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Article history: Wet deposition was measured in two urban areas of Brazil, Cubata ~o and Sa
~o Paulo megacity (MASP),
Received 4 August 2014 from July 2009 to August 2010. Cubat~ ao is characterized by the large and complex industrial sector and
Received in revised form MASP by a large vehicular fleet, and these different sources contributed to 15.5 106 and
10 November 2014
25.5 106 kg year1 of SO2 air emissions, respectively. The rainwater volume-weighted mean (VWM) pH
Accepted 12 November 2014
Available online 13 November 2014
values and [SO24 ] in Cubat~ao and in MASP were 4.8 and 7.1 mmol L1, and 5.3 and 24.5 mmol L1,
respectively. Regarding nitrogen content, the difference between reduced and oxidized nitrogen was
more pronounced in MASP, where more than 61% of total nitrogen scavenged as NHþ 4 . The wet-only
Keywords:
sulfur deposition in Cubata ~o was 17.0 kg S ha1 y1, which was 2.7-fold higher than that in MASP.
Rainwater chemistry
Urban air pollution Although the higher air pollutant emissions occur in MASP, the worst air quality and wet deposition has
Sulfur dioxide been observed in Cubata ~o due to the orographic conditions.
Sulfate © 2014 Elsevier Ltd. All rights reserved.
Megacity
1. Introduction (Migliavacca et al., 2004, 2005; Pelicho et al., 2006; Hono rio et al.,
2010, Coelho et al., 2011; Gioda et al., 2013).
Precipitation acidity has been widely studied, encompassing the Over the last century the Brazilian urban population has
causes and the harmful consequences to the ecosystems (Reuss, increased significantly, and currently, more than 80% of the total
1975; Fornaro and Gutz, 2006; Huang et al., 2008; Santos et al., population lives in urban areas (IBGE, 2012). Sa ~o Paulo State has
2011; Huo et al., 2012; Ceron et al., 2013; Xiao et al., 2013). These more than 40 million inhabitants, the largest vehicle fleet in the
studies reflect the complex interaction between the processes of country (20 million), 60% of all Brazilian sugarcane plantation and
atmospheric pollutant removal and the biogeochemical cycles, and over 30% of Brazilian Gross Domestic Product (GDP). The Sa ~o Paulo
how they are affected by local emissions and other factors (Fleming megacity (MASP) is the sixth largest metropolitan area in the world
et al., 2012). In Brazil, there are no established networks for with 20 million inhabitants and 20% of the total Brazilian vehicle
routinely monitoring wet deposition. Such studies come from sin- fleet (IBGE, 2010). Table 1 shows the population data for Sa ~o Paulo
gular initiatives in specific regions over restricted time periods ~o Paulo, with 11 million inhabitants, a population
State capital, Sa
density of 7400 per km2, and more than 6 million of vehicles. Ac-
cording to the environmental agency of S~ ao Paulo State (CETESB),
approximately 90% of MASP air pollutants emissions are due to the
* Corresponding author.
E-mail addresses: vieira.filho@live.com (M.S. Vieira-Filho), clehmann@illinois.
transportation sector, which burns a complex mixture of different
edu (C. Lehmann), adalgiza.fornaro@iag.usp.br (A. Fornaro). fuel types: gasohol (75% gasoline þ 25% anhydrous ethanol),
http://dx.doi.org/10.1016/j.atmosenv.2014.11.025
1352-2310/© 2014 Elsevier Ltd. All rights reserved.
M.S. Vieira-Filho et al. / Atmospheric Environment 101 (2015) 200e208 201
and a dry season from May to August (rainfall < 80 mm month1). ~o and MASP
3.1. Emissions trends in Cubata
The period of the present study was notable for heavy rain with
total of 1884 mm (2009) and 2125 mm (2010) of precipitation. Brazilian national air quality standards were established in 1990
Winter (dry) and summer (rainy) temperatures range from mod- (CONAMA resolution no.3, June 28, 1990) for several pollutants:
erate (average 16 C in July) to high (average 28 C in February). The total suspended particles (TSP), inhalable particle matter (PM10,
dominant wind directions are from the SE and SSE, with a monthly diameter < 10 mm), smoke, sulfur dioxide (SO2), nitrogen dioxide
average wind velocity of 7 km h1 (IAG/USP Meteorological (NO2), carbon monoxide (CO) and ozone (O3). Emissions controls
Station). were initiated earlier in 1972, primarily for TSP and SO2. At that
Cubat~ ao occupies an area of 143 km2 between Atlantic Ocean time, industrial sources were responsible for 74% of the SO2 emis-
and MASP, extending 15 km along the bottom of the Serra do Mar sions in MASP, which declined to 18% in 1990 when vehicular
slope, which reaches 700 me1000 m elevation, where MASP is emissions peaked. The SO2 emissions decreased sixteen-fold
located (Fig. 1). The Atlantic coastline along with the slope is (Table 2), from 1985 until 2009, with industrial sources account-
located along a transect from 225 south-west to 45 north-east. ing for 40% of total emissions in 2009. Implementation of new
This complex orographic structure and differences in surface tem- emissions control technologies was responsible for the decrease of
peratures define local air mass circulation systems and influence SO2 and PM emissions.
the air pollutants dispersion in the Cubata ~o region through sea The number of industrial sources in MASP has decreased sharply
breezes, slope and valley winds, plain and plateau winds (Klockow since the 1980's due to macro-economic factors and S~ ao Paulo State
et al., 1997). The annual climatological rainfall was 3330 mm from policies of taxation and restrictive environmental legislation. The
1937 to 2007, with the wet season from December to March deindustrialization process began in the early 1990's (Padua, 2009),
(rainfall > 300 mm month1) and the dry season from June to altering the region from an industrial to an economic capital,
August (rainfall < 150 mm month1). The rainiest years, 2009 and focusing on banks and services (Carlos, 2009). Despite the fact that
2010, had more rainfall, 3680 and 3930 mm, respectively. the total vehicular fleet increased more than 9-fold, no significant
M.S. Vieira-Filho et al. / Atmospheric Environment 101 (2015) 200e208 203
Table 2 and the sea-breeze, which favors the transport of air pollutants
Official (CETESB) estimates of atmospheric pollutants emissions of stationary (in- uphill were highlighted in the air pollutants studies Cubat~
ao during
dustrial) and mobile sources in the Metropolitan area of S~ao Paulo (MASP) and
Cubata~o City, 1985e2009. the 1980s and early 1990s (Bishoff-Gauss et al., 1998).
Emissions (1000 ton/year)a Fig. 3 shows the SO2 concentration by season in Centro and Vila
Parisi as a function of wind direction from January 2009 to
1985 Mobile 200.2 77.6 20.6 e e e
Stationary 25.2 205.1 71.2 22.3 28.6 86.2 December 2010. It is noteworthy that Centro had higher SO2 levels
1990 Mobile 399.4 77.1 36.1 e e e during the Winter and Autumn (the drier seasons) due to the
Stationaryb 14 17.1 31.6 17.4 18.1 31.7 absence of frequent rainfall events. Also the concentration
1997 Mobile 265.8 26.3 23.1 e e e threshold for the upper percentile 95e99% was significantly higher
Stationary 7.4 40.6 55.6
at Vila Parisi (600 mg m3) than at Centro (300 mg m3). For both
e e e
2000 Mobile 368 21.2c 32.5 e e e
Stationary e e e 18 30 54.7 sites the weaker wind from NE and NW during the first hours in the
2004 Mobile 356.5 20.8d 31.6 e e e morning (Fig. 2) suggested a higher contribution from emissions
Stationary e e e 18.3 20.7 3.8 sources in these directions. In contrast, SW winds of higher velocity
2009 Mobile 362.3 8.4e 31.4 e e e
and associated with sea-breeze were more likely to result in lower
Stationaryf 15.4 5.6 3.1 8.9 15.3 3.2
SO2 concentrations at both locations.
Obs.: The highest monthly SO2 99th percentile concentration was
a
Cetesb 1985, 1993, 1997, 2000, 2004 and 2009.
b
Consolidated industrial inventory in 1990 and not updated until 2008.
223 mg m3 at Vila Parisi air quality monitoring station in June
c
Gasoline C (gasoline þ 22% ethanol) with sulfur 800 ppm (mass) and metro- 2009. In contrast, this value was 36.8 mg m3 for the same period at
politan diesel with sulfur 1100 ppm (mass). Congonhas station, being the highest value, 54.1 mg m3, in August
d
Gasoline C (gasoline þ 22% ethanol) with sulfur 600 ppm (mass) and metro- 2009. Despite the high 99th percentile SO2 reading, the 24 h
politan diesel with sulfur 1100 ppm (mass).
e average did not exceed the NAAQS-Brazil for SO2 (80 mg m3) at
Top-down methodology, based on the global fuel consumption, was adopted
considering that all the sulfur contained in the fuel was transformed into SO2. Diesel either stations. Nevertheless, SO2 concentrations at Vila Parisi
and gasoline C with sulfur 350 ppm (mass). remain a cause for concern due to their elevated spikes.
f
Consolidated industrial inventory in 2008, number of industries evaluated are in
parentheses. 3.4. Wet deposition
winds in the afternoon (SW direction), and weak winds from the 2
SO4 ) in rainwater samples in MASP and Cubata ~o are shown as box-
opposite direction in the morning (NE direction). The mean hodo- whisker plots in Fig. 4c and d. The rainwater ionic composition in
graphs for both stations throughout the sampling campaign illus- Cubata ~o was dominated by sea salt, with sodium and chloride
trate the importance of secondary circulation associated with the concentrations exceeding all other ions. On the other hand, these
complex terrain (strong orographic changes due to the steep slope) species presented lower concentrations than other ions in MASP.
and the proximity to the ocean (land-sea breezes), which influence Nitrate (17.4 mmol L1) and sulfate (24.0 mmol L1) VWM concen-
the transport, dispersion, and wet removal of air pollutants. trations had similar volume weighted mean (VWM) concentrations
The total percentage of calm events (<1.0 ms1) were 21% and in Cubata ~o, while nitrate (16.3 mmol L1) was significantly higher
17% for Centro and Vila Parisi, respectively, in 2009; and 14% and than the sulfate (7.1 mmol L1) in MASP.
18% respectively in 2010. The diurnal wind profile was also The ammonium cation had the highest concentration among all
analyzed in both years; the nighttime periods accounted for more ions in MASP, besides being the only ion presenting higher con-
than 83% of the calm events in the Centro in both years, and 76% in centrations compared with those in Cubata ~o rainwater. The 25th
Vila Parisi. The wind velocities had similar patterns, increasing percentile of ammonium concentrations corresponded to the 50th
during the daylight (Fig. 2); and the mean velocities were 2.05 and percentile of the next higher ion on average (nitrate) in MASP
2.38 m s1 in Centro and Vila Parisi, respectively, which did not samples (Fig. 4ced). While Cubata ~o suffers with significant
favor air pollutant dispersion. The linkage between upslope winds ammonia emissions from fertilizer industries, MASP does not,
204 M.S. Vieira-Filho et al. / Atmospheric Environment 101 (2015) 200e208
Fig. 2. Mean hodographs (winds velocities and directions) for the Cubat~ao-Centro (left) and Vila Parisi (right) monitoring stations, from January 2009 to December 2010.
Fig. 3. Seasonal SO2 concentrations (mg m3) variation as a function of wind directions for the Cubata
~o-Centro (left) and Vila Parisi (right), from January 2009 to December 2010. The
colors represent the concentrations percentile for both sampling sites.
which suggests that ammonium concentration levels may not be total variance in the dataset. The second factor (F2) shows a positive
attributed to those sources. The reduction of nitrogen compounds correlation between Naþ, Mg2þ, and Cl, suggesting that a signifi-
(NOx) by three-way-catalysts has been considered a possible source cant amount of Mg2þ concentration was due to natural processes,
of NH3 emissions in the urban atmosphere (Tao Huai et al., 2003; and influenced by sea-breeze.
þ
Perrino, 2002; Fraser and Cass, 1998), which could explain the A case study with ratio (SO2 4 /Na ) higher than 2.0 was per-
disparity of ammonium in rainwater in MASP. formed to correlate relative sulfate maximums in precipitation
þ
from 95 rainwater samples. This high SO2 4 /Na ratio was observed
for 10 samples; the sequential precipitation events from January
~o
3.4.1. Sources apportionment of wet-only deposition in Cubata
18e22, 2010 (4 samples) were considered as a singular event for
Table 3 shows the multivariate analysis for the Cubat~ao rain-
this analysis. Wind data for 72 h preceding each rainfall event
water ion dataset. The first factor (F1) has a positive correlation
(Fig. 5) were evaluated and compared with the spatial distribution
between NHþ 2þ 2
4 , Ca , NO3 and SO4 ions indicating the importance ~o (Suppl. Fig. 1). It is
of air pollutants stationary sources in Cubata
of the neutralization process, and represented almost 37% of the
M.S. Vieira-Filho et al. / Atmospheric Environment 101 (2015) 200e208 205
Fig. 4. Major cations and anions identified and quantified in Cubata ~o (n ¼ 95) and MASP (n ¼ 58), from June 2009 to August 2010: (a) histogram of rainwater pH values and normal
distribution curves; (b) ionic balance (mel L1) and their linear fit; and box chart graphic for (c) cations and (d) anions, respectively. Horizontal box lines represent 25th, 50th and
75th percentile values; standard deviation depicted as error bars; (square) arithmetic mean.
noteworthy that the events from July 13 and 29, 2009 (Fig. 5aeb) 3.4.2. Worldwide deposition and concentration comparisons
had about 40% calm winds (<1 m s1), suggesting that lower speed The rainwater VWM NO 2
3 , SO4 and NHþ 4 concentrations in
winds could be a driver for higher rainwater sulfate deposition in Brazil are compared with those in other countries (Table 4). Among
Cubata~o due to stationary air masses. The third event on December all sites in Brazil, Balbina, Amazonia registered the lowest con-
8, 2009 (Fig. 5c) showed a distinct pattern with higher S and SE centrations, indicating a region with little anthropogenic emission
wind direction frequencies. However, the frequency of calm events influence. The ion VWM concentrations in Balbina presented levels
was significant (16%). The event on January 22, 2010 (Fig. 5e) comparable to those remote locations in the United States, such as
showed stronger winds from a northerly direction, which is the Denali National Park, Alaska and Olympic National Park, Wash-
location of the largest oil refinery (Suppl. Fig. 1). Events on January 8 ington State (Table 4). NO þ
3 and NH4 VWM concentrations in MASP
and February 23, 2010 (Fig. 5def) showed persistent N and NE wind and Cubata ~o were higher than those reported in the literature for
directions, where most of chemical industries and refineries are Brazil, and comparable to a previous study at Cubata~o from 1984 to
located. 1985. Also nitrate ion concentrations were comparable to those in
Table 3
~o, from June 2009 to August 2010.
Statistics data and factor analysis results for rainwater samples ionic composition in Cubata
industrial areas in the United States (Indiana and Ohio). NHþ 4 ion In addition, some recent studies about background regions
concentrations were higher than those in other locations except for presented values around 0.16 mg S L1 for a forest site in Eastern
Shanghai, China and Mexico City. Shanghai and Mexico City are Brazil and lower than 0.1 mg S L1 in the Amazonian region (Pau-
heavily urbanized and showed the highest sulfate, nitrate and liquevis et al., 2012). The VWM concentration for Cubata ~o was
ammonium levels. Notably, the study in Shanghai city reported 0.78 mg S L1 which exceeds the values reported for North America
rainwater samples with pH < 3.0, indicating a severe acid precipi- and was two times higher than others in Brazilian sites. The annual
tation attributed to large increase in the vehicular fleet and higher ~o was 17.0 kg S ha1 y1, which was 2.7-
sulfur deposition in Cubata
coal/fuel consumption (Huang et al., 2008). VWM concentrations of fold higher than that in MASP from May 2009 to June 2010.
SO2
4 in MASP were lower than those from urban and industrial
areas reported in Table 4.
SO24 VWM concentrations in Cubata ~o (present study) were 4. Conclusions
higher than those in all other locations except for Mexico City,
Cubat~ao (1984e1985), Shanghai and Jiangxi in China. These levels In this study, comparisons of rainwater ionic composition be-
were notably higher than those in some industrial areas in the tween two sampling sites showed higher concentrations of sulfate
United States. Porter and Wayne Counties in the U.S. are located and acidity in Cubat~ ao (industrial region) where topography and
close to heavily industrialized areas, with VWM concentrations of lower wind speeds associated with the sea-breeze circulation
1
4 above 13 and 16 mmol L , respectively, from 2010 until 2012.
SO2 hinder the dispersion of air pollutants. Although the higher air
These values were lower than that (24.5 mmol L1) observed in pollutant emissions in MASP, the worst air quality and wet depo-
Cubat~ao over the same period. sition has been observed in Cubata ~o due to the orographic condi-
A global assessment of precipitation chemistry was recently tions. The SO2 concentrations at Congonhas (MASP) were one-
reported showing regional sulfur (S) deposition trends for two fourth of Vila Parisi's levels, indicating that Cubata ~o concentra-
periods: (i) 2000e2002; and (ii) 2005e2007 (Vet et al., 2014). The tions are still a matter of concern and could result in severe air
VWM concentrations for the highest S emissions areas in Northeast pollution episodes. This is despite the fact that the air quality policy
of U.S. and Southeast of Canada ranged 0.30e0.81 mg S L1 from reduced the SO2 emissions more than 60% in Cubata ~o and 90% in
2000 to 2002 and 0.30e0.68 mg S L1 from 2005 to 2007. More- MASP since the 1980s. Local sources heavily influence wet depo-
þ
over, the highest VWM concentrations reported in Europe were sition chemistry, as evidenced by the SO2 4 /Na ratios.
around 1.0 mg S L1 for the latter period in Ukraine, Czech Republic Regarding the nitrogen content, the reduced form (NHþ 4 ) ex-
and Poland (Eastern Europe). Regarding South America, and spe- ceeds the amount of NO 3 in both sampling sites. Moreover, the
cifically Brazil, data from studies in early 1990's showed that the S difference between reduced and oxidized nitrogen is more pro-
VWM concentrations did not exceed 0.30 mg S L1 (Vet et al., 2014). nounced in Sa ~o Paulo, with more than 61% of total nitrogen scav-
enged as ammonium. The sulfate concentrations in Cubata ~o were
notably higher than data reported from several locations in Brazil
M.S. Vieira-Filho et al. / Atmospheric Environment 101 (2015) 200e208 207
Table 4
Nitrate, sulfate and ammonium volume weighted mean (VWM) concentrations for wet deposition reported from several studies divided by remote, marine, industrial, rural
and urban sites.
Obs.: 1-Present Study; 2- Abbas et al., 1993 and Moreira-Nordemann et al., 1986; 3- NADP, 2012; 4- Huneau et al., 2009; 5- Baez et al., 2007; 6- Pelicho et al., 2006; 7- Lara et al.,
2001; 8 Mphepya et al., 2004; 9- Sakugawa et al., 2000; 10- Santos et al., 2011; 11- Forti et al., 2000, 12- Pauliquevis et al., 2007.
and the United States. In terms of sulfur deposition, the annual wet- ez, A., Belmont, R., García, H.P., Torres, M.C., 2007. Chemical composition of
Ba
~o was 17.0 kg S ha1, which was 2.7-fold higher
only value in Cubata rainwater collected at a southwest site of Mexico City, Mexico. Atmos. Res. 83,
61e75.
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tems in air pollution in the area of Sao Paulo. J. Appl. Meteorol. 37, 269e287.
Carlos, A.F.A., 2009. A metro pole de Sa ~o Paulo no contexto da urbanizaça ~o con-
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