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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 [email protected]