Atmospheric Chemistry Atmospheric aerosol, air quality and climate: from the local to the global...

Atmospheric ChemistryAtmospheric Chemistry

Atmospheric aerosol, air quality Atmospheric aerosol, air quality and climate: from the local to the and climate: from the local to the

global scale global scale

Sandro FuzziSandro Fuzzi

Institute of Atmospheric Sciences and ClimateInstitute of Atmospheric Sciences and ClimateNational Research CouncilNational Research Council

BolognaBologna


The atmosphere: a multiphase systemThe atmosphere: a multiphase system

The atmosphere is a multiphase system, The atmosphere is a multiphase system, insofar as all three phases are insofar as all three phases are simultaneously present: gas, solid, liquidsimultaneously present: gas, solid, liquid

Dry aerosol constitutes the solid phaseDry aerosol constitutes the solid phase Wet aerosol and cloud/fog droplets Wet aerosol and cloud/fog droplets

constitute the liquid phaseconstitute the liquid phase


Aerosol: definitionAerosol: definition

““a stable suspension of solid and/or a stable suspension of solid and/or liquid in air”liquid in air”

Size interval Size interval

0.003 - 100 0.003 - 100 mm


Aerosol mass distributionAerosol mass distribution


Aerosol mass and number Aerosol mass and number concentrationsconcentrations

Aerosol type

Aerosol number

(N/cm3)

Aerosol mass

(g/m3)

Plume

107

102-105

Urban area 105-106 100-1000 Rural area 103-105 10-100 Remote area 100-500 10 Artic 10-1000 0.1-10 Anctartica 10-100 0.1


emission deposition

transport - transformation

surface

atmosphere

Cycle of atmospheric aerosolCycle of atmospheric aerosol


Emission of aerosol in the atmosphereEmission of aerosol in the atmosphere

Fragmentation processesFragmentation processes(primary aerosol, mostly super-micron size)(primary aerosol, mostly super-micron size)

Combustion processesCombustion processes(primary aerosol, wide size range)(primary aerosol, wide size range)

Conversion processesConversion processes(secondary aerosol, sub-micron size)(secondary aerosol, sub-micron size)


Global aerosol sources (Tg/yr)Global aerosol sources (Tg/yr)

NaturalNatural 30603060PrimaryPrimary Soil mobilization 1500 Soil mobilization 1500 Sea salt 1300Sea salt 1300

Volcanic aerosol 30Volcanic aerosol 30 Biological particles 50Biological particles 50Secondary Secondary Sulphate (conv. SO Sulphate (conv. SO22) 100) 100

Nitrate (conv. NONitrate (conv. NOXX) 20) 20 Organic aerosol (conv. BVOC) 60Organic aerosol (conv. BVOC) 60

AnthropogenicAnthropogenic 395395 PrimaryPrimary Industrial aerosol 100 Industrial aerosol 100 Fossil fuel combustion 25Fossil fuel combustion 25 Biomass burning 80Biomass burning 80SecondarySecondary Sulphate (conv. SO Sulphate (conv. SO22) 140) 140

Nitrate (conv. NONitrate (conv. NOXX) 40) 40 Organic aerosol (conv. AVOC) 10Organic aerosol (conv. AVOC) 10


Aerosol optical thicknessAerosol optical thicknessModerate Resolution Imaging Spectroradiometer (MODIS) Moderate Resolution Imaging Spectroradiometer (MODIS)

on NASA Terra satelliteon NASA Terra satellite

Jan.

Feb.Feb.

Mar

AprApr

July

Aug.

May

Sept.

AOT monthly averageyear 2001

AOT < 0.1remote atmosphere

AOT > 0.2polluted atmosphere


Aerosol optical thicknessAerosol optical thickness(June-August 2001)(June-August 2001)

0.1 0.2 0.3 0.4

ISAC-CNR - ROMA


Saharan dust plume (2 March 2002)Saharan dust plume (2 March 2002)SeaWIFFSSeaWIFFS satellitesatellite

dust

pollutionaerosol


Gas-to-particle-conversionGas-to-particle-conversion

Two or more gaseous species react Two or more gaseous species react producing a low vapor pressure producing a low vapor pressure compoundcompound

The new compound can:The new compound can:condense onto a pre-existing particlecondense onto a pre-existing particlenucleate forming a new ultra-fine particlenucleate forming a new ultra-fine particle


NucleationNucleation

Evidence of formation of “new” particles of a few Evidence of formation of “new” particles of a few nm size reported by Aitken already in 1897nm size reported by Aitken already in 1897

Measurements possible only in the last few years Measurements possible only in the last few years (DMPS)(DMPS)

Mechanisms proposed:Mechanisms proposed:binary nucleation (Hbinary nucleation (H22O-HO-H22SOSO44))

ternary nucleation (Hternary nucleation (H22O-HO-H22SOSO44-NH-NH33))

ion induced nucleationion induced nucleation


Formation and growth of ultra-fine Formation and growth of ultra-fine particles (Po Valley)particles (Po Valley)

00:00 10:30 13:30 18:00 24:00

Laaksonen et al., Geophys. Res. Lett., 2005


Frequency of nucleation in the Po ValleyFrequency of nucleation in the Po Valley

Event days (Classes (1+2+3)) / All days

0.00 %

10.00 %

20.00 %

30.00 %

40.00 %

50.00 %

60.00 %

70.00 %

Jan Feb Mar Apr May June July Aug Sep Oct Nov Dec

Months

Fre

quen

cy%


Gas/particle connectionGas/particle connection

0 25 500

25

50

-20

-15

-10

-505101520

VOC reduction %

NO

x re

duct

ion

%

PM 2.5

15-20

10-15

5-10

0-5

-5-0

-10- -5

-15- -10-20- -15

Meng et al., Science, 1997


Aerosol removalAerosol removal

Two series of mechanisms are responsible Two series of mechanisms are responsible for aerosol removal:for aerosol removal:

dry removal dry removal (sedimentation, turbulence, (sedimentation, turbulence, impact)impact)

wet removal wet removal (incorporation in clouds and (incorporation in clouds and deposition through precipitation)deposition through precipitation)


diameter (micrometers)

day

s

0.001

0.01

0.1

1

10

100

0.001 0.01 0.1 1 10 1000.1

1

10

100

1000

hou

rs

Brownian diffusioncoagulation sedimentation

accumulation mode

Aerosol residence timeAerosol residence time


Aerosol chemical compositionAerosol chemical composition

Unlike atmospheric gases, aerosols cannot be characterised by a single parameter such as concentration. Instead atmospheric aerosols are characterised by their physical, chemical and optical properties, as well as their state of mixture (internal or external) and phase (solid, liquid or ice).


Aerosol complexityAerosol complexity Various chemical species (elemental, organic

and inorganic) are present Solid, liquid and ice particles from a few

nanometers to a few hundred micrometers are present

Internally/externally mixed system exists Temporal (diurnal, seasonal and annual), and

spatial (long/lat and altitude) variability and systematic relationships need to be considered


Aerosol state of mixingAerosol state of mixing


Carbonaceous aerosolCarbonaceous aerosol

Until recently, only the inorganic Until recently, only the inorganic fraction of the aerosol was knownfraction of the aerosol was known

Now we know that carbonaceous Now we know that carbonaceous aerosols are ubiquitous and can aerosols are ubiquitous and can contribute from 20% to > 80% of the contribute from 20% to > 80% of the mass of fine aerosolmass of fine aerosol


Forms of carbon in the aerosolForms of carbon in the aerosol

black carbon (BC)black carbon (BC) organic carbon (OC)organic carbon (OC)

total carbon (TC) = BC + OCtotal carbon (TC) = BC + OC


Composition of fine aerosolComposition of fine aerosol

polluted continental areapolluted continental area40 40 g/mg/m33

biomass burningbiomass burning60 60 g/mg/m33

remote forested arearemote forested area3 3 g/mg/m33

remote marine arearemote marine area1 1 g/mg/m33

polluted marine areapolluted marine area6 6 g/mg/m33

OCOCBCBCinorganicinorganic


Sources of fine organic aerosol Sources of fine organic aerosol

PrimaryPrimarybiomass burningbiomass burningfossil fuelfossil fuelbiological material biological material (?)(?)

SecondarySecondaryanthropogenic VOC oxidationanthropogenic VOC oxidationbiogenic VOC oxidationbiogenic VOC oxidation


Global emissions of fine organic Global emissions of fine organic aerosol (Tg/y)aerosol (Tg/y)

Source E. North E. South Global biomass 28 26 54 (45-80) fossil fuel 28 0.4 28 (10-30) BVOC 8.2 7.4 16 (8-40) AVOC 0.45 0.15 0.6 (0.3-1.8) Tot. organic 64 34 98 (60-150) Tot. aerosol 600 200 800


Size-segregated aerosol chemical Size-segregated aerosol chemical compositioncomposition

Bologna - winter

D(m)

0.05 0.14 0.42 1.2 3.5 10

Ma

ss fractio

n (%

) 0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

mass(

g/m3)

0

5

10

15

20

25

30

35

INS WSOC WS_INORG

Cheju Island

D(m)

0 0.2 0.5 1.5 5.5 10

Mass fractio

n (%) 0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

mass(

g/m3)

3

4

5

6

7

8INS WSOC WS_INORG MINATROC

D(m)

0.05 0.14 0.42 1.2 3.5 10

Mass fraction (%

) 0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

mass(

g/m3)

0

2

4

6

8

10

INS WSOC WS_INORG

Hyytiala - QUESTNo nucleation events in boreal forest

D(m)

0.05 0.14 0.42 1.2 3.5 10

Mass fra

ction (%) 0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

ma

ss(g/m

3)

0

1

2

3

4

5

6

7

8

INS WSOC WS_INORG

Rondonia - SMOCCDry period

D(m)

0.05 0.14 0.42 1.2 3.5 10

Mass fraction (%

) 0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

mass(

g/m3)

0

5

10

15

20

25

30

35

40

INS WSOC WS_INORG

Mace HeadBloom period

D(m)

0.06 0.125 0.25 0.5 1 2 4 8 16

Mass fractio

n (%) 0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

mass(

g/m3)

0

1

2

3

4

5

6

INS WSOC WS_INORG

Continental polluted (Po Valley) Polluted site in Asia (Korea) Saharan dust (Mt. Cimone)

Finnish boreal forest Biomass burning in Amazzonia Marine remote site (Mace Head)


European aerosol climatologyEuropean aerosol climatology


0

20

40

60

80

100

120

Jun

gfr

au

joch

(C

H)

Se

vett

ijarv

i (F

IN)

Skr

ea

da

len

(N

)

Bir

ken

es

(N)

Asp

vre

ten

(S

)

Ch

au

mo

nt

(CH

)

Mo

na

gre

ga

(E

)

Illm

itz (

A)

Ha

rwe

ll (G

B)

Ho

he

np

eis

sen

be

rg (

D)

Me

lpitz

(D

)

Isp

ra (

I)

Wa

asm

un

ste

r (B

)

Zu

eri

ch (

CH

)

Ba

sel (

CH

)

Lo

nd

on

-B (

GB

)

Le

ipzi

g 9

7-9

9 (

D)

Ge

nt

(B)

Bo

log

na

(I)

Ba

rce

lon

a (

E)

Be

rn (

CH

)

Lo

nd

on

-M (

GB

)

Wie

n (

A)

PM

10 (

µg/

m³)

average

median

EU 24-hr limit value

2005 EU annual standard

2010 EU annual standard

0

20

40

60

80

100

120

Jun

gfr

au

joch

(C

H)

Se

vett

ijarv

i (F

IN)

Skr

ea

da

len

(N

)

Bir

ken

es

(N)

Asp

vre

ten

(S

)

Ch

au

mo

nt

(CH

)

Mo

na

gre

ga

(E

)

Illm

itz (

A)

Ha

rwe

ll (G

B)

Ho

he

np

eis

sen

be

rg (

D)

Me

lpitz

(D

)

Isp

ra (

I)

Wa

asm

un

ste

r (B

)

Zu

eri

ch (

CH

)

Ba

sel (

CH

)

Lo

nd

on

-B (

GB

)

Le

ipzi

g 9

7-9

9 (

D)

Ge

nt

(B)

Bo

log

na

(I)

Ba

rce

lon

a (

E)

Be

rn (

CH

)

Lo

nd

on

-M (

GB

)

Wie

n (

A)

PM

2.5

(µg/

m³)

average

median

USA annual standard

Compliance with Compliance with air quality air quality standardsstandards


y = 0.57x

y = 0.85x

0

10

20

30

40

50

60

70

80

90

100

110

120

0 10 20 30 40 50 60 70 80 90 100 110 120

PM 10 (µg/m³)

PM

2.5

(µ

g/m

³)

Sevettijarvi (FIN)

Skreadalen (N)

Birkenes (N)

Chaumont (CH)

Waasmunster (B)

Gent (B)

Bologna (I)

Zuerich (CH)

Basel (CH)

Barcelona (E)

Bern (CH)

0%

20%

40%

60%

80%

100%

Se

vettija

rvi (

FIN

)

Skr

ea

da

len

(N

)

Bir

ken

es

(N)

Pu

y d

e D

om

e (

F)

Ch

au

mo

nt (C

H)

Mo

na

gre

ga

(E

)

Wa

asm

un

ste

r (B

)

Me

lpitz

96

-99

(G

)

Isp

ra (

I)

Zu

eri

ch (

CH

)

Ba

sel (

CH

)

Ge

nt (

B)

Bo

log

na

(I)

Ba

rce

lon

a (

E)

Be

rn (

CH

)

PMPM1010 vs. PM vs. PM2.52.5


Seasonality of PMSeasonality of PM2.52.5 and N and Naa


Aerosol chemical compositionAerosol chemical composition


Aerosol size-segregated chemistryAerosol size-segregated chemistry

0

2

4

6

8

10

12

14

16

18

0.05-0.09 0.09-0.16 0.16-0.30 0.30-0.60 0.60-1.0 1.0-1.8 1.8-3.1 3.1-6.2 6.2-9.9

aerodynamic diameter (µm)

dM

/dL

og

Dp

(µ

g/m

³)

BC

OM

unacc.

NH4

nssSO4

sea salt

min. dust

Gent, Belgium

Marseille, France


Aerosol environmental effectsAerosol environmental effects

human healthhuman health vegetation and materialsvegetation and materials visibilityvisibility climateclimate hydrological cyclehydrological cycle


Effects on human healthEffects on human health

Mechanisms by which ihalable atmospheric Mechanisms by which ihalable atmospheric particles affect human health are still poorly particles affect human health are still poorly known. Two types of interactions can however be known. Two types of interactions can however be identified:identified: mechanicalmechanical: : inflammation ofinflammation of tissues or receptors tissues or receptors

chemicalchemical: : inflammation ofinflammation of tissues or receptors, tissues or receptors, damages of cellular tissues, mutagenesis of cellsdamages of cellular tissues, mutagenesis of cells

COST action 633: Particulate matter: Properties relatedCOST action 633: Particulate matter: Properties relatedto health effectsto health effects http://cost.cordis.lu/src/action_detail.cfm?action=633http://cost.cordis.lu/src/action_detail.cfm?action=633


Effects on vegetationEffects on vegetationand materialsand materials

Are mainly due to chemical reactions of Are mainly due to chemical reactions of particulate matter deposited on the surfaces particulate matter deposited on the surfaces activated by water (dew, fog, precipitation)activated by water (dew, fog, precipitation)

The reaction products in solution can then The reaction products in solution can then produce damages to materials and produce damages to materials and vegetation tissues vegetation tissues


Damage to leavesDamage to leaves


Damage to materialsDamage to materialsPortal figure of Herten Castle, Germany (1702)Portal figure of Herten Castle, Germany (1702)

1908 1968


1

10

100

1000

1 10 100 1000

Concentration (µg/m3)

Vis

ibil

ity

(km

)

range of actualconcentrations

of aerosol inthe atmosphere

Effect on visibilityEffect on visibility


Visibility on a Visibility on a clear and a hazy clear and a hazy

dayday

Denver, Colorado


Ji Parana, Ji Parana, BrasilBrasil


Aerosol-climateAerosol-climate The atmospheric aerosol The atmospheric aerosol

influences the Earth’s influences the Earth’s climate in two ways:climate in two ways:

direct effectdirect effect: reflecting : reflecting the incoming solar the incoming solar radiation back to space;radiation back to space;

indirect effectindirect effect: acts as : acts as CCN favoring formation CCN favoring formation of clouds which can also of clouds which can also reflect solar radiation back reflect solar radiation back to space . to space .

Both these mechanisms Both these mechanisms exert a cooling effect on exert a cooling effect on climateclimateaerosol sources


Climate forcingsClimate forcings


0 5 10 15 20 25 30 35

-30

-20

-10

0

10

20

reff

T [

oC

]

m]

Thai pre-mons

Israel dust

Australia urbanINDOEX polluted

Amazon smoke

Suppression of precipitationSuppression of precipitation

highconcentration

of aerosol

low concentrationof aerosol

thresholdfor productionof precipitation

Ramanathan et al.,Science, 2001

Visible and InfraRed Sensor (VIRS)Satellite NASA-Tropical Rainfall Measuring Mission (TRMM)


Microstructure of cloudsMicrostructure of clouds

NOAA –AVHRR satellitered = larger dropletsyellow = smaller droplets

South AustraliaPort Augusta power plant

Port Pirie lead smelter

Adelaide port

oil refineries

Rosenfeld, Science, 2000


Review on aerosols in EuropeReview on aerosols in EuropeA European Aerosol Phenomenology. 1: physical characteristics of particulate A European Aerosol Phenomenology. 1: physical characteristics of particulate

matter at kerbside, urban, rural and background sites in Europematter at kerbside, urban, rural and background sites in EuropeVan Dingenen, R., F. Raes, J.-P. Putaud, U. Baltensperger, E. Brüggemann, A. Charron, Van Dingenen, R., F. Raes, J.-P. Putaud, U. Baltensperger, E. Brüggemann, A. Charron, M.C. Facchini, S. Decesari, S. Fuzzi, R. Gehrig, H.-C. Hansson, R.M. Harrison, C. M.C. Facchini, S. Decesari, S. Fuzzi, R. Gehrig, H.-C. Hansson, R.M. Harrison, C. Hüglin, A.M. Jones, P. Laj, G. Lorbeer, W. Maenhaut, F. Palmgren, X. Querol, S. Hüglin, A.M. Jones, P. Laj, G. Lorbeer, W. Maenhaut, F. Palmgren, X. Querol, S. Rodriguez, J. Schneider, H.Rodriguez, J. Schneider, H.ten Brink, P. Tunved, K. Tørseth, B. Wehner, E. ten Brink, P. Tunved, K. Tørseth, B. Wehner, E. Weingartner, A. Wiedensohler and P. WåhlinWeingartner, A. Wiedensohler and P. Wåhlin

Atmos. Environ., 38, 2561-2577 (2004)Atmos. Environ., 38, 2561-2577 (2004)

A European Aerosol Phenomenology. 2: chemical characteristics of particulate A European Aerosol Phenomenology. 2: chemical characteristics of particulate matter at kerbside, urban, rural and background sites in Europematter at kerbside, urban, rural and background sites in EuropePutaud, J.-P., F. Raes, R. Van Dingenen J.-P. U. Baltensperger, E. Brüggemann, M.C. Putaud, J.-P., F. Raes, R. Van Dingenen J.-P. U. Baltensperger, E. Brüggemann, M.C. Facchini, S. Decesari, S. Fuzzi, R. Gehrig, H.-C. Hansson, C. Hüglin, P. Laj, G. Lorbeer, Facchini, S. Decesari, S. Fuzzi, R. Gehrig, H.-C. Hansson, C. Hüglin, P. Laj, G. Lorbeer, W. Maenhaut, N. Mihalopoulos, K. Müller, X. Querol, S. Rodriguez, J. Schneider, G. W. Maenhaut, N. Mihalopoulos, K. Müller, X. Querol, S. Rodriguez, J. Schneider, G. Spindler, H.Spindler, H.ten Brink, K. Tørseth, B. Wehner and A. Wiedensohlerten Brink, K. Tørseth, B. Wehner and A. Wiedensohler

Atmos. Environ., 38, 2579-2595 (2004)Atmos. Environ., 38, 2579-2595 (2004)


Reviews on organic aerosolReviews on organic aerosol

Organic aerosol and global climate modelling: A reviewOrganic aerosol and global climate modelling: A review

Kanakidou, M., J. H. Seinfeld, S. N. Pandis, I. Barnes, F. J. Dentener, M. Kanakidou, M., J. H. Seinfeld, S. N. Pandis, I. Barnes, F. J. Dentener, M. C. Facchini, R. van Dingenen, B. Ervens, A. Nenes, C. J. Nielsen, E. C. Facchini, R. van Dingenen, B. Ervens, A. Nenes, C. J. Nielsen, E. Swietlicki, J.P. Putaud, Y. Balkanski, S. Fuzzi, J. Hjorth, G. K. Moortgat, Swietlicki, J.P. Putaud, Y. Balkanski, S. Fuzzi, J. Hjorth, G. K. Moortgat, R. Winterhalter, C. E. L. Myhre, K. Tsigaridis, E. Vignati, E. G. R. Winterhalter, C. E. L. Myhre, K. Tsigaridis, E. Vignati, E. G. Stephanou, J. WilsonStephanou, J. Wilson

Atmos. Chem. Phys., 5, 1053-1123 (2005)Atmos. Chem. Phys., 5, 1053-1123 (2005)

A critical assessment of the current state of knowledge and research A critical assessment of the current state of knowledge and research needs on the role of organic aerosols in the atmosphere, climate, needs on the role of organic aerosols in the atmosphere, climate, and global changeand global changeFuzzi, S., M.O. Andreae, B. Huebert, M. Kulmala, Fuzzi, S., M.O. Andreae, B. Huebert, M. Kulmala, T. Bond, M. Boy, S.J. T. Bond, M. Boy, S.J. Doherty, A. Guenther, M. Kanakidou, K. Kawamura, V.-M. Kerminen, U. Doherty, A. Guenther, M. Kanakidou, K. Kawamura, V.-M. Kerminen, U. Lohmann, U. Pöschl, L.M. RussellLohmann, U. Pöschl, L.M. RussellAtmos. Chem. Phys., 6, 2017-2038 (2006)Atmos. Chem. Phys., 6, 2017-2038 (2006)


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Atmospheric Chemistry Atmospheric aerosol, air quality and climate: from the local to the global...

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