2015 international Training Course in Atmospheric Chemistry

Cartagena, Colombia, July, 2015

Atmospheric Aerosols
Size distribution - composition part III

International Atmospheric Chemistry - July 2015

TYPICAL U.S. AEROSOL SIZE DISTRIBUTIONS

Fresh
urban

Aged
urban
rural

remote
Warneck [1999]

Size Distribution
1500

dN/dD (m m-1cm-3)

dN/dD (m m-1cm-3)

1500

1000

500

1000

500

0
0

Dimetro (m m)

0,1

Dimetro (m m)

10

Size Distributions
dN/dD

dN/dlnD

dN/dlogD

2500

2000

dN/d??? (***)

(cm-3)
1500

(cm-3)

1000

500

(m m-1cm-3)
0
0,1

Dimetro (m m)

10

Diferences among distributions

20000
martimo
continental
16000

rural

-3

dN/dlogD (cm )

urbano
12000

8000

4000

0
0

0.2

0.4

0.6

D (m m)

0.8

Difference in the distributions

20000
martimo
continental
16000

rural

-3

dN/dlogD (cm )

urbano
12000

8000

4000

0
0.001

0.01

0.1

D (m m)

Differences in the distributions

200
martimo
continental
160

rural

-3

dN/dlogD (cm )

urbano
120

80

40

0
0.001

0.01

0.1

D (m m)

10

100000
martimo
continental

10000

rural
urbano

-3

dN/dlogD (cm )

1000
100
10
1
0.1
0.01
0.001

0.01

0.1

D (m m)

10

10
Nmero

dN-dM/dlogD

Massa

0
0.001

0.01

0.1

D (mm)

10

URBAN AND BIOMASS BURNING

25000

dN/dD (cm-3)

20000
SP min
SP mx
AM min
AM mx

15000
10000
5000
0
1

10

100

DIMETRO (nm)

1000

CONCENTRAO (??)

0.15
NMERO

0.12

REA
VOLUME

0.09
0.06
0.03
0
1.00

10.00

100.00

DIMETRO (nm)

1000.00

Size Distributions for Diesel particles.

Normalized Concentration (1/Ctotal)dC/dlogDp

0.25

Nuclei Mode - Usually

forms from volatile
precursors as exhaust
dilutes and cools

0.2

Fine Particles
Dp < 2.5 mm

Nanoparticles
Dp < 50 nm
Ultrafine Particles
Dp < 100 nm

In some cases this

mode may consist of
very small particles
below the range of
conventional
instruments, Dp < 10
nm

0.15

0.1

PM10
Dp < 10 mm

Accumulation Mode - Usually

consists of carbonaceous
agglomerates and adsorbed
material
Coarse Mode - Usually
consists of reentrained
particles, crankcase
fumes

0.05

0
1

10

100

1,000

10,000

Diameter (nm)

Number

Surface

Mass

Kittelson et al, 2002

DIURNAL CICLE
20000

So Paulo
dN/dlogD

15000
30
10000

100
300

5000

0
4

16

HORA LOCAL

20000

15000

dN/dlogD

12

30
10000

100
300

5000

0
14

18

22

HORA LOCAL

10

Rondnia

20

24

Distribuio de Tamanho Centro So Paulo

Variao temporal da concentrao do nmero de partculas, em funo do dimetro.

Albuquerque T., 2007

9
8

-3

Concentrao mdia (g.m )

7
6
5
4
3
2
1
0

1A

2A

3A

4A

5A

6A

7A

8A

9A

10A

Estgios

5,68

5,43

5,57

5,26

4,30

4,74

5,22

8,78

5,24

2,42

5,75

3,66

3,11

2,75

BC

0,02

0,02

0,03

0,05

0,04

0,11

0,18

1,47

0,73

0,49

2,19

0,05

0,02

0,02

Mass size distributions for aerosol collected at So Paulo

Mass size distribution.

Five modes can be see:
ultrafine; nucleation,
accumulation, fine and
coarse

Black Carbon distribution

Main distribution at nucleation
interval

Mass Size Distribution

Number Size Distribution

De 10 a 660 nm.

Almeida et al., 2014

Atmospheric Sciences Department - USP

Number Size Distributions

Cumulative Fraction

International Atmospheric Chemistry - July 2015

International Atmospheric Chemistry - July 2015

Composition

International Atmospheric Chemistry - July 2015

NARSTO, 2004

Annual mean PM2.5 concentrations (NARSTO, 2004)

Current air quality standard is 15 mg m-3

THE IMPORTANCE OF ORGANIC AEROSOL

NH4+

NO3-

Sulfate Organics

[Zhang et al., 2007]

Organic material contributes 20-50% of the total fine aerosol mass at continental mid-latitudes [Saxena and Hildemann, 1996;
Putaud et al., 2004] and as much as 90% in the tropical forested areas [Andreae and Crutzen, 1997; Talbot et al., 1988; 1990;
Artaxo et al., 1988; 1990; Roberts et al., 2001]

Temporal Variation of PM2.5 concentration in So Paulo

10000

Pb
Concentrao ng/m3

MP2.5

1000

Si
S
K

100

Ca
V

10

Fe
Ni

1
1977

1981

1983

1986

1989

1994

References since 1978 (Orsini et al.), etc.

1997

1998

1999

2003

2005

2008

2009

2012

Zn

Important public policies:

- Sulfur reduction in fuel and banning
of Pb
- Change the fuel in boilers
- Proconve (Program for Controlling
Vehicular emission)

Monthly variations in selected air pollutants in So Paulo. Solid regression lines show monthly mean concentrations used in
this paper. Error bars summarize the relative uncertainties in pollutant concentration measurements. Data are from the So
Paulo Environmental Company CETESB, 20002013 (http://www.cetesb.sp.gov.br/ar/qualidade-do-ar/32-qualar)
Perez et al., 2015, JGR

Concentration OC/EC & PM2.5

y = 2.1236x - 0.6739
R = 0.6735

60
50

Winter 2012

40

OC/PM2.5= 0.44
EC/PM2.5=0.13

30
20
10

Hetem, mestrado

0
0

10

15

20

25

Projeto NUANCE

CCN number distribution

Results show an increase in aerosol hygroscopicity in the

afternoon as a result of
aerosol photochemical processing, leading to an
enhancement of both organic and
inorganic secondary aerosols in the atmosphere, as well
as an increase in aerosol
average diameter.

Atmos. Chem. Phys. Discuss., 13, 3235332389, 2013

www.atmos-chem-phys-discuss.net/13/32353/2013/
doi:10.5194/acpd-13-32353-2013

Lidar Measurements and AOD

a)

b)

d)
c)

LIDAR Retroscatering,
September 12, 2012

gura 2 Medidas do perfil vertical da atmosfera da RMSP para o dia 12 de Setembro

Vertical Profile Setembro 12, 2012

de 2012, durante a campanha de medidas do projeto NUANCES-SP.

AOD mean

AOD July-September, 2012

AOD maximum

AOD minimum

Aqua Satellite

0,316 0,215

0,927 0,201

0,049 0,005

Terra Satellite

0,187 0,174

0,915 0,024

0,005 0,005

Lopes, 2013

Atmospheric Sciences Department - USP

Participao em % de MP2.5

Concentrao em ng/m3

Trace-element concentration

10000.0

1000.0

100.0

g/m3

10.0

1.0

100

10

0.1

0.01

0.001

SECONDARY ORGANIC AEROSOL (SOA)

PRIMARY BIOLOGICAL AEROSOL PARTICLES (PBAP)

Emission Inventory of Organic Aerosols

Botton-up approach
BSOA (biogenic SOA)

12-70 TgC/year

POA

35 TgC/year (9 anthropogenic) (25 biomass burning)

ASOA

2- 12 TgC/year

Total

50-90 TgC/year
The formation, properties and impact of secondary organic aerosol: current and
emerging issues

International Atmospheric Chemistry - July 2015

Atmos. Chem. Phys., 9, 51555236, 2009 www.atmos-chemphys.net/9/5155/2009/

WHICH VOCs ARE IMPORTANT SOA PRECURSORS?

Isoprene (C5H8)

Three factors:
1. Atmospheric Abundance
2. Chemical reactivity
3. The vapour pressure (or volatility)
of its products

Monoterpenes(C10H16)
Sesquiterpenes (C15H24)

Anthropogenic SOA-precursors = aromatics

(emissions are 10x smaller)

Estimativa da formao de Aerossis Orgnicos

Secundrios a partir dos dados medidos nos
experimentos de tneis. Em azul para o ano de 2004 e
em vermelho para o ano de 2011
International Atmospheric Chemistry - July 2015

PRIMARY BIOLOGICAL AEROSOL PARTICLES (PBAP)

BACTERIA

VIRUSES

POLLEN
FUNGUS

PLANT
DEBRIS

ALGAE

Jaenicke [2005] suggests may be as large a source as dust/sea salt (1000s Tg/yr)
May act as CCN and IN [Diehl et al., 2001; Bauer et al., 2003; Christiner et al., 2008]

Pollen Spores in So
Paulo

(Drum)
Fita

Burkard
7-day Recording Sampler
ROGERS et al., 2001

Lamina

Lminas
Msc. Ana Paula Mendes

Metodology:
Deuteromicetos
Ascomicetos

Mitsporos

Ascsporo

Myxomicetos

Basidiomicetos

Basidisporo

HAINES et al., 2000; Imagens: VALERO, 2013; GUIMARES, 2008; ONTARIO CROPIPM, 2009; ROCA, 2015

results: spores
A Pithomyces chartarum;

K: Diatrypaceae
Grande;

B: Venturia sp.;

L: Ascsporo de 2
clulas sem cor;

C: Torula sp.;

M:
Paraphaeosphaeria
Michotii

D: Basidisporo colorido
indet.;

N: Basidisporos
hialino grande;

E: Spegazzinia sp.;

O:
Aspergillus/Penicilli
um like

F: Myxomyceto;

P: Cladosporium sp.;

G: Gliomastix sp.;

Q: Ascsporo de 4
clulas sem cor;

H: Ascsporo de 4 clulas
com cor;

R: Drechslera-like;

I: Ganoderma sp.;

S: Xylariaceae;

J: Epicoccum nigrum;

T: Periconia sp.

Fluorescent biological aerosol (FBA) particles, which can be

regarded as a lower-limit proxy for PBA particles

Secondary organic aerosol (SOA)

droplets that were formed by atmospheric
oxidation
and gas-to-particle conversion of biogenic
volatile organic compounds) and in which no
other chemical components were detectable; (ii)
SOA-inorganic particles composed of secondary
organic material mixed with sulfates and/or
chlorides
from regional or marine sources ; (iii)
primary biological aerosol (PBA) particles, such
as plant fragments or fungal spores;
(iv) mineral dust particles consisting mostly of
clay minerals from the Sahara desert; or
(v) pyrogenic carbon particles that exhibited
characteristic
agglomerate structures and originated
from regional or African sources of biomass
burning
or fossil fuel combustion (6).

Some examples aerosol

characterization

Metropolitan Area of So Paulo - MASP

MASP= So Paulo city + 38 cities
19 million inhabitants
7,2 million vehicles
2000 significative industrial plants
8000 km2

Metropolitan Area of So Paulo

Area: 8051 km2

Lat=-23.6o

Urb: 1500 km2

Lon=- 46.7o

Pop: 23 million people

Vehicles:
million
Vehicles:>> 67 million

Atmospheric Sciences Department - USP

Distance from the sea-shore: 70 km

55% gasohol

Metropolitan
Region of So
Paulo

Population:~ 20 million
inhabitants.
Area: 8511 km2

4% ethanol hidrated
85% light-duty fleet
38% flex

Vehicular fleet: 7 million

3% diesel
2% diesel
12% motorcycles

Atmospheric Sciences Department - USP

Important questions
Expansion of urban areas and population growth

Silva Dias et al., (2011)

Very dense urban area

Contrast between urban and

suburban areas

Atmospheric Sciences Department - USP

Official Data Emission Inventory in the Metropolitan Area of So Paulo for Regulated
Pollutants

Atmospheric Sciences Department - USP

Source: CETESB

Some studies in Brazil

Which are the sources of particles (PM2.5)
Importance of vehicular contribution for PM2.5

Health Impact of vehicular emission

Motivation: the health impacts of atmospheric aerosols

Inhalation of particles: asthma, increase of respiratory symptoms, pulmonary and cardiovascular diseases.

The increase in PM concentration

is associated to an increase in
mortality

http://aerosol.ees.ufl.edu/atmos_aerosol/section
07-2.html

Relative risk adjusted to total mortality and PM2.5 concentrations in six cities.
During two periods: 1 from 1974 to 1989 and 2 from 1990 to 1998.
P=Portage, T=Topeka, W=Watertown, L=St. Louis, H=Harriman, S= Steubenville.

Metropolitan Area
So Paulo
Rio de Janeiro
Belo Horizonte
Porto Alegre
Curitiba
Recife

Population (million)
19.9
11.8
5.0
9.8
3.2
3.8

Area (thousand km2)

7.9
5.6
0.9
4.1
15.4
2.8

Recife

Belo Horizonte

So Paulo
Porto Alegre

Rio de Janeiro
Curitiba

PM2.5 Average mass concentration

July 2007 October 2008
Concentrations in g/m3

PM2.5

Std Dev

Black Carbon

Std Dev

BC/PM2.5

So Paulo

30

13

10

0.33

Rio de Janeiro

19

11

0.17

Belo Horizonte

17

0.28

Porto Alegre

16

12

0.22

Curitiba

17

0.27

Recife

12

0.17

MP2.5

Andrade et al., 2011

Ions composition

Concentration (ug/m3)

10.0

1.0

0.1

0.0

Ions

Curitiba

Rio Janeiro

Recife

So Paulo

Belo Horizonte

Porto Alegre

Mass Balance
The inorganic compounds were considered in the oxidazied form:
Al2O3, SiO2, K2O, CaO3, TiO, VO, MnO2, Fe2O3, NiO,
Cu2O, ZnO, Se, Br, Sr, Zr, Pb
+ ions
+BC

Crustal

Rio de Janeiro

So Paulo

Crustal
Ions
BC
ND

So
Paulo
Ions BC ND

Rio de Janeiro

Belo Horizonte

Porto Alegre

Crustal

Crustal
Ions
BC
ND

Crustal
Ions
BC
ND

Porto Alegre

Curitiba

Recife

Belo Horizonte

Crustal
Ions
BC
ND

Curitiba

Crustal
Ions
BC
ND

Recife

Receptor Modeling
Meteorological data

Air quality

Multivariate Methods
Principal Component Analysis

Source profile

Risk Analysis

Muchas Gracias!