EFFECTS OF EMISSIONS ON CURRENT AND FUTURE RAINFALL PATTERNS IN SOUTHEAST BRAZIL

Arnaldo A. Cardoso Institute of Chemistry, São Paulo State University, Proc 2008/58073-5

Collaborating institutions: I. Química UNESP (Andrew G. Allen and Raquel F. P. Nogueira); I. Química USP (Lilian Rothschild); I. GeologiaUNICAMP (Bernardino R. de Figueiredo and Jacinta Enzweiler); FFCL

Ribeirão Preto USP(Maria L. A. M. Campos and Maria E. Queiroz); IPMET UNESP (Gerhard Held and Ana M. G. Held); Grupo Eletricidade

Atmosférica INPE (Kleber P. Naccarato)

Novembro 2013

1

Steps to reduce manual harvest in São Paulo State

The Sao Paulo State area of 248 x 106 km2.

Population (2000) 37 million (2010) ~ 41 million inhabitants (1.1X)

GDP (2000) US$ 210 billion (2010) US$ 620 billion. (3X)

Economy is based on agriculture and associated industries.

The world’s largest contiguous area of sugar cane cultivation 45,900 km2

(2010/2011)

Mechanization Process of the Sugar Cane Harvesting

Impact of economic transformation in São Paulo State

2

Aerosol Sources

Soil dust (35%) A

Sea spray (35%)

Transport (11%) A

Biomass burning (8%) A

Biogenic (6%) A

Industrial dust (4%)

Volcanoes (1%)

[A = Agriculture]

3

Aerosols and Human Health

• Cardiovascular and respiratory disease

• Asthma, bronchitis, pneumonia

• Lung cancer• Correlation between

ambient concentrations and occurrence of respiratory disease

• Highest correlation for fine particles (<1 m)

• Higher content of toxic components (PAHs, metals)

• At highest risk: children, the elderly

4

Aerosols Are Essential…Aerosols Are Essential…

Aerosols Are Essential…

• Component of biogeochemical cycling

• Nutrient transfers and inputs

• Regulation of radiativefluxes

• Cloud formation

• Vector for bio-mobility

• Atmospheric buffering

5

Map showing the location of the field measurement station in São Paulo State

6

Sampling station at UNESP campus, Araraquara, and

instrumentation installed

7

0

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

SO42-

K+

May Jun Jul Sep Oct Nov Dec Jan Feb Mar

2010

Conc

entr

atio

n (µ

g m

-3)

higher biomass burning lower biomass burning

2011

Concentrations of sulfate and potassium in total suspended particulates (TSP)

J. Geophys. Res. Atmos., (2013) 118, 8675–86878

0

20

40

60

80

Ae

ros

ol m

as

s c

on

ce

ntr

ati

on

(

g m

-3)

May Jun Jul Sep Oct Nov Dec Jan Feb Mar

0.3-1.0

1.0-5.0

5.0->10

2010 2011

Mass concentrations of aerosols in three size fractions (0.3-1.0 , 1.0-5.0, and 5.0->10.0 µm)

J. Geophys. Res. Atmos., (2013) 118, 8675–86879

10

0,00

25,00

50,00

75,00

100,00

18 10 5,6 3,2 1,8 1 0,56 0,32 0,18 0,1 0,056 0

D50 Diâmetro (um)

Cá

lcio

(n

g /

m-3

)

Outono

Inverno

Primavera

Verão

0,00

200,00

400,00

600,00

800,00

1000,00

18 10 5,6 3,2 1,8 1 0,56 0,32 0,18 0,1 0,056 0

D50 Diâmetro (um)

Su

lfa

to (

ng

m-3

)

Outono

Inverno

Primavera

Verão

0,00

50,00

100,00

150,00

200,00

250,00

18 10 5,6 3,2 1,8 1 0,56 0,32 0,18 0,1 0,056 0

D50 Diâmetro (um)

Nit

rato

(n

g m

-3)

Outono

Inverno

Primavera

Verão

0,00

7,00

14,00

21,00

28,00

35,00

18 10 5,6 3,2 1,8 1 0,56 0,32 0,18 0,1 0,056 0

D50 Diâmetro (um)

Ma

gn

és

io (

ng

m-3

)

Outono

Inverno

Primavera

Verão

Atmospheric chemistry: atmospheric acidity

Fine particles are acidic, containing secondary nitrates, sulfates and organic species

Larger particles exhibit an anion deficit with basic property

Environ. Sci. Technol. (2005) 39, 5293-530111

12

Aerosol phosphorus and potassium concentrations, cumulative monthly precipitation, and monthly average wind speed

Cluster analysis dendrogram obtained using Pearson correlation coefficients, at a 95% confidence level.

Environ. Sci. Technol. under review13

14

Deposição natural

Deposição seca para floresta tropical (kg (N) ha-1 a-1) de NO2-N, HNO3-N, NH3-N, NO3--N

and NH4+-N em seis regiões do Estado de São Paulo (2008-2009)

Environmental Pollution (2011) 159, 1190-119

(a)

0

50

100

150

200

250

31

/12

2/1

4/1

6/1

8/1

10

/1

12

/1

14

/1

16

/1

18

/1

20

/1

22

/1

24

/1

26

/1

28

/1

30

/1

1/2

Ma

ss

co

nc

en

tra

tio

n (g

m-3

)

(13

48

)

(41

8)

(36

2)

(16

46

)

0

50

100

150

200

250

30

/6

2/7

4/7

6/7

8/7

10

/7

12

/7

14

/7

16

/7

18

/7

20

/7

22

/7

24

/7

26

/7

28

/7

30

/7

Ma

ss

co

nc

en

tra

tio

n (g

m-3

)

(27

1)

(82

1)

(35

4)

(84

8)

(32

4)

(41

2)

(64

5)

(42

8)

(76

5)

(b)

Aerosol mass concentrations (PM10 ) (a) January 2011 (summer season), and (b) July 2010 (winter season), showing nighttime peaks in concentrations.

J. Geophys. Res. Atmos., (2013) 118, 8675–868715

Nighttime/daytime ratios of measured chemical species concentrations

0

10

20

30

40

50

60

70

80

90

0.1 1 10 100

Dp (m)

Min

c

Summer

Winter

Nighttime aerosol mass increases (Minc) during summer and winter vs particle diameter (Dp).

J. Geophys. Res. Atmos., (2013) 118, 8675–868716

Cl- NO3- PO4

3- SO42- C2O4

2- Na+ NH4+ K+ Mg2+ Ca2+ WSOC

1st Quartile 0.018 0.221 0.000 0.677 0.000 0.041 0.623 0.200 0.044 0.259 5.329

Median 0.043 0.444 0.000 0.975 0.000 0.087 1.200 0.403 0.120 0.538 9.155

3rd Quartile 0.131 1.136 0.000 1.959 0.082 0.140 2.101 0.730 0.206 0.890 16.817

Mean 0.209 0.996 0.043 1.635 0.080 0.101 1.427 0.727 0.162 0.692 11.783

SD 0.398 1.281 0.120 1.783 0.197 0.074 1.114 1.021 0.169 0.548 8.838

Descriptive statistics for concentrations (g m-3) of chemical species

Particle size fraction (m)

0.3-0.5 0.5-1.0 1.0-3.0 3.0-5.0 5.0-10.0 >10.0

Cl- -0.191 0.084 0.224 0.243 -0.109 -0.213

NO3- 0.054 0.228

0.347a

(0.389)b

0.399

(0.237)-0.063 -0.175

SO42- 0.297

0.401

(0.529)

0.497

(0.610)

0.464

(0.301)0.223 0.089

Na+ 0.000 -0.106 -0.066 0.222 0.095 0.044

NH4+ 0.219

0.378

(0.532)0.255 0.024 -0.049 -0.083

K+ 0.020 0.2220.399

(0.302)

0.484

(0.194)0.082 -0.081

Mg2+ 0.003 0.067 0.2380.448

(0.216)0.127 -0.029

Ca2+ 0.179 0.2800.369

(0.447)

0.471

(0.301)0.280 0.140

WSOC0.397

(0.252)

0.454

(0.643)

0.441

(0.581)0.326 0.112 0.028

Pearson correlation coefficient (r) aerosol mass conc. vs chemical species conc, during periods of aerosol mass conc. peaks.

17

KCl 84.2% K2SO4 96% KNO3 93% mixtures K+ 80-90%

NH4NO3 62% (NH4)2SO4 80.0% NH4HSO4 40.0% (NH4)3H(SO4)2

69.0%

K2CO3 43% KNO3 93%

Deliquescence relative humidity (DRH), 298 K

Reaction with HNO3

J. Geophys. Res. Atmos., (2013) 118, 8675–868718

0

100

200

300

1100

1200

levo

gluc

osan

(ng

m-3

)

0

2

4

6

8

10

12 day

night

WSO

C (

g m

-3)

48h

24h

24h

48h

Conc of levoglucosan (1,6-anhydro--D-glucopyranose), and WSOC for day, night, 24 h, and 48 h sampling of aerosol at the Ourinhos site in São Paulo State

Atmospheric Environment (2012) 61, 562-56919

0

10

20

30

40

50

60

70

80

90

100

27/Aug/1004/Aug/10

pe

rce

nta

ge

20/Aug/10

PM<0.49 μm

0.49 μm<PM<0.95 μm

0.95 μm<PM<1.5 μm

1.5 μm<PM<3.0 μm

3.0 μm<PM<7.2 μmPM>7.2μm

Levoglucosan amounts in different size fractions of the aerosol collected at Ourinhos.

Atmospheric Environment (2012) 61, 562-56920

21

Conc levoglucosan (■), mannosan (○), and galactosan (●) in aerosol , 24-h periods

levoglucosan mannosan galactosan0

100

200

300

400

500

600

700

800

day (n = 16)

nigth (n = 16)

levo

gluc

osan

(ng

m-3

)

0

20

40

60

80

100

120

mannosan or galactosan (ng m

-3)-200

-100

0

100

200

300

400

500

levoglu

cosa

n (

ng m

-3)

non-harvest

Oct

Sep

FebJan

Dec

Nov

harvest14/09/2010

12/01/2011

non-h

Dec

FebJan

Nov

Oct

Aug

July

June

May

Apr

Mar

harvest

0

10

20

30

40

50

60

70

80

man

no

san o

r galacto

san (n

g m

-3)

Concentrations of the anhydrosugars daytime (n=16) and nighttime (n=16)

Atmospheric Environment under review

22

0

10

20

30

40

50

60

70

80

90

100

PM<0.49 m

0.49<PM<0.95 m

0.95<PM<1.5 m

1.5<PM<3.0 m

3.0<PM<7.2 m

per

cen

tag

e le

vo

glu

cosa

n (

%)

PM>7.2 m

0

50

100

150

200

250

300

350

400

levo

glu

cosan

(ng

m-3)

0

10

20

30

40

50

60

70

80

90

100

PM<0.49 m

0.49<PM<0.95 m

0.95<PM<1.5 m

1.5<PM<3.0 m

3.0<PM<7.2 m

per

cen

tag

e m

ann

osa

n (

%)

PM>7.2 m

0

10

20

30

40

50

60

70

80

man

no

san (n

g m

-3)

14/0

9/20

10

01/1

0/20

10

21/1

1/20

11

30/1

1/20

11

07/1

2/20

11

09/0

1/20

12

18/0

1/20

12

25/0

1/20

12 -- -- --0

10

20

30

40

50

60

70

80

90

100

PM<0.49 m

0.49<PM<0.95 m

0.95<PM<1.5 m

1.5<PM<3.0 m

3.0<PM<7.2 m

per

cen

tag

e g

alac

tosa

n (

%)

PM>7.2 m

0

10

20

30

40

50

60

galacto

san (n

g m

-3)

A

B

C

Total concentrations (■) and percentages of A) levoglucosan, B) mannosan, and C) galactosanin different size fractions of the aerosol collected over 24-h periods.

levoglucosan mannosan galactosan0

50

100

150

200

250

levoglu

cosa

n (n

g m

-3)

man

nosan

or g

alactosan

(n

g m

-3)

harvest (n = 48)

non harvest (n = 25)

0

10

20

30

40

Concentrations levoglucosan, mannosan, and galactosan in aerosol samples collected from harvest and non-harvest period

Atmospheric Environment under review

23

0 1 2 3 4 5 6 7 8 9 100

1

2

3

Me

an

co

nce

ntr

atio

n

(ng

.m-3

)

Diurnal

Nocturnal

BbF Fla BaA Pyr Chr Phe BaP Acy Nap 1 2 30

1

2

3

Bzo9-Ant

Me

an

co

nce

ntr

atio

n (

ng

.m-3

)

Diurnal

Nocturnal

9-Flu

oxy-PAH compounds

0 2 4 60

1

2

3

Me

an c

oncentr

ation (

ng.m

-3)

Diurnal

Nocturnal

9NPhe 2NFla 2NNap 7NBaA 9NAnt 2NPyr

Diurnal and nocturnal variation of PAH compounds in the airborne aerosols

nitro-PAH compounds PAH compounds

Atmospheric Environment in press

24

In situ formation

Biomassburning

Nitro-PAH

PAH

9-Flu 9-Ant

Bzo

NOCTURNAL

Another

source(s) ?

2-NPyr2-NFla

other

In situ formation

Vehicular emission

Nitro-PAH

PAH

9-Flu 9-Ant

Bzo

DIURNAL

2-NPyr2-NFla

other

Lost by photolysis

Schematic proposal for the main sources of PAH and their nitro and oxy- derivatives in atmospheric particulate matter of the Araraquara region during daytime and nighttime

Atmospheric Environment in press

25

28/6

/12

19:1

0

30/6

/12

4:30

1/7/

12 1

8:40

3/7/

12 4

:00

4/7/

12 1

3:40

5/7/

12 2

3:00

7/7/

12 8

:20

0

20

40

60

80

100 Um, Rel,(%)

Aitken

Accumulation

RH

(%

)

0.00

1.50x106

3.00x106

4.50x106

6.00x106

7.50x106

Pa

rticle

s (#

cm

-3)

28/6

/12

19:1

0

30/6

/12

4:30

1/7/

12 1

3:50

2/7/

12 2

3:10

4/7/

12 8

:50

5/7/

12 1

8:10

7/7/

12 4

:10

0

5

10

15

20

25

30

35

40 NO2_Avg

Aitken

Accumulation

NO

2

0

1x106

2x106

3x106

4x106

5x106

6x106

7x106

8x106

Partic

les (#

cm

-3)

Fig 1. Correlação entre umidade relativa e adistribuição de partículas para o modo deAitken e acumulação

Fig 2. Correlação entre a concentração de dióxido denitrogênio e a distribuição de partículas para o modode Aitken e acumulação

26

28/6

/12

19:1

0

30/6

/12

4:30

1/7/

12 1

3:50

2/7/

12 2

3:10

4/7/

12 8

:50

5/7/

12 1

8:10

7/7/

12 4

:10

0

50

100

150

200

250

300

350 WindDir

Aitken

AccumulationW

in D

ir

0.0

2.0x106

4.0x106

6.0x106

8.0x106

1.0x107

1.2x107

1.4x107

1.6x107

1.8x107

2.0x107

Partic

les (#

cm

-3)

Correlação entre a direção do vento e a distribuição de partículas para omodo de Aitken e acumulação

Localização do sítio de amostragem

27

0

200

400

600

800

0 200 400 600

Co

ncn

. (c

m-3

)

Dp (nm)

18/10/2011

0

50

100

150

200

0 200 400 600

Co

ncn

. (c

m-3

)

Dp (nm)

11/10/2011

Examples of events characterized by Aitken (left) and accumulation (right) modes in the size distribution

-0.50

-0.40

-0.30

-0.20

-0.10

0.00

0.10

14

,6

19

,5

25

,9

34

,6

46

,1

61

,5 82

10

9,4

14

5,9

19

4,6

25

9,5

34

6

46

1,4

61

5,3

Co

rr. (

R)

Dp (nm)-0.20

-0.10

0.00

0.10

0.20

14

,6

19

,5

25

,9

34

,6

46

,1

61

,5 82

10

9,4

14

5,9

19

4,6

25

9,5

34

6

46

1,4

61

5,3Co

rr. (

R)

Dp (nm)

2. Correlations obtained between re (Aqua data) and the size distributed aerosol number concentration during Aitken mode (left) and accumulation mode (right) events.

28

Aitken (n=7) Accumulation (n=25)

Aerosol size fraction (nm) r p r p

18.1-23.3 0.166 0.722 0.154 0.462

24.1-31.1 0.298 0.516 0.043 0.838

32.2-41.4 0.409 0.362 -0.212 0.308

42.9-55.2 0.567 0.184 -0.446 0.025

57.3-73.7 0.576 0.176 -0.471 0.018

76.4-98.2 0.417 0.352 -0.382 0.059

101.8-131 0.179 0.701 -0.278 0.179

135.8-174.7 0.222 0.632 -0.165 0.432

181.1-232.9 0.369 0.415 -0.104 0.621

241.4-310.6 0.393 0.383 -0.091 0.666

322-414.2 0.363 0.423 -0.095 0.651

429.4-552.3 0.331 0.468 -0.134 0.522

Coeficiente de correlação de Pearson (r) e valores –p para correlação entre re (raioefetivo da gotícula da nuvem) e concentração numérica de aerossol para o modo deAitken e acumulação durante Agosto 2011 – novembro 2012.

Valores em negrito são diferentes de zero com nível de significancia =0.05

29

Composição química de PM10 durante o período da safra (maio-novembro), comparando os anos 2003 e 2010

FUTURO E INCERTEZAS

Redução de queima / aumento de mecanização nas plantações

Redução nas emissões de carbono elementar (aerossol) Emissões da poeira de solo Resíduos orgânicos como fontes de carbono orgânico, NH3, esporos de fungos, bacterias etcAumento na emissão/deposição de NH3 e NH4

+

Formação de aerossol secundário NH4 NO3

Alterações nas propriedades radiativas e capacidade NCN dos aerossóis Mudanças no albedo da superfície Redução na emissão/deposição de K+ / PO4

3- / (NOx / NO3- )

Acidez da atmofera

30

31

Students

Caroline Sacaramboni (scientific initiation); Diogo Camargo Borsoi (technical);

master's degree: Marcelo Cardoso Ferreira, Daniely de Godoy Silva and Michele

Lima de Souza; doctorate: Roberta Cerasi Urban, Leticia Caetano, Michele Lima de

Souza , Daniely de Godoy Silva, Patrícia de Oliveira and Kelly de Souza.