QUALITAT DE L’AIRE

Barcelona, 07/02/2017

Xavier Querol, IDAEA-CSIC

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id aidæid aidid aidæInstitute of Environmental Assessment and Water Research

CONSEJO SUPERIOR DE INVESTIGACIONES CIENTÍFICAS SPANISH RESEARCH COUNCIL

http://www.idaea.csic.es/

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CSIC es un organismo de investigación público multi-disciplinar afiliado al Ministerio de Economía y Competitividad de España, con su propia personalidad legal (Agencia Estatal) y presencia a lo largo del territorio nacional.

Objetivos y función del CSIC (R.D. 140/1993, de 29 de Enero ) :

• Preparar y desarrollar proyectos de investigación científica y tecnológica

• Asesoramiento en la definición de objetivos de investigación científica y tecnológica para apoyar decisiones de la administración sobre cuestiones de innovación científica y tecnológica

• Desarrollar investigación científica básica

• Colaborar con las universidades en aspectos de investigación y de formación

• Desarrollar programas de formación científica y tecnológica

• Colaborar con el Programa Nacional de I+D en tareas de asesoramiento y administración que le sean asignadas

Institute of Environmental Assessment and Water Research

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Mission:

Study the natural and anthropogenically-induced changes in the ecosystems, mainly those involving toxicity increases in organisms and humans, by means of chemical and geochemical techniques

Leading roles in the application of:

- analytical chemistry

- geochemistry and hydrology

- molecular biology

- methods for the study of environmental problems

Departamental structure:

2 departments:

- Environmental Chemistry

- Geosciences

IDAEA

Institute of Environmental Assessment and Water Research

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A. Fuels, combustion and combustion by-products

• Mass balances for trace pollutants in combustion and gasification power plants

• Study of the fate of trace pollutants during waste disposal

DEPARTMENT OF GEOSCIENCES: 2 research lines

B. Atmospheric Geochemistry

• Long term measurements for aerosol-climate studies; increase the number of measuring parameters (EUSAAR, CIRCE, GRACCIE, ACTRIS)

• Research on urban/industrial aerosols towards health impact assessment (APHEKOM, APHEIS, INTARESE)

• Implementation of new instrumentation for the development of new research lines on aerosol and health.

• Policy implementation assessment (ETC-ACM, national and EU administrations)

Institute of Environmental Assessment and Water Research

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id aidæid aidid aidæ Research team on Geochemistry

Department of Geosciences

25 staff (6 permanent scientists)

Research tools: R&D projects in National and EC calls, & contracts with administrations & companies

Research focus: Atmospheric pollution Waste management and recycling

Institute of Environmental Assessment and Water Research

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• Permanent gases, con t>1000 years: N2 (78%v), O2 (21%v) and noble gases

• Variable gaseous species, 100<t>1 years: CO2 (395 ppmv), CH4, H2, N2O, O3

• Highly Variable gaseous species, t<1 year H2O(v): CO (<1ppmv), NO2, NH3, SO2 (ppbv), H2S,…..

Residence time (t)

Blue colour due to light dispersion by air molecules

Troposphere: meteorological processes take place, 8km (poles) and 18km (equator)

70% atmosphere weight, T gradient of 6,5°C/km

The atmosphere

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1855. Austria, Germany - Enacted laws against pollution with specific

exemptions for air and water!

1872. Robert Angus Smith - "Air and Acid Rain: The Beginnings of a Chemical

Climatology" - First use of the term "acid rain".

1895. Earliest known US air pollution law making illegal the "showing of visible

vapor" as exhaust from steam automobiles.

1911. Crowther and Ruston - Tie together acid rain and combustion.

1956. British Clean Air Act

1963. US Clean Air Act (CAA)

1965. Title II (US CAA) Motor Vehicle Air Pollution Control Act

1977. Amendments to CAA look for carcinogenic materials (POMS, PNAs).

1980. US/Canada Memorandum of Intent to develop a bilateral approach to the

acid rain problem.

1987. Montreal protocol to reduce CFC production (ozone destruction in

upper atmosphere)

1987-1997. US NAAQS, 2003 review.

1996 and 2008- EU Air Quality Directives

Ca. 1800 BC. Earliest documented impact of anthropogenic air pollution on human

beings. The Beauty of Loulan’s lungs were extensively damaged by sand dust and

campfire smoke.

Ca. 500 BC. Lao Tzu states impact of man on environment, including air quality.

Ca. 300 AD. Local Roman magistrate passes laws regulating certain sources of air

pollution in York, England. (breweries, meat slaughtering)

1180. Moses Maimonides - Describes air pollution in cities and its effects on man.

1272. Edward I - Banned use of "sea coal ". Parliament ordered punishment by

torturing and hanging of people who sold and burned the outlawed coal.

1390 (?) Richard II - Regulated and restricted use of coal in London.

1420 (?) Henry V - Ditto.

1661. John Evelyn - Earliest extant treatise on air pollution. "Fumifugium; or the

Inconvenience of the Air and Smoke of London Dissipated; Together with Some

Remedies Humbly Proposed".

1692. Robert Boyle - " a General History of the Air ", mentions "nitros or salino-

sulphureous spirits".

1772. Hales- Analysis of dew and rain, noted that "the air is full of acid and

sulphurus particles".

1734. Linne (Sweden) - Studied effects of an iron smelter on local air.

1775. Sir Percival Pott - Intuited that soot has a carcinogenic component causing

high incidence of cancer of the scrotum in chimney sweeps.

1852. Robert Angus Smith - Noted three zones of air pollution; fields and open

country with carbonate and ammonia, ammonium sulfate in suburbs, and acid

sulfate and sulfuric acid in town.

Historic Dates on Air Quality

Atmospheric pollution

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“Comparar aire de ciudades con el aire de los desiertos y las tierras áridas es como comparar las aguas que son podridas y turbias con las limpias y puras. En la ciudad, a causa de la altura de sus edificios, lo angosto de sus calles y de todo lo que se vierte desde sus habitantes y sus líquidos…… el aire se torna estancado, espeso, brumoso y neblinoso… Si el aire se altera alguna vez ligeramente, el estado del Espíritu Psíquico será alterado perceptiblemente.” Maimónides (Rabi Mose Ben MAIMON) médico sefardí cordobés, 1135-1204

Atmospheric pollution

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RD, 102/2011, 28th January, for Air Quality & Protection of the Atmosphere:

“Atmospheric Pollution”: The occurrence in atmosphere of matter, substances or energy that may imply risk or damage for the safety or health of human beings, the environment……..”

Atmospheric pollution

Bearing in mind:

• Not all harmful substances in atmosphere are already known

• For some components there is not a threshold for human protection

• Many activities and process (natural and anthropogenic) emit atmospheric pollutants

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id aidæid aidid aidæ The scales of the atmospheric pollution

Planetary-Global: Global warming and climate change

Destruction of stratospheric ozone

Macro-meso scale: Transport and acidification

Tropospheric ozone

Micro-scale: Urban air quality,

local impact of industrial

emissions

Atmospheric pollution

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Industrial processes, incineration

Chemical, metallurgical, petrochemical, mineral food, incineration

Fe, P, Al,

Si, Ca,..

Cu, Zn, Hg, V, Ni

F-, NH3, As, Pb, Cl-

Stationary sources

combustion

Power plants, heating, industry V, Ni (As, Se,..)

Various

Agriculture, fires, biomass combustion

NH3, K+

CO2, CO, HC, NOx, PM,

Corg+Celem, SO2

H+

Transport

Road, air, rail, fuel storage,………..

UF-PM, Sb,

Ba (Pb), Cl-

Biogenic, re-suspension, marine, lightening, volcanoes, fires

Natural emissions Cl-, Na+

Other: Harbor (shipping) emissions Air transport Construction-demolition Domestic and residential

EMISSION SOURCES AND TRACERS

Atmospheric pollution

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Emission characteristics

Pollutant load

T and V of emission

High of emission

ATMOSPHERIC DIFUSION OR DISPERSION

Meteorological features

Atmospheric stratification, W-V, W-D, convection

Topographic and local effects

Marine and slope breeze, topographic obstacles

0

20

40

60

80

µg/m

3

SO2 O3 NO2

00 12 00 12 00 12 00 12 00 12 00 12 00 12 00 12 00 12 00 12 00 12 00 12

January February March April May June July August September October November December

LLODIO

Atmospheric pollution

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id aidæid aidid aidæ EUROPEAN THEMATIC STRATEGY

Emissions levels

emission sources (natural, anthropogenic..)

primary pollutants (SO2, NOx, HC, PM,…)

standards Control measures

1996-1999

minimization strategies

new standards

target levels

new standards

2005-2010

2013-2014 (2020)

Local and global effects Impact on receptors,

epidemiology

measuring (concentration and meteorology)

Levels in ambient air

meteorology, dispersion, transport,...

chemical transformation

(secondary pollutants: O3, PAN, HNO3, H2SO4)

Modelling and integrated assessment

Atmospheric pollution

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id aidæid aidid aidæ ENVIRONMENTAL STANDARDS FOR AIR QUALITY

Directive 1999/30/EC SO2, NO2, NOx, PM10, Pb (PM2.5??)

Directive 2000/69/EC benzene, CO Directive 2002/03/EC O3

Directive 2004/107/EC PAH, Cd, As, Ni, Hg (PM2.5) Directive Clean Air for Europe and Air Quality, 2008/50/EC & 2004/107/EC

Deadlines: 2005-2010, 2015, 2020

MOTHER DIRECTIVE 1996/62/CE

Emission

Ambient air

RD, 102/2011 (Spanish legisltaion)

IPPC Integrated Prevention and Pollution Control, substituted by the Industrial Emissions Directive (IED)

DIRECTIVES 1996/61/EC, 2008/1/EC, 2010/75/EC 2002/51/EC, 2006/120/EC 1998/69/EC, 2002/80/EC, 2007/715/EC 2001/80/CE 2001/81/CE EU 2015/2193

EURO standards for vehicles

Large Combustion Plants National Emission Ceilings Medium scale combustion plants

REVISION IN 2013 & 2014

REVISION OF AQ DIRECTIVE DELAYED UNTIL 2020 EVEN WHEN WHO (REVIHAAP+HRAPIE PROJECTS)

RECOMMENDED CHANGING PM2.5 AND SOME TARGET VALUES TO LIMIT VALUES

Atmospheric pollution

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CRITICAL PARAMETRES (INFRINGEMENTS)

293 °K , 101,3 kPa,

Directive 2008/50/EC, RD 102/2011 except PM and metals, Evriron. Cond.

Hourly 350 µg/m3 SO2 24 times per year Daily 125 µg/m3 SO2 3 times per year Annual prot. ecos. 20 µg/m3 SO2 not exceeding annual and mean 1 Oct-31 Mar Hourly 200 µg/m3 NO2 8 times per year Annual 40 µg/m3 NO2 not exceeding Annual prot. vegetation 30 µg/m3 NOx (reported as NO2) not exceeding Annual 5 µg/m3 Benzene not exceeding Mean 8-h max. in a day 10 mg/m3 CO not exceeding Annual 500 ng/m3 Pb not exceeding Annual 40 µg/m3 PM10 not exceeding Daily 50 µg/m3 PM10 n<35 per year Annual (25 and 20 (18) µg/m3 PM2.5) not exceeding 2010-2020 (reducing 20% PM2.5 triennial for mean of urban background)

ENVIRONMENTAL STRANDARDS FOR AIR QUALITY

2004/107/EC, RD 102/2011

Annual 6 ng/m3 As not exceeding Annual 20 ng/m3 Ni not exceeding Annual 5 ng/m3 Cd not exceeding Annual 1 ng/m3 Benzo[]pirene not exceeding

Atmospheric pollution

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AOT40 [expressed in (µg/m3·h] = as sum of the difference between hourly levels exceeding 80 µg/m3 and 80 µg/m3 along a given period using only hourly values measured between 8.00 and 20.00 h, Central Europe Time (CET), for every day.

Target value Protection human health Maximum of 8 h means of a day 120 µg/m3 O3 not exceeding 25 day/year mean for 3 years Target Value Protection of vegetation AOT40, hourly values from Mayo to July 18.000 µg/m3·h O3 not exceeding as a mean of 5 years (c) Information threshold value: hourly 180 µg/m3 O3

Alert threshold value : hourly 240 µg/m3 O3

High levels out of urban agglomerations or in external urban areas

ENVIRONMENTAL STRANDARDS FOR AIR QUALITY

Atmospheric pollution

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Atmospheric pollution

2008/50/EC WHO (2006) guide lines RD 102/2011 Hourly 350 µg/m3 SO2 -- 24 times per year Daily 125 µg/m3 SO2 -- 3 times per year Hourly 200 µg/m3 NO2 EC-WHO coincide 18 times per year Annual 40 µg/m3 NO2 EC-WHO coincide not exceeding Annual 5 µg/m3 C6H6 EC-WHO coincide not exceeding Mean 8-h max. in a day 10 mg/m3 CO EC-WHO coincide not exceeding Annual 500 ng/m3 Pb EC-WHO coincide not exceeding Annual 40 µg/m3 PM10 20 µg/m3 PM10 not exceeding Annual 25 µg/m3 PM2.5 10 µg/m3 PM2.5 not exceeding Max 8 h means of a day 120 µg/m3 O3 100 µg/m3 O3 not exceeding 25 day/year mean for 3 years BaP annual 1 ng/m3 BaP 0.12 ng/m3 BaP not exceeding

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NO2 annual limit value

The problem of NO2

30/11/2015

2013 2014

http://www.eea.europa.eu/publications/air-quality-in-europe-2016

N2 atmosfèric + alta T+ O2=NO2

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Causas de superación del VLA de NO2:

promedio 2001-2009 (53 estaciones)

63%

29%

3% 2%2% 1%

Heavy traffic

Proximity to a major road

Local industry

Quarrying/mining

Domestic heating

Industrial accident

Non-industrial accident

Natural source

Winter sanding

African dust

Local petrol station

Parking facility

Benzene storage

Industry

0

10

20

30

40

50

60

70

80

90

100

FONERS

BARCELO

NA

CORNELL

A

STA P

ERPETU

A

L'HOSPIT

ALE

T

MONTC

ADA

STA C

OLO

MA

ST A

NDREU

EL

PRAT

BADALO

NA

BARCELO

NA

ST A

DRIÀ

B.

BARCELO

NA

TERRASSA

MOLL

ET

SABADELL

BARCELO

NA

BARCELO

NA

BADALO

NA

NO

2 (

µg

/m3)

2005 2006 2007 2008 2009 2010CATALUNYA

Valor límite desde 2010

0

10

20

30

40

50

60

70

80

90

100

ALC

OBENDAS

MADRID

GETAFE

MADRID

MADRID

COSLA

DA

MADRID

MADRID

MADRID

MADRID

ALC

ORCÓN

COSLA

DA

GETAFE

MADRID

NO

2 (

µg

/m3)

2005 2006 2007 2008 2009 2010COMUNIDAD DE MADRID

Valor límite desde 2010

0

10

20

30

40

50

60

70

80

90

100

CASTE

LLÓ

VALE

NCIA

VALE

NCIA

VALE

NCIA

VALE

NCIA

LEON

SALA

MANCA

SEGOVIA

PALE

NCIA

SEVILLA

GRANADA

GRANADA

ZARAGOZA

ZARAGOZA

AVILES

OVIE

DO

LAS P

ALMAS

A C

ORUÑA

NO

2 (

µg

/m3

)

2005 2006 2007 2008 2009 2010CC AA: VALENCIA, CASTILLA Y LEÓN

ANDALUCÍA, ARAGÓN, ASTURIAS, GALICIA

Valor límite desde 2010

•MADRID, COSLADA, GETAFE, LEGANÉS

•BARCELONA, BARBERÀ DEL V., MARTORELL, MONTCADA I R.,

ST. ANDREU DE LA B., MOLLET DEL VALLÈS, ST ADRIÀ DE BESÒS,

SABADELL, STA. COLOMA G., TERRASSA

•PALMA DE MALLORCA

•GRANADA, SEVILLA

2011

http://www.magrama.gob.es/es/calidad-y-evaluacion-ambiental/temas/atmosfera-y-calidad-del-aire/Informe_evaluaci%C3%B3n_calidad_aire_Espa%C3%B1a_2012_final_v2_tcm7-299046.pdf

2013: ZONAS CON SUPERACIÓN VALOR LIMITE ANUAL 2014: ZONAS CON SUPERACIÓN VALOR LIMITE ANUAL

2013 & 2014

The problem of NO2

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id aidæid aidid aidæ The problem of NO2

2015: ZONAS CON SUPERACIÓN VALOR LIMITE ANUAL 2015: ZONAS CON SUPERACIÓN VALOR LIMITE HORARIO

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• Dosimeter NO2 Palmes • Molecular diffusion • Absorbent = 20% TEA in H2O • Analysis: colorimetry

Length 7.1 cm

Absorber at

closed end

Open end for

sampling

Length 7.1 cm

Absorber at

closed end

Open end for

sampling

The problem of NO2

Levels

NO2 MAY-JUNE 2008 (120 PASSIVE

DOSIMETRES)

The problem of NO2

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id aidæid aidid aidæ NO2, high spatial variability

The problem of NO2

Levels

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id aidæid aidid aidæ Fabra - Barceloneta

The problem of NO2 NO2 MAY-JUNE 2008 (120 PASSIVE DOSIMETRES)

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The problem of NO2

0

1

2

3

4

5

6

Bar

celo

na

Mad

rid

Val

ènci

a

Am

ster

dam

Bel

grad

e

Ber

lin

Ber

n

Bo

logn

a

Bu

dap

est

Sto

ckh

olm

Fire

nze

Fran

kfu

rt

Gen

oa

Ham

bu

rg

Hel

sin

ki

Lon

do

n20

07

Luxe

mb

urg

Mila

n

Mu

nic

h

Nap

oli

Osl

o

Pra

ha

Ro

ma

Tori

no

Wie

n

Zuri

ch

Cars x 1000 / km2

Very high density of vehicles (#/km2), But also >50% of vehicles circulating in the city come from outside

0

500

1000

1500

2000

2500

3000

Ba

rce

lon

a

Ma

dri

d

Va

lèn

cia

Am

ste

rda

mB

elg

rad

e

Be

rlin

Be

rnB

olo

gn

a

Bu

da

pe

st

Sto

ckh

olm

Fire

nze

Fra

nk

furt

Ge

no

a

Ha

mb

urg

He

lsin

ki

Lon

do

n2

00

7

Luxe

mb

urg

Mil

an

Mu

nic

h

Na

po

li

Osl

o

Pra

ha

Ro

ma

To

rin

o

Wie

n

Zu

rich

Cars x1000

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Madrid

Barcelona

500m

El Problema de NO2

Napoli

Why so high NO2?

The problem of NO2

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id aidæid aidid aidæ El Problema de NO2 Why so high NO2?

The problem of NO2

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32/11/2016

http://www.eea.europa.eu/publications/air-quality-in-europe-2016

The problem of NO2

Atmospheric particulate matter (PM): heterogeneous solid and/or liquid material present in suspension into the atmosphere

• Health impact • Ecosystems • Climate change • Building materials • Visibility

The problem of PM

A comparative risk assessment of burden of disease and

injury attributable to 67 risk factors and risk factor clusters

in 21 regions, 1990–2010 (Lancet 2012)

The problem of PM

Haywood and Boucher (2000)

Climate Modulation: influence in the radiative balance

Direct effect Scattering & absorption

Indirect effect Scattering by formation of condensation nuclei

Semi-direct Effect

Climate effects of PM

IPCC, 2013

Climate effects of PM

+3.21

-0.69

+0.33

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Shindell et al (2012) Science 315

The problem of PM

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Impact on ecosystems

Slamba Poremba, Poland (C. Martin, The Environmental Picture Library)

PM EFFECTS

The problem of PM

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Weathering of building materials

The problem of PM

PM EFFECTS

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26/03/00

26/02/00

VISIBILITY

The problem of PM

PM EFFECTS

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1. Process of formation: Primary particles: directly emitted to the atmosphere as a solid Secondary particles: produced into the atmosphere from gaseous precursors example: SO2 (g) oxidation SO4

2- (s) 2. Origin: Natural particles Anthropogenic particles (human activities)

CLASSIFICATION OF ATMOSPHERIC PARTICLES

The problem of PM

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The problem of PM

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The problem of PM

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Process of oxidation SO2 H2SO4 and NOx HNO3

Homogeneous (gas to particle)

Heterogeneous (gas-H2O-particle)

Maximal velocities (summer, max hv): 6%SO2h-1, 18%NO2h-1 34%SO2day-1, 98%NO2day-1

Dry oxidation (homogeneous) Generation of oxidant radicals

O3+hν (solar) O* O*+H2O 2OH Oxidation

SO2+OH+m HOSO2+m HOSO2+O2 HO2+SO3

SO3+H2O H2SO4

NO+O3 NO2+O2 NO2+OH+m HNO3+m

Reaction

Wet oxidation (dissolution of gases, mainly SO2) (condensation nuclei, fog, precipitation, ‘wet aerosol films’) Oxidants: H2O2 (pH<5), O3 (pH>5), O2 (catalysers, Cl, m) Oxidation

HCOH+hv (solar) H+HCO* HCO*+O2 HO2 + CO* (formaldehyde)

HO2 + HO2 H2O2+O2

2SO2 + 2H2O SO32-+HSO3

-+3H+

HSO3- + H2O2 HSO4

-+H2O

Maximal velocities (summer, max hv): 270%SO2h-1 (H2O2) 410%SO2h-1 (O3)

Nucleation

Condensation

The problem of PM

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PRIMARY

• Natural

re-suspension (loc/ext) evap./precip.

• Anthropogenic

direct emissions

fugitive emissions

SECONDARY

• Natural

natural sulphate

biogenic emissions

• Anthropogenic

PM from gas by nucleation condensation evaporation

SO4=, NO3

-, NH4+, H+

Corg, metals

0.1 µm 1.0 µm 10 µm 25 µm

PM ORIGIN

SiO2,Al2O3,Fe2O3,TiO2

CaCO3, NaCl, Corg, metals

0.1 µm 1.0 µm 10 µm 25 µm

(Soot)

The problem of PM

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id aidæid aidid aidæThe problem of PM

Vo

lcanic +

Bio

gen

ic su

lfate,7

8

Bio

genic SO

A,

25

Tera grams / Year, Andreae and Rosenfeld (2008) and Durant et al. (2010)

Mineral dust 1600

Sea spray 10130

Primary A

nth

r+Nat

nitrate,1

8

An

thro

po

gen

ic su

lfate, 1

22

An

tho

p.

SOA

,3.5

Secondary

Volcanic* dust, 200

Biological POA, 35

BC Biomass burning, 6

POA Biomass burning, 54

POA Fossil fuels, 4

Industrial dust, 100

BC Fossil fuels, 4.5

Natural Anthropogenic

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Secondary Inorganic aerosols NH4

+ SO4

2- NO3

-

Crustal-mineral Al2O3 Mg Ti Fe K SiO2 CO3

2-

P Ca

Sea spray Na+ Cl- SO4

2-

Carbonaceous aerosols (OM and EC)

Trace elements As, Ba, Bi, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Ga, Gd, Ge, Hf, La, Li, Mn, Mo, Nd, Ni, Pb, Pr, Rb, Sb, Sc, Se, Sm, Sn, Sr, Ta, Th, Ti, Tl, U, V, W, Yb, Zn, Zr

PM ORIGIN

The problem of PM

Bioaerosol (natural)

pollen

Vegetal debris, insects, bacteria,….

The problem of PM

Sea spray

NaCl

Sodium, potassium, magnesium chloride, sodium, magnesium sulphate ,

DMS

The problem of PM

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TEM-EDX analysis

The problem of PM

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Scale = 500nm

fly ash

glass Magnetite

The problem of PM

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Quartz Clay minerals (kaolinite, Illite, Chlorite, ((Paligorskite, Smectite)) Feldespars Other silicate minerals (talc, pirophillite,….) Carbonate minerals (calcite, dolomite) Phosphates, oxides, gypsum,….

PM ORIGIN

The problem of PM

combustion power plant

SI, Al, S, K, Fe, Ti

quartz

SI, S, Fe

The problem of PM

Marine aerosols

Natural minerals

Bioaerosols + biogenic

Natural Background

x

x

x

x

x

x

x

x

NH4NO3

(NH4)2SO4

Long Range Transp.

x

x

Carbonaceous

NH4NO3

(NH4)2SO4

Carbonaceous (Soot, mainly road traffic)

Local emissions

Pavement, demolition, constr.

Carbonaceous (fuel-oil ash)

Heavy metals

Interaction among species

The problem of PM

PM10 daily limit value 2013

The problem of PM

PM10 daily limit value 2014

30/11/2015

32/11/2016

http://www.eea.europa.eu/publications/air-quality-in-europe-2016

http://www.magrama.gob.es/es/calidad-y-evaluacion-ambiental/temas/atmosfera-y-calidad-del-aire/Informe_evaluaci%C3%B3n_calidad_aire_Espa%C3%B1a_2012_final_v2_tcm7-299046.pdf

Zonas con superaciones 2012 valor límite diario

2012: ZONAS CON SUPERACIÓN VALOR LÍMITE DIARIO 2012: ZONAS CON SUPERACIÓN VALOR LÍMITE ANUAL

2013: ZONAS CON SUPERACIÓN VALOR LÍMITE DIARIO

2013

2013: ZONAS CON SUPERACIÓN VALOR LÍMITE ANUAL

The problem of PM

2014: ZONAS CON SUPERACIÓN VALOR LÍMITE DIARIO

The problem of PM

ZONAS CON SUPERACIONES VALOR LÍMITE DIARIO PM10 2015

ZONAS CON SUPERACIONES VALOR LÍMITE ANUAL

PM10 2015

PM10 (annual mean)

1. Road Traffic is the main source contributing to PM10: 31-38% (ATH 23%) 1.1. Vehicle exhaust + traffic related NO3

- are the main causes: 21-29% (ATH 15%) 1.2. Non-exhaust vehicle emissions are also relevant: 8-11% 2. Regional OC and/or SO4

2- dominated pollution: 20-26% (POR-TR 10%) 3. Local dust : 10-19% 4. Biomass burning very relevant in POR & FI (14-16%), less in ATH (7%) and negligible in BCN 5. Industry BCN 11%, 4-5%, ATH <1% 6. Non traffic-NO3

- 6-8% (2% POR) 7. Shipping 4% in coastal sites 8. African dust ATH 14%, 1-4% 9. Sea salt POR 13%, 4-8% 10. Anthropogenic dust (Local dust + Non exhaust) reaches 19-25%

PM2.5 (annual mean)

1. Road Traffic is the main source contributing to PM2.5: 28-39% (ATH 22%) 1.1. Vehicle exhaust + traffic related NO3

- are the main causes: 25-34% (ATH 17%) 1.2. Non-exhaust vehicle emissions are also relevant: 5-9% (BCN&FI 1-2% ) 2. Regional OC and/or SO4

2- dominated pollution: 19-37% (POR 13%) 3. Local dust: POR 16%, 2-6% 4. Biomass burning very relevant in MLN, FI & POR (18-21%), less in ATH (10%) and negligible in BCN 5. Industry 5-12%, ATH <1% 6. Non traffic-NO3

- 3-6% (POR 1%) 7. Shipping 5-7% in coastal sites 8. African dust: ATH 6%, <1% 9. Sea salt POR 5%, <1-3%, 10. Anthropogenic dust (Local dust + Non exhaust) reaches 10-21%, BCN 7%, FI 4%

36-45% (ATH 15%) 30-34% (ATH 6%) 18-29% (ATH 3%, POR 6%) BCN 19%, 2-6% POR 27%, 1-4% POR & FI (25-30%), ATH 1%, negligible in BCN BCN 17%, <1-3% BCN & FI 7-9% (1-2% POR & ATH) 3-4% in coastal sites ATH 52%, 1% ATH 7%, 1-3% 11-33%, ATH 4%

PM10 (days of exceedance)

32-42% (ATH 11%) 31-40% (ATH 10%) 1-7% BCN & MLN 11-22%, 2-6% POR 22%, 1-2% POR, FI & MLN (26-33%), <2% BCN 18%, <1-3% BCN, FI & MLN 6-9% (1-3% POR & ATH) 6-10% in coastal sites ATH 45%, 1% <1%-1% POR 15, 3-9%

PM2.5 (days of PM10 exceedance)

The problem of PM

The problem of Benzo-α-pirene

BaP target annual value BaP 2013

2013 2014

32/11/2016

http://www.eea.europa.eu/publications/air-quality-in-europe-2016

2014

The problem of Benzo-α-pirene

BaP valor objetivo anual, 2015

Manlleu, 1.35 ng/m3

The problem of Benzo-α-pirene

Manlleu BaP

ida

idæid aidid

aidæ

id aidæid aidid aidæ El problema de l’ozó

http://www.geo.sunysb.edu/ess-workshops/lesson-plans.html

ida

idæid aidid

aidæ

id aidæid aidid aidæThe problem of ozone

ida

idæid aidid

aidæ

id aidæid aidid aidæO3

The problem of ozone

ida

idæid aidid

aidæ

id aidæid aidid aidæOzone, annual target triennial mean

30/11/2015

The problem of ozone 2015

32/11/2016

http://www.eea.europa.eu/publications/air-quality-in-europe-2016

2013

2014

ida

idæid aidid

aidæ

id aidæid aidid aidæ

63

Evolución día 15-16 julio

NO2 O3

OUTDOOR AND INDOOR PARTICLE CONCENTRATIONS IN

SCHOOLS OF BARCELONA DURING THE BREATHE STUDY

QUEROL X.1, RIVAS I.1,2, BOUSO L.2, RECHE C.2, AMATO F.1, VIANA M.1, MORENO T.1, PANDOLFI M.1,

ALASTUEY A., ÁLVAREZ M.2, SUNYER J.2,

1 Institute of Environmental Assessment and Water Research, IDAEA, CSIC, Barcelona, Spain 2 Centre de Recerca en Epidemiologia Ambiental CREAL-UPF, Barcelona, Spain

Zurich, 30th June 2015

xavier.querol@idaea.csic.es

Objectives of BREATHE

Exposure to air pollution at school

PLoS Med. 2015;12(3):e1001792

Dashed line = high traffic air pollution

Continuous line = low traffic air pollution

Gray shading = 95% CIs

ERC-Advanced Grant, PI: Jordi Sunyer

CREAL

OBJECTIUS

• Characterizing children exposure to urban air pollutants in schools

• Identification and quantification of the main sources of these pollutants affecting

indoor and outdoor environments

• Defining factors affecting PM (including UFP) levels and composition in both

indoor and outdoor environments: road traffic emissions, ventilation and type of

playground

• Characterize children’s daily BC exposure and sources

Objectives on ambient air & exposure

ERC-Advanced Grant,

Leader of the exposure studies:

Xavier Querol, IDAEA-CSIC

• Two simultaneous schools & a urban

background reference station of

Palau Reial (UB)

• Simultaneously in indoor and outdoor

school environments

• Sampling in teaching hours (9 to 17h),

from Monday to Thursday

• 2 campaigns at each school:

- 1 week/school in winter-spring

- 1 week/school in fall-winter

Monitoring sites

Measurement periods 1. February to June 2012

2. September 2012 to February 2013

Metodology: Measurements

36 schools in Barcelona

3 schools in Sant Cugat

SCHOOLS

DUSTTRAK DRX

HIGH-VOLUME SAMPLERS

MICROAETH® AE51

MINIDISC

GRADKO NO2 TUBES

GRIMM

HIGH-VOLUME SAMPLERS

MAAP

WCPC

NSAM

GRADKO NO2 TUBES

PM2.5

PM2.5

COMPONENTS

BC

N

SIZE

LDSA

NO2

Metodology: Measurements & sampling

UB REFERENCE SITE

H2O leaching

Ion Chromat.:

NO3-, Cl-, SO4

=

Colorimetry FIA and ICP-AES:

NH4+, K+, Ca2+,

Mg2+,…

Acidic digestion (HF:HNO3:HClO4)

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

Mass determined: 75-85% PM2.5

Metodology: Chemical analysis

Rivas I., et al ., 2014. Child exposure to indoor and outdoor air pollutants in schools. Environment International 69, 200–212.

Results: Mean levels

NO2 outdoor levels for the rest of schools in Barcelona = 50 µg·m-3

• High levels of PM2.5 in schools Local (school) emission of PM2.5

• Mean levels of pollutants are intermediate between traffic and urban

background sites

INDOOR OUTDOOR UB REF. STATION

Mean SD Mean SD Mean SD

NO2

(µg·m-3) 30 13 47 19 41 20

PM2.5 (µg·m-3)

37 16 29 24 17 8

N (pt·cm-3)

15625 6673 23614 9514 14665 6034

EBC (µg·m-3)

1.3 0.9 1.4 1.1 1.3 0.8

Results: PM2.5 source apportionment

Mineral sources

Results: PM2.5 source apportionment

PM2.5 (µg/m3) Paved playground

Unpaved playground

Reference site 0.6

Schools (outdoor) 2.5 16.0

Schools (indoor) 3.6 9.1

Indoor resuspension

Increases indoors PM2.5 by 5-6 µg/m3

Reference Station BREATHE Schools

EC levels perimeter Low High

Results: Spatial variation

PM2.5 BC

NO2 UFP

EBC (µg·m3)

< 1.25 1.25 – 1.60

> 1.60

PM2.5 (µg·m3)

< 24 24 – 32

> 32

NO2 (µg·m3)

< 42

42 – 53 > 53

N (103 pt·cm3)

< 18 18 - 24

> 24

Estació referència Escoles BREATHE

EC levels perimeter Low High

Results: Spatial variation

EBC (µg·m3)

< 1.15 1.15 – 1.55

> 1.55

PM2.5 (µg·m3)

< 34 34 – 50

> 50

NO2 (µg·m3)

< 22

22 – 34 > 34

N (103 pt·cm3)

< 13 13 - 18

> 18

PM2.5 BC

NO2 UFP

PERSONAL EXPOSURE TO EBC

- EBC median concentration is higher in personal monitoring than in the fixed station (school indoor, school outdoor, urban background)

classroom playground other commuting home

02

00

04

00

06

00

08

00

01

00

00

EBC from personal monitoring by children location

EB

C (

ng

/m3

)

01

00

02

00

03

00

0

EBC concentrations

classroom school playground UB personal

EB

C (

ng

/m3

)

- Highest EBC median concentrations found during commuting

Results: Levels of BC Children’s exposure

Results: Levels of BC

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

2022

23

24

25

26

27

28

29

30

31

32

33

3435

36

37

38

39

40

4575000

4580000

4585000

4590000

420000 425000 430000 435000

long

lat 0.2

a 0.2

hour

bo40

, bi4

0

500

1000

1500

2000

2500

0 6 12 18 23

bo40 bi40

hour

bO39

, bi3

9

200

400

600

800

1000

1200

0 6 12 18 23

bO39 bi39

hour

bO38

, bi3

8

500

1000

1500

0 6 12 18 23

bO38 bi38

hour

bO36

, bi3

6

1000

1500

2000

2500

3000

3500

0 6 12 18 23

bO36 bi36

hour

bO35

, bi3

5

200

400

600

800

1000

1200

0 6 12 18 23

bO35 bi35

hour

bO37

, bi3

7

1000

2000

3000

4000

0 6 12 18 23

bO37 bi37

hour

bO31

, bi3

1

2000

3000

4000

5000

6000

0 6 12 18 23

bO31 bi31

hour

bO34

, bi3

4

500

1000

1500

2000

0 6 12 18 23

bO34 bi34

hour

bO33

, bi3

3

500

1000

1500

2000

0 6 12 18 23

bO33 bi33

hour

bO32

, bi3

2

500

1000

1500

2000

2500

0 6 12 18 23

bO32 bi32

hour

bO30

, bi3

0

500

1000

1500

2000

2500

0 6 12 18 23

bO30 bi30

hour

bo29

, bi2

9

1000

2000

3000

4000

0 6 12 18 23

bo29 bi29

hour

bo28

, bi2

8

1000

2000

3000

0 6 12 18 23

bo28 bi28

hour

bo27

, bi2

7

1000

1500

2000

2500

3000

3500

0 6 12 18 23

bo27 bi27

hour

bo26

, bi2

6

500

1000

1500

0 6 12 18 23

bo26 bi26

hour

bo25

, bi2

5

500

1000

1500

2000

2500

3000

0 6 12 18 23

bo25 bi25

hour

bo24

, bi2

4

500

1000

1500

2000

2500

3000

0 6 12 18 23

bo24 bi24

hour

bo23

, bi2

3

1000

2000

3000

4000

5000

0 6 12 18 23

bo23 bi23

hour

bo20

, bi2

0

1000

2000

3000

4000

5000

6000

0 6 12 18 23

bo20 bi20

hour

bo22

, bi2

2

500

1000

1500

2000

2500

3000

0 6 12 18 23

bo22 bi22 hour

bo19

, bi1

9

1000

2000

3000

4000

0 6 12 18 23

bo19 bi19

hour

bo18

, bi1

8

500

1000

1500

2000

0 6 12 18 23

bo18 bi18

hour

bo17

, bi1

7

1000

2000

3000

4000

0 6 12 18 23

bo17 bi17

hour

bo15

, bi1

5

1000

2000

3000

4000

0 6 12 18 23

bo15 bi15

hour

bo14

, bi1

4

0

500

1000

1500

2000

2500

0 6 12 18 23

bo14 bi14

hour

bo13

, bi1

3

1000

2000

3000

4000

5000

6000

0 6 12 18 23

bo13 bi13

hour

bo12

, bi1

2

1000

2000

3000

4000

5000

0 6 12 18 23

bo12 bi12

hour

bo11

, bi1

1

1000

2000

3000

4000

0 6 12 18 23

bo11 bi11

hour

bo10

, bi1

0

500

1000

1500

0 6 12 18 23

bo10 bi10

hour

bo9,

bi9

1000

2000

3000

4000

5000

6000

0 6 12 18 23

bo9 bi9

hour

bo8,

bi8

500

1000

1500

2000

0 6 12 18 23

bo8 bi8

hour

bo7,

bi7

200

400

600

800

1000

1200

1400

0 6 12 18 23

bo7 bi7

hour

bo5,

bi5

500

1000

1500

0 6 12 18 23

bo5 bi5

hour

bo4,

bi4

200

400

600

800

1000

1200

0 6 12 18 23

bo4 bi4

hour

bO3,

bi3

1000

1500

2000

0 6 12 18 23

bO3 bi3

hour

bo2,

bi2

500

1000

1500

2000

2500

3000

0 6 12 18 23

bo2 bi2

hour

bo1,

bi1

500

1000

1500

2000

2500

0 6 12 18 23

bo1 bi1

x

y

40

39

38

1

4 35

7

815

11

14

3 25

5

28

9 23

1327

18

2

31

34

26

12

3632

37

19

29

33

17

10

20

2224

30

hour

bo6,

bi6

500

1000

1500

0 6 12 18 23

bo6 bi6

hour

bo16

, bi1

6

1000

2000

3000

4000

5000

6000

0 6 12 18 23

bo16 bi16

16

6

Daily cyles from 0 to 23h

EBC Indoor

EBC Outdoor

p

bc

1.0

1.5

2.0

2.5

0 20 40 60

r

bc

1.0

1.5

2.0

2.5

10 20 30 40

R2=0.61 R2=0.32

EBC

(µ

gm-3

)

Percentage of area used for the road network

Percentage of area used for parks

Results: Levels of BC & ultrafine patyicles

y = 584.1x + 6913.7R² = 0.3082

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

0 5 10 15 20 25 30 35 40 45

Ou

tdo

or

N b

y d

istr

ict

(#cm

-3)

Percentage of roads by district (%)

y = -267.34x + 28128R² = 0.3393

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

0 10 20 30 40 50 60 70 80

Ou

tdo

or

N b

y d

istr

ict

(#cm

-3)

Percentage of green areas by district (%)

Correlation between average EBC levels and ultrafine particle concentrations at different districts of the city of Barcelona and the percentage of surface area used for the road network and for parks

Closed windows Opened windows

y = 0.4977x + 7.6411R² = 0.5136

y = 0.5405x + 2.2478R² = 0.6122

0

20

40

60

80

100

120

0 20 40 60 80 100 120

indoor (µg·m-3)

outdoor (µg·m-3)

NO2

y = 0.5761x + 0.5922R² = 0.3949

y = 1.1187x - 0.1451R² = 0.9548

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

0.0 1.0 2.0 3.0 4.0 5.0

indoor (µg·m-3)

outdoor (µg·m-3)

EC

y = 0.2716x + 7555.4R² = 0.2201

y = 0.5913x + 6562.3R² = 0.3452

0

10000

20000

30000

40000

50000

60000

0 10000 20000 30000 40000 50000 60000

indoor (pt·cm-3)

outdoor (pt·cm-3)

N

y = 0.2252x + 43.839R² = 0.1102

y = -0.0252x + 46.549R² = 0.0017

0

20

40

60

80

100

120

140

0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0

indoor (µg·m-3)

outdoor (µg·m-3)

PM2.5

Outdoor measurements carried out more distant from highly traffiqued roads than indoor measurements

Indoor

Outdoor

Results: Infiltration of pollutants

MOLTES GRÀCIES PER LA VOSTRA ATENCIÓ!!!!!

Barcelona, 07/02/2017

xavier.querol@idaea.csic.es