atmospheric chemistry cloud multiphase processes and their impact on climate maria cristina facchini...
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Atmospheric ChemistryAtmospheric Chemistry
Cloud multiphase processes and their impact on climate
Maria Cristina Facchini Maria Cristina Facchini
Istituto di Scienze dell’Atmosfera e del Clima - C.N.R.Istituto di Scienze dell’Atmosfera e del Clima - C.N.R.
Bologna, ItalyBologna, Italy
Atmospheric ChemistryAtmospheric Chemistry
AcknowledgementsAcknowledgements
M. Mircea, S. Fuzzi, S. Decesari, E. MattaM. Mircea, S. Fuzzi, S. Decesari, E. Matta ISAC-CNR, Bologna, ItalyISAC-CNR, Bologna, Italy
R.J. CharlsonR.J. CharlsonUniversity of Washington, Seattle, USAUniversity of Washington, Seattle, USA
A. Nenes, J.A. SeinfeldA. Nenes, J.A. Seinfeld California Institute of Technology, Pasadena, USACalifornia Institute of Technology, Pasadena, USA
S.L. CleggS.L. CleggUniversity of East Anglia, Norwich, UKUniversity of East Anglia, Norwich, UK
M. KulmalaM. KulmalaUniversity of Helsinki, Helsinki, FinlandUniversity of Helsinki, Helsinki, Finland
E. TagliaviniE. TagliaviniUniversity of Bologna, ItalyUniversity of Bologna, Italy
Atmospheric ChemistryAtmospheric Chemistry
Clouds and climateClouds and climate Clouds are the most important factor Clouds are the most important factor
controlling the Earth albedo and hence the controlling the Earth albedo and hence the temperature of our planet temperature of our planet
Cloud optical properties are controlled by Cloud optical properties are controlled by size/number of droplets which in turn are size/number of droplets which in turn are governed by the “availability “ of aerosol governed by the “availability “ of aerosol particles to serve as CCNparticles to serve as CCN
Atmospheric ChemistryAtmospheric Chemistry
Clouds and climate 2Clouds and climate 2 Changes in cloud optical properties induced by man’s Changes in cloud optical properties induced by man’s
activity are at the moment highly uncertainactivity are at the moment highly uncertain
Atmospheric ChemistryAtmospheric Chemistry
Parameters influencing CDNParameters influencing CDN Many years ago, Twomey suggested that the Many years ago, Twomey suggested that the
most important parameter influencing cloud most important parameter influencing cloud droplet number (CDN) is aerosol number droplet number (CDN) is aerosol number concentration, while aerosol chemical concentration, while aerosol chemical composition has a relatively minor effectcomposition has a relatively minor effect
Recently, model and experimental results Recently, model and experimental results have induced to revisit this assumption and to have induced to revisit this assumption and to re-examine the relative importance of the re-examine the relative importance of the different factors influencing CDN distributiondifferent factors influencing CDN distribution
Atmospheric ChemistryAtmospheric Chemistry
CDN and aerosol number CDN and aerosol number
The number of CDN is The number of CDN is not a “linear” function of not a “linear” function of aerosol number aerosol number (Ramanathan et (Ramanathan et alal., ., ScienceScience, 2001), 2001)
The large degree of The large degree of variation suggests that variation suggests that cloud properties are cloud properties are controlled by many controlled by many different factors different factors
Atmospheric ChemistryAtmospheric Chemistry
The issue The issue
how does the chemistry of the cloud how does the chemistry of the cloud multiphase system influence multiphase system influence formation and evolution of the formation and evolution of the cloud droplet population ?cloud droplet population ?
Atmospheric ChemistryAtmospheric Chemistry
RH
Dry particlewet aerosol
Cloud droplet
gas phase
R R
……an intuitive picture of cloud an intuitive picture of cloud chemistrychemistry
Absorbing material
Soluble fraction chemical composition
Atmospheric ChemistryAtmospheric Chemistry
Cloud formationCloud formation
Atmospheric thermodynamic Atmospheric thermodynamic parameters (moisture availability, parameters (moisture availability, updraft velocity, temperature, etc.)updraft velocity, temperature, etc.)
Aerosol properties: Aerosol properties: classically, the classically, the controlling chemical variables are controlling chemical variables are CCN size distribution and water CCN size distribution and water soluble masssoluble mass
Atmospheric ChemistryAtmospheric Chemistry
Theory of cloud formationTheory of cloud formation
TrR
vas
g
ww
2exp
aw = water activity = surface tensionw = water molar volume
Atmospheric ChemistryAtmospheric Chemistry
Water activityWater activity
1000exp
mww
Ma
orginorgorgorginorginorga
orginorgorgorginorginorg
wgas
waer
wgaswaerw
a
aaa
? ?for inorganic aqueouselectrolytic solutions
Only one paper:Clegg et al.,J. Aerosol Sci.,2001
Atmospheric ChemistryAtmospheric Chemistry
Modified Köhler equationModified Köhler equation
norginorg jj
jj
ii
ii
Ns
sw
w
ws
M
m
Mm
rr
MrRT
Ms
)(4
321 33
Kelvin term
Raoult term
Atmospheric ChemistryAtmospheric Chemistry
Chemical factors controlling cloud Chemical factors controlling cloud formationformation
Not simply inorganic soluble salts Not simply inorganic soluble salts influence cloud formationinfluence cloud formation
Soluble or slightly soluble organics Soluble or slightly soluble organics influence equilibrium water vapor influence equilibrium water vapor pressure and decrease surface tension pressure and decrease surface tension of the dropletsof the droplets
Soluble gases condensation Soluble gases condensation ((Charlson et al., Charlson et al., Science 2001Science 2001))
Atmospheric ChemistryAtmospheric Chemistry
Aerosol chemical compositionAerosol chemical composition
Spring - Summer
SO414%
other ions9%
NO311%
NH47%
WSOC18%
WINC19%
unk22%
Atmospheric ChemistryAtmospheric Chemistry
Organic aerosols andOrganic aerosols andKöhler theoryKöhler theory
Organic aerosols influence Organic aerosols influence equilibrium supersaturation by:equilibrium supersaturation by:““adding” soluble materialadding” soluble materialdecreasing surface tension with respect to pure decreasing surface tension with respect to pure
water or an inorganic salt solutionwater or an inorganic salt solution
Atmospheric ChemistryAtmospheric Chemistry
Speciation of organic aerosolSpeciation of organic aerosol
The traditional analytical approach has The traditional analytical approach has usually been individual compound usually been individual compound speciation, but less than 10% of OC mass speciation, but less than 10% of OC mass has been accounted forhas been accounted for
A new method using functional group A new method using functional group analysis has been developed which accounts analysis has been developed which accounts for up to 90% of OC mass for up to 90% of OC mass (Decesari et (Decesari et alal., ., J. Geophys. ResJ. Geophys. Res., 2000)., 2000)
Atmospheric ChemistryAtmospheric Chemistry
Organic solutes in cloudsOrganic solutes in clouds WSOC are a complex mixture of highly oxidised, WSOC are a complex mixture of highly oxidised,
multifunctional compounds with residual aromatic multifunctional compounds with residual aromatic nuclei and aliphatic chainsnuclei and aliphatic chainsNeutral compoundsNeutral compounds: mainly aliphatic polyols, polyethers, : mainly aliphatic polyols, polyethers,
sugars;sugars;Mono-/di-acidsMono-/di-acids: hydroxylated aliphatic acidic compounds;: hydroxylated aliphatic acidic compounds;PolyacidsPolyacids: unsaturated polyacidic compounds both : unsaturated polyacidic compounds both
aliphatic and aromatic with a minor content of hydroxyl aliphatic and aromatic with a minor content of hydroxyl groupsgroups
This information can be used to construct a set of This information can be used to construct a set of model compoundsmodel compounds
Atmospheric ChemistryAtmospheric Chemistry
Why model compounds?Why model compounds?
Too often the physical and chemical Too often the physical and chemical properties of atmospheric OC are simulated properties of atmospheric OC are simulated in models using compounds which are not in models using compounds which are not representative of the physical realityrepresentative of the physical reality
Modellers need a synthetic information of a Modellers need a synthetic information of a few model compounds which can be used to few model compounds which can be used to simulate in a quantitative way the whole simulate in a quantitative way the whole OC of aerosol and cloudsOC of aerosol and clouds
Atmospheric ChemistryAtmospheric Chemistry
CHCH22 CHCH33
38 %38 %
CHCH
OHOH
31 %31 %9 %9 %OO
CC CHCH22CHCH22
21 %21 %
ArAr
8 %8 %
CHCH
HOHO
9 %9 %
CHCH22 CHCH22
42 %42 %
CHCH22
OHOH
OO
41 %41 %
ArAr
50 %50 %
CHCH
HOHO
5 %5 %
CHCH22 CHCH22
23 %23 %
CHCH22OHOH
OO
23 %23 %
ArAr
neutral fractionneutral fraction
mono-/di-acidsmono-/di-acids
polyacidspolyacids
(Fuzzi et al., GRL, 2001)
Atmospheric ChemistryAtmospheric Chemistry
Modified Köhler equationModified Köhler equation
norginorg jj
jj
ii
ii
Ns
sw
w
ws
M
m
Mm
rr
MrRT
Ms
)(4
321 33
Kelvin term
Atmospheric ChemistryAtmospheric Chemistry
C(mol l-1)
1e-4 1e-3 1e-2 1e-1
(m
N m
-1)
50
55
60
65
70
75
Surface tension measurements Surface tension measurements
cloudTenerifeACE-2
fogPo Valley
cloud ACE-ASIA
= K - T ln (1+ C)
Atmospheric ChemistryAtmospheric Chemistry
0.1 1 10
Sa
tura
tion
ra
tio
0.999
1.000
1.001
1.002
1.003
1.004
1.005
1.006
0.05 m
0.1 m
0.3 m
inorganic only
inorganic+organic
inorganic+organic+
Effect of organics on SEffect of organics on Scc
fromMircea et al.,Tellus, 2001
Atmospheric ChemistryAtmospheric Chemistry
Trace gas dissolutionTrace gas dissolution
Laaksonen et al., JAS, 1998
HNO3
Atmospheric ChemistryAtmospheric Chemistry
Modelling of chemical effectsModelling of chemical effects
marine case polluted case
-0.04
-0.02
0.00
0.02
0.04
0.06
0.08
Max
imum
alb
edo
chan
ge,
R*
10 cm/s
30 cm/s
100 cm/s
300 cm/s
insoluble
organicno
organicwith
5 ppbHNO3
2conc.
0.1 m s-1
0.3 m s-1
1.0 m s-1
3.0 m s-1
-0.04
-0.02
0.00
0.02
0.04
0.06
0.08
R*
10 cm/s
30 cm/s
100 cm/s
300 cm/s
insoluble
organicno
organicwith
5 ppbHNO3
2conc.
Max
imum
alb
edo
chan
ge,
R*
0.1 m s-1
0.3 m s-1
1.0 m s-1
3.0 m s-1
(Nenes et al., GRL in press)
Atmospheric ChemistryAtmospheric Chemistry
0.1 m/s
1 m/s
10 m/s
CCN(m-3)
1e+8 1e+9
z(m
)
0
100
200
300
400
500
Effect of size segregated Effect of size segregated chemical compositionchemical composition
See poster Mircea et al., Session B
Dotted line: bulk compositionSolid line: size-segr. compostion
Atmospheric ChemistryAtmospheric Chemistry
Water activity of Water activity of multicomponent solutionsmulticomponent solutions
data fromClegg et al.,J. Aerosol Sci.,2001r(m)
0.1 1 10
satu
ratio
n m
ixin
g ra
tio
1.000
1.002
1.004
1.006
1.008
1.01070% lectovicite+30% maleic acid
0.05 m
0.1 m
modifiedKoher theory
aw Cleggtreatment
as above +measured
Atmospheric ChemistryAtmospheric Chemistry
Conclusions Conclusions
Dissolution of gases, dissolution of soluble Dissolution of gases, dissolution of soluble and slightly soluble organics and the and slightly soluble organics and the associated decrease of associated decrease of influence droplet influence droplet populationpopulation
There are many conditions in the There are many conditions in the atmosphere in which chemical factors atmosphere in which chemical factors influence/control cloud microphysics to the influence/control cloud microphysics to the same extent as cloud dynamics and/or same extent as cloud dynamics and/or aerosol number concentration aerosol number concentration
Atmospheric ChemistryAtmospheric Chemistry
……still neededstill needed
data on physical and chemical properties of data on physical and chemical properties of aerosol are needed for different areas and aerosol are needed for different areas and aerosol typesaerosol types
thermodynamic data and models of thermodynamic data and models of aaww for for the complex cloud droplet solutions are the complex cloud droplet solutions are neededneeded
Atmospheric ChemistryAtmospheric Chemistry
Model compounds molar Model compounds molar composition (%)composition (%)
pinonaldehyde 16pinonaldehyde 16levoglucosan 9levoglucosan 9catechol 2catechol 2azelaic acid 14azelaic acid 14hydroxy-benzoic acid 15hydroxy-benzoic acid 15-hydroxy-butyric acid 3-hydroxy-butyric acid 3fulvic acid 41fulvic acid 41
(Fuzzi et al., GRL, in press)
Atmospheric ChemistryAtmospheric Chemistry
Models neutral compoundsModels neutral compounds
pinonaldehydepinonaldehydehydratedhydrated
levoglucosanlevoglucosan
cathecolcathecol
OH
OH
O
OHHO
OO
HO
HO
HO
Atmospheric ChemistryAtmospheric Chemistry
Models mono-/di-acidsModels mono-/di-acids
azelaic acidazelaic acid
-hydroxy-butyric acid-hydroxy-butyric acidhydroxy-benzoic acidhydroxy-benzoic acid
HO
O
OH
O
HO O
OH
OH
OH
O
Atmospheric ChemistryAtmospheric Chemistry
HO OO
OH
OH
O
OH
OOOHO
O
OOH
OH
O
Model polyacidsModel polyacids
fulvic acidfulvic acid