EFFECTS OF EMISSIONS ON CURRENT AND FUTURE … fileeffects of emissions on current and future...
Transcript of EFFECTS OF EMISSIONS ON CURRENT AND FUTURE … fileeffects of emissions on current and future...
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.