermined: 4,4;15%

undetermined: 3,2;15%

0

20

40

60

80

100

120

140

PM

2.5

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

N<2

0nm

PM2.5 N13-20 nm

0

20

40

60

80

100

120

PM

2.5

0

10000

20000

30000

40000

50000

60000

70000

N<8

00nm

PM2.5 N13-800 nm

0

20

40

60

80

100

120

140

01/02/04 02/02/04 03/02/04 04/02/04 05/02/04 06/02/04 07/02/04 08/02/04

PM

2.5

0

20

40

60

80

100

120

Dp-m

ax

PM2.5 DpN max

High impact of African dustotbreaks on PM2.5 No in n concentration!!!!!

Number/mass concentration: February 2004

Agradecimientos: Organización Seminario Calidad Aire España

Ministerio de Medio Ambiente y Ministerio de Educación y CienciaCCAA: Andalucía, Baleares, Canarias, Castilla-León, Castilla la Mancha, Cataluña, Euskadi, Extremadura, Galicia, Madrid, Murcia, ValenciaENDESA-Andorra-Teruel

Gracias por su atención !xavier.querol@ija.csic.es