Perrone M.G.1, Larsen B.R.2, Ferrero L.1, Sangiorgi G.1, De Gennaro G.3, Udisti R.4, Zangrando R.5, Gambaro A.5,6and Bolzacchini E.1
1Research Center POLARIS, University of Milano-Bicocca, DISAT, P.zza della Scienza 1, 20126 Milan
2European Commission Joint Research Center, IHCP, Via E. Fermi 2749, Ispra (VA) 21020, Italy
3Department of Chemistry, University of Bari, Via Orabona 4, 70126 Bari, Italy
4Department of Chemistry, University of Florence, Via della Lastruccia 3, 50019 Sesto F.no, Florence
5Institute for the Dynamics of Environmental Processes-CNR, Dorsoduro 2137, 30123 Venice, Italy
6Department of Environmental Sciences, University of Venice, Santa Marta 2137, 30123, Venice, Italy contact author: grazia.perrone@uimib.it
Chemical mass balance modelling for the source estimation of high PM2.5 concentrations in Milan, Northern Italy
SAMPLING SITES SAMPLING SITES
EAC-2012 European Aerosol Conference 2012, 2-7 Sept 2012, Granada
urban site, Milano (MI) rural site, Oasi Le Bine (OB)
remote mountain site, Alpe S. Colombano (ASC)
SO4=
8.9
NO3- 29.8
NH4+
12.3 Ca++, Mg++
1.1 K+
0.6 Fe,Al,Zn
1.1 trac e elements 0.5 OM 34.5 EC 13.2 unaccounted
-2.1
MI-SPRING
SO4=
22.4
NO3- 3.6
NH4+
11.6 Ca++, Mg++
0.6 K+
0.5 Fe,Al,Zn
2.9 trace elements 0.4 OM 30.6 EC 14.6
unaccounted 12.8
MI-SUMMER
SO4=
4.5 NO3- 17.2
NH4+
6.4
Ca++, Mg++
0.5 K+
0.8
Fe,Al,Zn 2.2 trace elements 0.4 OM 34.5 EC 13.2
unaccounted 20.4
MI-FALL
SO4=
6.4
NO3- 20.6
NH4+
9.1 Ca++, Mg++
0.3 K+
1.0 Fe,Al,Zn
0.9 trace elements 0.4 OM 38.4 EC 11.8
unac counted 11.1
MI-WINTER
SO4=
16.9
NO3- 21.7
NH4+
14.6 Ca++, Mg++
0.6 K+
0.7 Fe,Al,Zn
1.8 trace elements 0.2
OM 30.3 EC 4.0
unaccounted 9.2
OB-SPRING
SO4=
28.9
NO3- 3.7 NH4+
15.8 Ca++, Mg++
0.7 K+
0.6 Fe,Al,Zn
3.2 trace elements 0.3
OM 30.3 EC 4.9
unaccounted 11.5
OB-SUMMER
SO4=
8.2
NO3- 28.4
NH4+
10.8 Ca++, Mg++
0.2 K+
0.9 Fe,Al,Zn
1.2 trace elements 0.3
OM 30.3 EC 4.0
unacc ounted 15.6
OB-FALL
SO4=
8.4
NO3- 26.1
NH4+
12.0 Ca++, Mg++
0.3 K+
1.2 Fe,Al,Zn
0.8 trace elements 0.4
OM 30.4 EC 3.1
unac counted 17.2
OB-WINTER
SO4=
23.9
NO3- 6.1
NH4+
14.8 OM 43.4 EC 1.6 unaccounted
4.4 ASC-SPRING
SO4=
22.8
NO3- 2.7
NH4+
13.2
Ca++, Mg++
Fe,Al,Zn trace
OM 37.0 EC 1.9 unaccounted
4.9 ASC-SUMMER
SO4=
12.2 NO3- 6.8 NH4+
4.6 Ca++, Mg++
0.3
K+
0.2 Fe,Al,Zn
12.3
trace OM
49.8 EC 1.4 unaccounted
11.5
ASC- WINTER
CHEMICAL COMPOSITION OF PM2.5 CHEMICAL COMPOSITION OF PM2.5
urban
rural
remote OM (OC ×1.6)
OM (OC ×1.8)
OM (OC ×2.1)
OM SPECIATION OM SPECIATION
2.4 8.0
1.5 2.2
0 2 4 6 8 10 12
SPRING SUMMER FALL WINTER
%OM
C2-C5 DICARBOXYLIC ACIDS MI
0.4 0.3
0.8 0.7
0.0 0.2 0.4 0.6 0.8 1.0
SPRINGSUMMER FALL WINTER
%OM
n-ALKANES MI
0.04 0.04 0.12 0.15
0.0 0.1 0.2 0.3 0.4 0.5
SPRINGSUMMER FALL WINTER
%OM
PAHs MI
1.2 0.5
8.6
4.6
0 2 4 6 8 10
SPRING SUMMER FALL WINTER
%OM
LEVOGLUCOSAN MI
10.2 10.4
2.8 2.8
0 2 4 6 8 10 12
SPRING SUMMER FALL WINTER
%OM
C2-C5 DICARBOXYLIC ACIDS OB
0.3 0.4 0.6
0.9
0.0 0.2 0.4 0.6 0.8 1.0
SPRINGSUMMER FALL WINTER
%OM
n-ALKANES OB
0.04 0.01
0.09 0.38
0.0 0.1 0.2 0.3 0.4 0.5
SPRINGSUMMER FALL WINTER
%OM
PAHs OB
0.7 0.2
7.4
5.0
0 2 4 6 8 10
SPRING SUMMER FALL WINTER
%OM
LEVOGLUCOSAN OB
10.2 10.6
2.2 2
4 6 8 10 12
%OM
C2-C5 DICARBOXYLIC ACIDS ASC
0.1 0.6
0.7
0.2 0.4 0.6 0.8 1.0
%OM
n-ALKANES ASC
0.1 0.2 0.3 0.4 0.5
%OM
PAHs ASC
2 4 6 8 10
%OM
LEVOGLUCOSAN ASC
urban
rural
remote In Europe, the recent Air Quality Directive (2008/30/CE)
establishes an annually averaged PM2.5 concentration of 25 µg m-3, which will be the legal limit value from 2015
onwards. With the aim of designing effective PM2.5 reduction strategies, information on the strength of
impacting sources is required.
INTRODUCTION INTRODUCTION
Daily low volume gravimetric sampling (2006-09) at a:
See
See forfor referencereference::
Perrone MG et al. , 2012 “Sources of high PM2.5 concentrations in Milan, Northern Italy: Molecular Marker data and CMB modelling”
Science of the Total Environment 414, 343-345
Ca++, Mg++
1.7 K+
0.6 Fe,Al,Zn
3.1 trace elements 0.2
Ca++, Mg++
K+ 1.6 0.4 Fe,Al,Zn trace 14.7 elements 0.8
trace elements 0.9
0 2
SPRING SUMMER WINTER
0.1 0.0 0.2
SPRINGSUMMER WINTER
0.02 0.00 0.02
0.0 0.1
SPRINGSUMMER WINTER
0.2 0.1 0.4
0 2
SPRING SUMMER WINTER
THE SOURCE
THE SOURCE APPORTIONMENT STUDY APPORTIONMENT STUDY
Receptor model :Chemical Mass Balance CMB (CMB 8.2 EPA)
5 primary sources:
- traffic TR
- biomass burning BB
- natural gas combustion NGC - resuspension ROAD DUST RD - plant debris PD
13 fitting species:
* EC
* elements: Al, Fe, Pb, Si
* 8 trace organic markers: levoglucosan, PAHs (BbF, BkF, BeP, IcdP, BghiP), n-alkanes (C29, C31)
Result
Result--1 OC source estimation 1 OC source estimation
0 2 4 6 8 10 12 14 16 18
Sp Su F W Sp Su F W Sp Su W
MI OB ASC
OC (µµµµg m-3)
primary organic carbon (POC) : CMB-POC secondary organic carbon (SOC):
CMB-SOC = Total OC – CMB-POC
Result
Result--2 PM.5 source estimation 2 PM.5 source estimation
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
SP SU F W SP SU F W SP SU W
MI OB ASC
PM2.5 (µµµµg m-3)
secundary ammonium secundary nitrate secundary sulphate CMB-SOA sea salt RD PD NGC BB TR 95%
81%
87%
80%
87%
75%
88% 79%
68% 79%
73%
secondary organic aerosol (SOA):
CMB-SOA = ambient OM – CMB-POM
CONCLUSION
The TR contribuition to [OC] was 40-60% at the MI urban site (all seasons)
The seasonal contribution ofBBsources to [OC] was 70-80%
during fall(F) and winter(W) at OB rural site
70-95% of PM2.5 concentration was apportioned by sources At the urban and the rural site:
45-65% of PM2.5 from primary sources in F-W 65-75% of PM2.5 from secondary sources in SP-SU At the ASC remote site:
60-90%of PM2.5 from secondary sources (SOA: 30-40%) The contribution of major pollution sources to ambient PM2.5 at
three sites in Northern Italy were estimated by CMB model.
In Milan, TR was the strongest primary source (17-24%) for PM2.5, together with secondary inorganic and organic aerosol
(21-54%) and BB including residential heating (1-30%).
