PM10
“Contribution of natural sources to PM levels in Europe” JRC ISPRA, 12th-13th October 2006
CONTRIBUTION OF NATURAL SOURCES TO AIRBORNE PARTICULATE MATTER IN CENTRAL ITALY
Ivo ALLEGRINI, Cinzia PERRINO C.N.R. Institute of Atmospheric Pollution Montelibretti (Rome)
NATURAL SOURCES sea-spray, volcanoes, desert dust, biogenic aerosol DESERT DUST Amount: 80-120 million tons /year from Sahara to Europe Main sources: Algeria, Morocco, Lybia, Tunisia Average duration of the events: 2-4 days Deposition: 5-15 g/m2 per year CONTRIBUTION OF NATURAL SOURCES TO PM Models (trajectories: HYSPLIT, DREAM) Dust profile detection (LIDAR) Statistical methods (source apportionment) Study of the meteorological situation Number and dimensions of particles Chemical analysis C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
Chemical analysis of macrocomponents
Only a few components constitutes more than 1% of PM: ¾ A few metals: Al, Si, Fe ¾ The main anions: Cl-, NO3-, SO4=, CO3¾ The main cations:Na, NH4+, K+, Mg++, Ca++ ¾ Elemental carbon ¾ Organic material (20-60% of PM but hundreds of species)
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
“Fine Dust” A research project funded by the Lazio Region October 2004 – July 2005 (daily sampling – analysis of the 140 most interesting days) MONTELIBRETTI semi-rural station VITERBO urban station FONTECHIARI regional background station
ROMA VILLA ADA urban background station
ROMA MONTEZEMOLO traffic station
C. Perrino
LATINA urban station
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
3-step procedure: 1.
Mixing properties of the lower atmosphere Natural radioactivity monitoring
2. Size distribution of particulate matter Optical particle counter
3. Chemical composition of particles Analysis of metals, ions, carbon compounds
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 1: Mixing properties of the lower atmosphere URANIUM238 DECAY CHAIN
PBL MIXING MONITOR
RADON
222
[φ (t )] ≅ k SHORT-LIVED RADON PROGENY (β DECAY)
PM10 MASS CONCENTRATION - urban background station 70 60
ug/m3
50 40 30 20 10 0 15
16
17
18
19
20
21
22
23
24
25
DECEMBER 2003
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
26
27
28
29
30
31
During warm months natural radioactivity shows a well-defined and modulated temporal pattern (all days are similar: nocturnal stability and convective mixing during the day)
NATURAL RADIOACTIVITY 2500
COUNTS / MINUTE
During cold months high-pressure periods are sporadic and advection often occurs. Diurnal mixing is weak and of limited duration.
2000
1500
1000
500
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
DECEMBER
STEP 1: Mixing properties of the lower atmosphere
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 1: Mixing properties of the lower atmosphere
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 1: Mixing properties of the lower atmosphere Starting from natural raadioactivity values we can develop Atmospheric Stability Indexes… PM10 ROMA - Villa Ada 90 SPERIMENTALE EXPERIMENTAL FORECASTED PREVISTO
80 70
μg / m
3
60 50 40 30 20 10 0 GENNAIO, NOVEMBRE, DICEMBRE 2004
… for each day, they give the probability, from the meteorological point of view, for the occurrence of an atmospheric pollution event C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 1: Mixing properties of the lower atmosphere PM10 ROMA - VILLA ADA 100 90
sperimentale EXPERIMENTAL
80
FORECASTED previsto ISA
μg/m
3
70 60 50 40
In the case of natural events
30
(e.g. desert dust)
10
20
0
the values of the
1
2
3
4
5
6
Atmospheric Stabilty Index do not match PM concentration
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
7
8
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 DICEMBRE 2004
STEP 1: Mixing properties of the lower atmosphere N A T U R AL R AD IO A C T IV IT Y 350 0
300 0
Night-time stability
250 0
200 0
150 0
100 0
50 0
0 1
2
3
4
5
6
7
8
9
10 1 1 1 2 1 3 14
15
16 1 7 1 8 1 9 20
O T T OTTOBRE O B R E 20 04
21
22
23 2 4 2 5 26
27
28
29 3 0 3 1
2004
N A T U R AL R AD IO A C T IV IT Y 3 5 00
3 0 00
2 5 00
Nighttime and daytime stability
2 0 00
1 5 00
1 0 00
5 00
0 1
C. Perrino
2
3
4
5
6
7
8
9
advection
1 0 1 1 12 13 14 1 5 1 6 1 7 18 19 20 21 2 2 2 3 2 4 2 5 26 27 28 2 9 3 0 3 1 D ICE M B R E 22004 0 04 DICEMBRE
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
VILLA ADA - PM10
80
80
70
70
60
60
50
50
40
40
30
30
20
20
10
10
0
0
GENNAIO GENNAIO
FEBBRAIO FEBBRAIO
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29
VILLA ADA - PM10
VILLA ADA - PM10
50
40
40
30
30
A N N O
20
20
10
10
0
0
AGOSTO AGOSTO
LUGLIO LUGLIO
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
VILLA ADA - PM10
VILLA ADA - PM10 50
50
40
40
40
30
30
30
20
20
20
10
10
50
70
VILLA ADA - PM10
VILLA ADA - PM10 50
3
90
μg/m
μg/m
3
VILLA ADA - PM10 90
60
3
40
μg/m
μg/m
3
50
30 20
10
10 0
0
MARZO MARZO
APRILE APRILE
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
VILLA ADA - PM10
VILLA ADA - PM10 50
50
40
40
30
0
0
SETTEMBRE
OTTOBRE OTTOBRE
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 SETTEMBRE
VILLA ADA - PM10
VILLA ADA - PM10
100
70
90 60
80 50
70 60
40
μg/m
3
30
2 0 0 4
50 30
40
20
20
30
20
10
10
0
0
MAGGIO
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 MAGGIO
20 10
10 0
0
GIUGNO GIUGNO
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
NOVEMBRE NOVEMBRE
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
WINTERTIME STABILITY (night and day) SUMMERTIME STAILITY (nigth) SAHARAN DUST (DREAM model) C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
DICEMBRE DICEMBRE
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
FIRST REMARK
The mixing properties of the lower atmosphere are a key factor in determining PM concentration level and its time variations An increase of PM concentration during advection conditions may indicate a natural event C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
3-step procedure: 1. Mixing properties of the lower atmosphere
Natural radioactivity monitoring 2. Size distribution of particulate matter
Optical particle counter 3. Chemical composition of particles
Analysis of metals, ions, carbon compounds
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 2: Size distribution of particulate matter Optical Particle Counter 70000
1400
0.3 - 0.5 µ
60000
1200
> 1.5 m
in the coarse ( > 1,5 μm) and the fine (0,3 – 0,5 μm)
N / litro
between the number of particles
1000
40000
800
30000
600
20000
400
10000
200
0
0 8-Oct
ranges:
9-Oct
10-Oct
11-Oct
12-Oct
13-Oct
14-Oct
Optical Particle Counter 0.12
An increase of this ratio indicates a natural event
Rapporto >1.5 m / 0.3 - 0.5 m 0.10
0.08
0.06
0.04
0.02
0.00 8-Oct
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
9-Oct
10-Oct
11-Oct
12-Oct
13-Oct
14-Oct
N / litro
Evaluation of the ratio
50000
STEP 2: Size distribution of particulate matter S IZ E R A T IO :
> 1 .5 / 0 .3 -0 .5
10 9 8
Daily average ratio
R * 100
7 6 5 4 3
between the number of particles
2 1 0 1
in the coarse ( > 1,5 μm)
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 O C TO B E R 2004 S IZ E R A T IO :
> 1 .5 / 0 .3 -0 .5
10
and the fine (0,3 – 0,5 μm)
9 8
ranges
R * 100
7 6 5 4 3 2 1 0 1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 N O V E M B E R 2004 S IZ E R A T IO :
> 1 .5 / 0 .3 -0 .5
10
IDENTIFICATION OF
9 8
NATURAL EVENTS
R * 100
7 6 5 4 3 2 1 0
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 D E C E M B E R 2004
3-step procedure: 1. Mixing properties of the lower atmosphere
Natural radioactivity monitoring 2. Size distribution of particulate matter
Optical particle counter 3. Chemical composition of particles
Analysis of metals, ions, carbon compounds
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles
Crustal metals
PM10
PM2.5
Teflon filter
Quartz filter
ED-XRF
Termooptical analyser
Organic carbon Elemental carbon
Extraction
Ion chromatography
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
Anions and cations
STEP 3: Chemical composition of particles
Chemical characterisation: 1. Anions and cations
Ion chromatography (IC)
(NO3-, SO4=, Cl-, Na+, Ca++, Mg++, K+, NH4+)
2. Elemental carbon and organic carbon compounds (EC, OC)
Termo-optical analyser
3. Crustal metals (major components) (Si, Al, Fe, Ca, K)
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
X-ray fluorescence (ED-XRF)
MASS CONCENTRATION OF PM10 IN MONTELIBRETTI (ROME) MEASURED BY THE DUST MONITOR (blue) AND RECONSTRUCTED BY THE CHEMICAL ANALYSES (red)
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles
4 main sources [sea-spray aerosol] = (Na+ + Cl-) * 1.176
[SO4= Mg Ca K]
[crustal] = (1.89 Al + 2.14 Si + 1.4 Ca + 1.2 K + 1.36 Fe) * 1.12 [primary anthropogenic compounds] = EC * 2
[OM]
[secondary compounds] = NH4+ + SO4= + NO3- + (OM – EC)
OM = α OC C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
α = 1.6 ÷ 2.1
[Mg Na Ti]
STEP 3: Chemical composition of particles
100 PRIM. ANTHR. COMP.
90
SECONDARY COMP.
CONCENTRAZIONE (µg/m3)
80
SEA-SALT CRUSTAL MATTER
70 60 50 40 30 20 10 0 PM10 - ROME TRAFFIC STATION
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles
CONCENTRAZIONE DI SALE MARINO - ROMA MONTEZEMOLO 12
(µg/m3)
10 8 6 4 2 C.N.R. Institute of Atmospheric Pollution – Rome0 (ITALY)
STEP 3: Chemical composition of particles
Sea-spray events: • NaCl concentration increases from 1-2% to 20-40% • the coarse/fine ratio increases • they occur in advection conditions (generally clean air masses) • PM10 concentretion is low; the increase due to sea-salt is generally < 10 ug/m3 • generally they do no cause exceedances • they have low impact on PM2.5 concentration
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles
CONCENTRAZIONE DI CRUSTALE - LATINA TASSO
60
(µg /m 3)
50 40 30 20 10 C.N.R. Institute of Atmospheric Pollution – Rome (ITALY) 0
STEP 3: Chemical composition of particles
Saharan dust events: • crustal matter concentration increases from 10-20% to over 50% • the coarse/fine ratio increases • they begin in advection conditions (but re-suspension may increase the time
duration of the episode) • PM10 concentretion can be very high (up to more than 100 ug/m3) • they often cause exceedances • they also generally cause an increase of PM2.5 concentration
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles S IZ E R A T IO :
> 1 .5 / 0 .3 -0 .5
10 9
38.0 μg/m3
8
R * 100
7
58.8 μg/m3
6 5 4 3
IDENTIFICATION
2 1 0
AND
1
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
S IZ E R A T IO :
> 1 .5 / 0 .3 -0 .5
10 9 8 7 R * 100
NATURAL
3
O C TO B E R 2004
CHARACTERISATION OF
2
6 5 4 3 2
EVENTS:
1 0 1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 N O V E M B E R 2004 S IZ E R A T IO :
SEA-SPRAY
10
146.4 μg/m3
9 8 7 R * 100
AFRICAN DUST
> 1 .5 / 0 .3 -0 .5
6 5 4 3 2 1 0
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 D E C E M B E R 2004
SECOND REMARK
Natural events can be identified from an increase of the coarse-to-fine ratio The nature of the event is detected by the chemical analysis
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 3: Chemical composition of particles CARBONIO ELEMENTARE - LAZIO 30
%ECNEL PM.2.5
25 20 15 10 5 0
ELEMENTAL CARBON
OT T OBRE 2004 - LUGLIO 2005
PRIMARY ANTHROPOGENIC POLLUTANTS
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 3: Chemical composition of particles
Average % composition of PM10 in the Lazio region C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
THIRD REMARK
For primary anthropogenic pollutants we cannot identify “events” Their concentration depends on the proximity to the emission sources and their concentration variations mainly depend on the dispersion capacity of the lower atmosphere
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 3: Chemical composition of particles SOLFATO NEL PM 10 - LAZIO
SULPHATE
% SOLFATO NEL PM10
30
20 15 10 5 0
SECONDARY
OTTOBRE 2004 - LUGLIO 2005
SECONDARY PM CONCENTRATION - ROME TRAFFIC STATION
POLLUTANTS
60 CONCENTRATION (µg/m3)
C. Perrino
25
48 36 24 12 0
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 3: Chemical composition of particles
Average % composition of PM10 in the Lazio region C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles
PM10 SEA SALT CRUSTAL MATTER PRIMARY ANTHROP. SECOND. ORGANIC SECOND. INORGANIC
CONCENTRATIO N (µg/m3 )
50
40
30
20
10
0 ROME TRAFFIC
ROME URBAN BACKGROUND
SEMI-RURAL
REGIONAL BACKGROUND
Secondary pollutants are homogeneously distributed at least on a regional scale. C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
FOURTH REMARK
For secondary pollutants we cannot identify “events” Their concentration is homogeneous on a regional scale and their concentration variations mainly depend on the dispersion capacity of the lower atmosphere
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
AFRICAN DUST OUTBREAK - JUNE 2006
June 16
June 22
June 29 C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
June 24
July 2
AFRICAN DUST OUTBREAK - JUNE 2006
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
AFRICAN DUST OUTBREAK - JUNE 2006
Montelibretti - PM 10 100
80
AUTOMATIC MONITOR SUM OF CHEMICAL DETERMINATIONS
3
CONCENTRATION (µg/m )
90
70 60 50 40 30 20 10 0 1 2 3 4 5 6 7 8 9 1011 12 1314 15 1617 18 1920 21 2223 24 2526 27 2829 30 1 2
June - July 2006
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
AFRICAN DUST OUTBREAK - JUNE 2006 MONTELIBRETTI – PM10 80 70
CONCENTRATION (µg/m3)
60
SEA-SPRAY PRIMARY ANTHROP. SECONDARY ORG. SECONDARY INORG. CRUSTAL
50 40 30 20 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 1 2
JUNE - JULY 2006
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
AFRICAN DUST OUTBREAK - JUNE 2006 19 GIUGNO 2006 - PM10: 40.1 μg/m
3
ORG. SEC. 34%
INORG. SEC. 13%
MARE 1%
ANTR. PRIM. 11% CRUSTALI 41%
28 GIUGNO 2006 - PM10: 86.5 μg/m3
INORG. SEC. 16%
ORG. SEC. 17% ANTR. PRIM. 5%
MARE 1%
INORG. SEC. 34%
1 LUGLIO 2006 - PM10: 59.6 mg/m3 ORG. SEC. 19%
CRUSTALI 61%
SO4=: 22 % 90 80
MARE 2%
ANTR. PRIM. 5% CRUSTALI 40%
CONCENTRAZIONE (µg/m3)
70
AEROSOL MARINO ANTROP. PRIMARI SECONDARI ORG. SECONDARI INORG. CRUSTALI
60 50 40 30 20 10 0
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
17/6 18/6 19/6 20/6 21/6 22/6 23/6 24/6 25/6 26/6 27/6 28/6 29/6 30/6 1/7 GIUGNO - LUGLIO 2006
2/7
… some answers ….but many questions….
Re-suspension of deposited desert dust: still a natural event? Desert dust particles coated with anthropogenic sulphate: are
they natural? THANK YOU FOR YOUR ATTENTION !
Crustal particles generated locally: are they natural? Secondary particles formed by the reaction between biogenic particles and anthropogenic species: are they natural?
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
THANK YOU FOR YOUR ATTENTION !
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
CONTRIBUTION OF NATURAL SOURCES TO AIRBORNE PARTICULATE MATTER IN CENTRAL ITALY
Ivo ALLEGRINI, Cinzia PERRINO C.N.R. Institute of Atmospheric Pollution Montelibretti (Rome)
NATURAL SOURCES sea-spray, volcanoes, desert dust, biogenic aerosol DESERT DUST Amount: 80-120 million tons /year from Sahara to Europe Main sources: Algeria, Morocco, Lybia, Tunisia Average duration of the events: 2-4 days Deposition: 5-15 g/m2 per year CONTRIBUTION OF NATURAL SOURCES TO PM Models (trajectories: HYSPLIT, DREAM) Dust profile detection (LIDAR) Statistical methods (source apportionment) Study of the meteorological situation Number and dimensions of particles Chemical analysis C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
Chemical analysis of macrocomponents
Only a few components constitutes more than 1% of PM: ¾ A few metals: Al, Si, Fe ¾ The main anions: Cl-, NO3-, SO4=, CO3¾ The main cations:Na, NH4+, K+, Mg++, Ca++ ¾ Elemental carbon ¾ Organic material (20-60% of PM but hundreds of species)
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
“Fine Dust” A research project funded by the Lazio Region October 2004 – July 2005 (daily sampling – analysis of the 140 most interesting days) MONTELIBRETTI semi-rural station VITERBO urban station FONTECHIARI regional background station
ROMA VILLA ADA urban background station
ROMA MONTEZEMOLO traffic station
C. Perrino
LATINA urban station
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
3-step procedure: 1.
Mixing properties of the lower atmosphere Natural radioactivity monitoring
2. Size distribution of particulate matter Optical particle counter
3. Chemical composition of particles Analysis of metals, ions, carbon compounds
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 1: Mixing properties of the lower atmosphere URANIUM238 DECAY CHAIN
PBL MIXING MONITOR
RADON
222
[φ (t )] ≅ k SHORT-LIVED RADON PROGENY (β DECAY)
PM10 MASS CONCENTRATION - urban background station 70 60
ug/m3
50 40 30 20 10 0 15
16
17
18
19
20
21
22
23
24
25
DECEMBER 2003
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
26
27
28
29
30
31
During warm months natural radioactivity shows a well-defined and modulated temporal pattern (all days are similar: nocturnal stability and convective mixing during the day)
NATURAL RADIOACTIVITY 2500
COUNTS / MINUTE
During cold months high-pressure periods are sporadic and advection often occurs. Diurnal mixing is weak and of limited duration.
2000
1500
1000
500
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
DECEMBER
STEP 1: Mixing properties of the lower atmosphere
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 1: Mixing properties of the lower atmosphere
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 1: Mixing properties of the lower atmosphere Starting from natural raadioactivity values we can develop Atmospheric Stability Indexes… PM10 ROMA - Villa Ada 90 SPERIMENTALE EXPERIMENTAL FORECASTED PREVISTO
80 70
μg / m
3
60 50 40 30 20 10 0 GENNAIO, NOVEMBRE, DICEMBRE 2004
… for each day, they give the probability, from the meteorological point of view, for the occurrence of an atmospheric pollution event C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 1: Mixing properties of the lower atmosphere PM10 ROMA - VILLA ADA 100 90
sperimentale EXPERIMENTAL
80
FORECASTED previsto ISA
μg/m
3
70 60 50 40
In the case of natural events
30
(e.g. desert dust)
10
20
0
the values of the
1
2
3
4
5
6
Atmospheric Stabilty Index do not match PM concentration
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
7
8
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 DICEMBRE 2004
STEP 1: Mixing properties of the lower atmosphere N A T U R AL R AD IO A C T IV IT Y 350 0
300 0
Night-time stability
250 0
200 0
150 0
100 0
50 0
0 1
2
3
4
5
6
7
8
9
10 1 1 1 2 1 3 14
15
16 1 7 1 8 1 9 20
O T T OTTOBRE O B R E 20 04
21
22
23 2 4 2 5 26
27
28
29 3 0 3 1
2004
N A T U R AL R AD IO A C T IV IT Y 3 5 00
3 0 00
2 5 00
Nighttime and daytime stability
2 0 00
1 5 00
1 0 00
5 00
0 1
C. Perrino
2
3
4
5
6
7
8
9
advection
1 0 1 1 12 13 14 1 5 1 6 1 7 18 19 20 21 2 2 2 3 2 4 2 5 26 27 28 2 9 3 0 3 1 D ICE M B R E 22004 0 04 DICEMBRE
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
VILLA ADA - PM10
80
80
70
70
60
60
50
50
40
40
30
30
20
20
10
10
0
0
GENNAIO GENNAIO
FEBBRAIO FEBBRAIO
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29
VILLA ADA - PM10
VILLA ADA - PM10
50
40
40
30
30
A N N O
20
20
10
10
0
0
AGOSTO AGOSTO
LUGLIO LUGLIO
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
VILLA ADA - PM10
VILLA ADA - PM10 50
50
40
40
40
30
30
30
20
20
20
10
10
50
70
VILLA ADA - PM10
VILLA ADA - PM10 50
3
90
μg/m
μg/m
3
VILLA ADA - PM10 90
60
3
40
μg/m
μg/m
3
50
30 20
10
10 0
0
MARZO MARZO
APRILE APRILE
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
VILLA ADA - PM10
VILLA ADA - PM10 50
50
40
40
30
0
0
SETTEMBRE
OTTOBRE OTTOBRE
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 SETTEMBRE
VILLA ADA - PM10
VILLA ADA - PM10
100
70
90 60
80 50
70 60
40
μg/m
3
30
2 0 0 4
50 30
40
20
20
30
20
10
10
0
0
MAGGIO
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 MAGGIO
20 10
10 0
0
GIUGNO GIUGNO
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
NOVEMBRE NOVEMBRE
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
WINTERTIME STABILITY (night and day) SUMMERTIME STAILITY (nigth) SAHARAN DUST (DREAM model) C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
DICEMBRE DICEMBRE
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
FIRST REMARK
The mixing properties of the lower atmosphere are a key factor in determining PM concentration level and its time variations An increase of PM concentration during advection conditions may indicate a natural event C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
3-step procedure: 1. Mixing properties of the lower atmosphere
Natural radioactivity monitoring 2. Size distribution of particulate matter
Optical particle counter 3. Chemical composition of particles
Analysis of metals, ions, carbon compounds
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 2: Size distribution of particulate matter Optical Particle Counter 70000
1400
0.3 - 0.5 µ
60000
1200
> 1.5 m
in the coarse ( > 1,5 μm) and the fine (0,3 – 0,5 μm)
N / litro
between the number of particles
1000
40000
800
30000
600
20000
400
10000
200
0
0 8-Oct
ranges:
9-Oct
10-Oct
11-Oct
12-Oct
13-Oct
14-Oct
Optical Particle Counter 0.12
An increase of this ratio indicates a natural event
Rapporto >1.5 m / 0.3 - 0.5 m 0.10
0.08
0.06
0.04
0.02
0.00 8-Oct
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
9-Oct
10-Oct
11-Oct
12-Oct
13-Oct
14-Oct
N / litro
Evaluation of the ratio
50000
STEP 2: Size distribution of particulate matter S IZ E R A T IO :
> 1 .5 / 0 .3 -0 .5
10 9 8
Daily average ratio
R * 100
7 6 5 4 3
between the number of particles
2 1 0 1
in the coarse ( > 1,5 μm)
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 O C TO B E R 2004 S IZ E R A T IO :
> 1 .5 / 0 .3 -0 .5
10
and the fine (0,3 – 0,5 μm)
9 8
ranges
R * 100
7 6 5 4 3 2 1 0 1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 N O V E M B E R 2004 S IZ E R A T IO :
> 1 .5 / 0 .3 -0 .5
10
IDENTIFICATION OF
9 8
NATURAL EVENTS
R * 100
7 6 5 4 3 2 1 0
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 D E C E M B E R 2004
3-step procedure: 1. Mixing properties of the lower atmosphere
Natural radioactivity monitoring 2. Size distribution of particulate matter
Optical particle counter 3. Chemical composition of particles
Analysis of metals, ions, carbon compounds
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles
Crustal metals
PM10
PM2.5
Teflon filter
Quartz filter
ED-XRF
Termooptical analyser
Organic carbon Elemental carbon
Extraction
Ion chromatography
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
Anions and cations
STEP 3: Chemical composition of particles
Chemical characterisation: 1. Anions and cations
Ion chromatography (IC)
(NO3-, SO4=, Cl-, Na+, Ca++, Mg++, K+, NH4+)
2. Elemental carbon and organic carbon compounds (EC, OC)
Termo-optical analyser
3. Crustal metals (major components) (Si, Al, Fe, Ca, K)
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
X-ray fluorescence (ED-XRF)
MASS CONCENTRATION OF PM10 IN MONTELIBRETTI (ROME) MEASURED BY THE DUST MONITOR (blue) AND RECONSTRUCTED BY THE CHEMICAL ANALYSES (red)
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles
4 main sources [sea-spray aerosol] = (Na+ + Cl-) * 1.176
[SO4= Mg Ca K]
[crustal] = (1.89 Al + 2.14 Si + 1.4 Ca + 1.2 K + 1.36 Fe) * 1.12 [primary anthropogenic compounds] = EC * 2
[OM]
[secondary compounds] = NH4+ + SO4= + NO3- + (OM – EC)
OM = α OC C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
α = 1.6 ÷ 2.1
[Mg Na Ti]
STEP 3: Chemical composition of particles
100 PRIM. ANTHR. COMP.
90
SECONDARY COMP.
CONCENTRAZIONE (µg/m3)
80
SEA-SALT CRUSTAL MATTER
70 60 50 40 30 20 10 0 PM10 - ROME TRAFFIC STATION
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles
CONCENTRAZIONE DI SALE MARINO - ROMA MONTEZEMOLO 12
(µg/m3)
10 8 6 4 2 C.N.R. Institute of Atmospheric Pollution – Rome0 (ITALY)
STEP 3: Chemical composition of particles
Sea-spray events: • NaCl concentration increases from 1-2% to 20-40% • the coarse/fine ratio increases • they occur in advection conditions (generally clean air masses) • PM10 concentretion is low; the increase due to sea-salt is generally < 10 ug/m3 • generally they do no cause exceedances • they have low impact on PM2.5 concentration
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles
CONCENTRAZIONE DI CRUSTALE - LATINA TASSO
60
(µg /m 3)
50 40 30 20 10 C.N.R. Institute of Atmospheric Pollution – Rome (ITALY) 0
STEP 3: Chemical composition of particles
Saharan dust events: • crustal matter concentration increases from 10-20% to over 50% • the coarse/fine ratio increases • they begin in advection conditions (but re-suspension may increase the time
duration of the episode) • PM10 concentretion can be very high (up to more than 100 ug/m3) • they often cause exceedances • they also generally cause an increase of PM2.5 concentration
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles S IZ E R A T IO :
> 1 .5 / 0 .3 -0 .5
10 9
38.0 μg/m3
8
R * 100
7
58.8 μg/m3
6 5 4 3
IDENTIFICATION
2 1 0
AND
1
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
S IZ E R A T IO :
> 1 .5 / 0 .3 -0 .5
10 9 8 7 R * 100
NATURAL
3
O C TO B E R 2004
CHARACTERISATION OF
2
6 5 4 3 2
EVENTS:
1 0 1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 N O V E M B E R 2004 S IZ E R A T IO :
SEA-SPRAY
10
146.4 μg/m3
9 8 7 R * 100
AFRICAN DUST
> 1 .5 / 0 .3 -0 .5
6 5 4 3 2 1 0
C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 D E C E M B E R 2004
SECOND REMARK
Natural events can be identified from an increase of the coarse-to-fine ratio The nature of the event is detected by the chemical analysis
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 3: Chemical composition of particles CARBONIO ELEMENTARE - LAZIO 30
%ECNEL PM.2.5
25 20 15 10 5 0
ELEMENTAL CARBON
OT T OBRE 2004 - LUGLIO 2005
PRIMARY ANTHROPOGENIC POLLUTANTS
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 3: Chemical composition of particles
Average % composition of PM10 in the Lazio region C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
THIRD REMARK
For primary anthropogenic pollutants we cannot identify “events” Their concentration depends on the proximity to the emission sources and their concentration variations mainly depend on the dispersion capacity of the lower atmosphere
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 3: Chemical composition of particles SOLFATO NEL PM 10 - LAZIO
SULPHATE
% SOLFATO NEL PM10
30
20 15 10 5 0
SECONDARY
OTTOBRE 2004 - LUGLIO 2005
SECONDARY PM CONCENTRATION - ROME TRAFFIC STATION
POLLUTANTS
60 CONCENTRATION (µg/m3)
C. Perrino
25
48 36 24 12 0
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
STEP 3: Chemical composition of particles
Average % composition of PM10 in the Lazio region C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
STEP 3: Chemical composition of particles
PM10 SEA SALT CRUSTAL MATTER PRIMARY ANTHROP. SECOND. ORGANIC SECOND. INORGANIC
CONCENTRATIO N (µg/m3 )
50
40
30
20
10
0 ROME TRAFFIC
ROME URBAN BACKGROUND
SEMI-RURAL
REGIONAL BACKGROUND
Secondary pollutants are homogeneously distributed at least on a regional scale. C.N.R. Institute of Atmospheric Pollution – Rome (ITALY)
FOURTH REMARK
For secondary pollutants we cannot identify “events” Their concentration is homogeneous on a regional scale and their concentration variations mainly depend on the dispersion capacity of the lower atmosphere
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
AFRICAN DUST OUTBREAK - JUNE 2006
June 16
June 22
June 29 C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
June 24
July 2
AFRICAN DUST OUTBREAK - JUNE 2006
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
AFRICAN DUST OUTBREAK - JUNE 2006
Montelibretti - PM 10 100
80
AUTOMATIC MONITOR SUM OF CHEMICAL DETERMINATIONS
3
CONCENTRATION (µg/m )
90
70 60 50 40 30 20 10 0 1 2 3 4 5 6 7 8 9 1011 12 1314 15 1617 18 1920 21 2223 24 2526 27 2829 30 1 2
June - July 2006
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
AFRICAN DUST OUTBREAK - JUNE 2006 MONTELIBRETTI – PM10 80 70
CONCENTRATION (µg/m3)
60
SEA-SPRAY PRIMARY ANTHROP. SECONDARY ORG. SECONDARY INORG. CRUSTAL
50 40 30 20 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 1 2
JUNE - JULY 2006
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
AFRICAN DUST OUTBREAK - JUNE 2006 19 GIUGNO 2006 - PM10: 40.1 μg/m
3
ORG. SEC. 34%
INORG. SEC. 13%
MARE 1%
ANTR. PRIM. 11% CRUSTALI 41%
28 GIUGNO 2006 - PM10: 86.5 μg/m3
INORG. SEC. 16%
ORG. SEC. 17% ANTR. PRIM. 5%
MARE 1%
INORG. SEC. 34%
1 LUGLIO 2006 - PM10: 59.6 mg/m3 ORG. SEC. 19%
CRUSTALI 61%
SO4=: 22 % 90 80
MARE 2%
ANTR. PRIM. 5% CRUSTALI 40%
CONCENTRAZIONE (µg/m3)
70
AEROSOL MARINO ANTROP. PRIMARI SECONDARI ORG. SECONDARI INORG. CRUSTALI
60 50 40 30 20 10 0
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
17/6 18/6 19/6 20/6 21/6 22/6 23/6 24/6 25/6 26/6 27/6 28/6 29/6 30/6 1/7 GIUGNO - LUGLIO 2006
2/7
… some answers ….but many questions….
Re-suspension of deposited desert dust: still a natural event? Desert dust particles coated with anthropogenic sulphate: are
they natural? THANK YOU FOR YOUR ATTENTION !
Crustal particles generated locally: are they natural? Secondary particles formed by the reaction between biogenic particles and anthropogenic species: are they natural?
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
THANK YOU FOR YOUR ATTENTION !
C. Perrino
C.N.R. Istituto sull’Inquinamento Atmosferico – Montelibretti (Roma)
