cartagena part3 aerosols composition

Atmospheric Aerosols

Size distribution - composition part III

International Atmospheric Chemistry - July 2015

2015 international Training Course in Atmospheric Chemistry

Cartagena, Colombia, July, 2015

TYPICAL U.S. AEROSOL SIZE DISTRIBUTIONS

Fresh

urban

Aged

urban rural

remote Warneck [1999]

Size Distribution

0

500

1000

1500

0 1 2 3

Dimetro (mm)

dN

/dD

(m

m-1cm

-3)

0

500

1000

1500

0,1 1 10

Dimetro (mm)

dN

/dD

(m

m-1cm

-3)

Size Distributions

0

500

1000

1500

2000

2500

0,1 1 10

Dimetro (mm)

dN

/d??? (**

*)

dN/dD dN/dlnD dN/dlogD

(cm-3

)

(mm-1

cm-3

)

(cm-3

)

Diferences among distributions

0

4000

8000

12000

16000

20000

0 0.2 0.4 0.6 0.8 1

D (mm)

dN/dlog

D (cm

-3 )

martimo

continental

rural

urbano

Difference in the distributions

0

4000

8000

12000

16000

20000

0.001 0.01 0.1 1

D (mm)

dN/dlog

D (cm

-3 )

martimo

continental

rural

urbano

Differences in the distributions

0

40

80

120

160

200

0.001 0.01 0.1 1 10

D (mm)

dN/dlog

D (cm

-3 )

martimo

continental

rural

urbano

0.01

0.1

1

10

100

1000

10000

100000

0.001 0.01 0.1 1 10

D (mm)

dN/dlog

D (cm

-3 )

martimo

continental

rural

urbano

02

4

6

8

10

0.001 0.01 0.1 1 10

D (mm)

dN-d

M/d

logD

Nmero

Massa

URBAN AND BIOMASS BURNING

0

5000

10000

15000

20000

25000

1 10 100 1000

DIMETRO (nm)

dN

/dD

(cm

-3)

SP min

SP mx

AM min

AM mx

00.03

0.06

0.09

0.12

0.15

1.00 10.00 100.00 1000.00

DIMETRO (nm)

CO

NC

EN

TR

A

O

(??) NMEROREA

VOLUME

Size Distributions for Diesel particles.

0

0.05

0.1

0.15

0.2

0.25

1 10 100 1,000 10,000

Diameter (nm)

Nor

mal

ized

Con

cent

ratio

n (1

/Cto

tal)d

C/d

logD

p

Number Surface Mass

Fine Particles

Dp < 2.5 mm

Ultrafine Particles

Dp < 100 nm

Nanoparticles

Dp < 50 nm

Nuclei Mode - Usually

forms from volatile

precursors as exhaust

dilutes and cools

Accumulation Mode - Usually

consists of carbonaceous

agglomerates and adsorbed

material

Coarse Mode - Usually

consists of reentrained

particles, crankcase

fumes

PM10

Dp < 10 mmIn some cases this

mode may consist of

very small particles

below the range of

conventional

instruments, Dp < 10

nm

Kittelson et al, 2002

DIURNAL CICLE

0

5000

10000

15000

20000

4 8 12 16 20 24

HORA LOCAL

dN

/dlo

gD

30

100

300

0

5000

10000

15000

20000

14 18 22 2 6 10

HORA LOCAL

dN

/dlo

gD 30

100

300

So Paulo

Rondnia

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

Albuquerque T., 2007

Distribuio de Tamanho Centro So Paulo

01

2

3

4

5

6

7

8

9Conce

ntra

o m

dia

(g.m

-3)

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

I 1A 2A 3A 4A 5A 6A 7A 8A 9A 10A A B C

Mass size distributions for aerosol collected at So Paulo

Black Carbon distribution

Main distribution at nucleation

interval

Mass size distribution.

Five modes can be see:

ultrafine; nucleation,

accumulation, fine and

coarse

Almeida et al., 2014

Number Size Distribution De 10 a 660 nm.

Mass Size Distribution

Atmospheric Sciences Department - USP

Number Size Distributions

Cumulative Fraction


Composition

NARSTO, 2004

Annual mean PM2.5 concentrations (NARSTO, 2004)

Current air quality standard is 15 mg m-3

THE IMPORTANCE OF ORGANIC AEROSOL

[Zhang et al., 2007] Sulfate Organics

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]

NH4+ NO3-

110

100

1000

10000

1977 1981 1983 1986 1989 1994 1997 1998 1999 2003 2005 2008 2009 2012

Co

nce

ntr

ao

ng

/m3

Temporal Variation of PM2.5 concentration in So Paulo

MP2.5

Si

S

K

Ca

V

Fe

Ni

Zn

S

Pb

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

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

Winter 2012

Projeto NUANCE

y = 2.1236x - 0.6739

R = 0.6735

0

10

20

30

40

50

60

0 5 10 15 20 25

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

Hetem, mestrado

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

CCN number distribution

AOD mean 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

AOD July-September, 2012

LIDAR Retroscatering, September 12, 2012

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

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

a) b)

c)

d)

Vertical Profile Setembro 12, 2012

Lopes, 2013

Lidar Measurements and AOD


1.0

10.0

100.0

1000.0

10000.0

Co

nce

ntr

a

o e

m n

g/m

3

g/m3

0.001

0.01

0.1

1

10

100

Pa

rtic

ipa

o

em

% d

e M

P2

.5

Tra

ce-e

lem

ent

con

cen

trat

ion

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

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

Isoprene (C5H8)

Monoterpenes(C10H16)

Sesquiterpenes (C15H24)

WHICH VOCs ARE IMPORTANT SOA PRECURSORS?

Anthropogenic SOA-precursors = aromatics

(emissions are 10x smaller)

Three factors:

1. Atmospheric Abundance

2. Chemical reactivity

3. The vapour pressure (or volatility)

of its products


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

PRIMARY BIOLOGICAL AEROSOL PARTICLES (PBAP)

POLLEN

BACTERIA VIRUSES

FUNGUS

ALGAE PLANT

DEBRIS

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]

Burkard

7-day Recording Sampler

Pollen Spores in So Paulo

Lamina

(Drum) Fita

Lminas ROGERS et al., 2001 Msc. Ana Paula Mendes

Ascomicetos

Basidiomicetos Basidisporo

Ascsporo

Myxomicetos

Deuteromicetos Mitsporos

Metodology:

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/Penicillium 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.

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). Fluorescent biological aerosol (FBA) particles, which can be

regarded as a lower-limit proxy for PBA particles

Some examples aerosol

characterization

Metropolitan Area of So Paulo - MASP

Metropolitan Area of So Paulo

Area: 8051 km2

Urb: 1500 km2

Pop: 23 million people

Vehicles: > 6 million

Distance from the sea-shore: 70 km

Lat=-23.6o

Lon=- 46.7o

Vehicles: > 7 million

MASP= So Paulo city + 38 cities

19 million inhabitants 7,2 million vehicles 2000 significative industrial plants 8000 km2


Metropolitan Region of So

Paulo

Population:~ 20 million inhabitants.

Area: 8511 km2

Vehicular fleet: 7 million

85% light-duty fleet

55% gasohol

4% ethanol hidrated

38% flex

2% diesel

3% diesel

12% motorcycles


Important questions

Expansion of urban areas and population growth

Silva Dias et al., (2011)

Very dense urban area

Contrast between urban and suburban areas


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

Pollutants

Source: CETESB Atmospheric Sciences Department - USP

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 cardio-vascular diseases.

The increase in PM concentration is associated to an increase in mortality

http://aerosol.ees.ufl.edu/atmos_aerosol/section07-2.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.

Recife

Belo Horizonte

Rio de Janeiro So Paulo Curitiba

Porto Alegre

Metropolitan Area Population (million) Area (thousand km2)

So Paulo 19.9 7.9

Rio de Janeiro 11.8 5.6

Belo Horizonte 5.0 0.9

Porto Alegre 9.8 4.1

Curitiba 3.2 15.4

Recife 3.8 2.8

MP2.5

PM2.5 Std Dev Black Carbon Std Dev BC/PM2.5

So Paulo 30 13 10 6 0.33

Rio de Janeiro 19 11 3 2 0.17

Belo Horizonte 17 7 5 3 0.28

Porto Alegre 16 12 4 4 0.22

Curitiba 17 8 4 3 0.27

Recife 12 3 2 1 0.17

PM2.5 Average mass concentration July 2007 October 2008 Concentrations in g/m3

Andrade et al., 2011

0.0

0.1

1.0

10.0

Co

nce

ntr

atio

n (

ug

/m3)

Ions

Curitiba Rio Janeiro Recife So Paulo Belo Horizonte Porto Alegre

Ions composition

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

So Paulo

Crustal Ions BC ND

So Paulo

Rio de Janeiro

Crustal

Ions

BC

ND

Rio de Janeiro Belo Horizonte

Crustal

Ions

BC

ND

Belo Horizonte

Porto Alegre

Crustal

Ions

BC

ND

Porto Alegre Curitiba

Crustal

Ions

BC

ND

Curitiba

Recife

Crustal

Ions

BC

ND

Recife

Multivariate Methods

Principal Component Analysis

Receptor Modeling

Meteorological data Air quality

Source profile

Risk Analysis

Muchas Gracias!

cartagena part3 aerosols composition

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