Contribution of Long and Mid-Range Trans
Contribution of Long and Mid-Range Trans
Contribution of Long and Mid-Range Trans
Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv
h i g h l i g h t s
The wet-only deposition was continuously measured for four consecutive years.
The long-range transport potassium compounds contribution was evaluated by backward trajectories.
The bias in the estimate of non-sea salt fraction for rainwater samples is discussed regarding the Cl depletion and pH.
The potassium and sodium ions in rainwater had a significant contribution from the local anthropogenic sources.
a r t i c l e i n f o a b s t r a c t
Article history: The surface winds and backward trajectories were analyzed to investigate sources of sodium and po-
Received 2 January 2013 tassium ions measured in rainwater in the metropolitan area of São Paulo (MASP), Brazil, from July-2002
Received in revised form to December-2005. In this study, we evaluated the chemical composition of 315 rainwater samples with
17 May 2013
focus on precipitation events with high concentrations of sodium and potassium, with cations concen-
Accepted 19 May 2013
trations, at least 1.5 times higher than the sulfate and nitrate concentrations. In the results from the total
samples, the Naþ and Kþ volume weighted mean (VWM) concentrations were 10.4 and 3.2 mmol L1,
Keywords:
respectively, while for the excess events, the concentrations were 32.4 and 11.1 mmol L1. From the 31
Rainwater
Sea-salt
sodium excess events, 45% showed an influence from ocean air masses by the wind direction evaluation
Biomass burning while 57% of backward trajectories for 7 potassium excess events indicated a contribution of biomass
Backward trajectories burning air masses from the northwestern region of the São Paulo State. Although some excess events
HYSPLIT pointed the pattern of long-range transport, they represented less than 15% of total samples. The results
Long-range transport suggest that the megacity itself is predominantly involved in the process of emission and removal of the
compounds and the influence of external components are limited to circumstantial events.
Ó 2013 Elsevier Ltd. All rights reserved.
1352-2310/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.atmosenv.2013.05.047
300 M.S. Vieira-Filho et al. / Atmospheric Environment 79 (2013) 299e307
Lamb, 2003). In another study, the ionic composition of precipita- natural processes. The assessments for potassium and sodium
tion was evaluated through analysis and identification of synoptic compounds sources are mixed and little is known about the
air masses trajectories in a rural area of Spain. Alkaline rainwater anthropogenic emissions of these species in urban areas. Therefore,
(mean pH 7.2) was associated with air masses from Africa. Neutral this study aims to improve the discussion of possible relations from
rainwater (average pH 5.5) was associated with local events, and local or external sources in atmospheric samples.
acid rain events originated from the Atlantic Ocean (average pH 4.8)
and Europe (pH 4.4) with high ionic concentrations. However, the 2. Methodology
acid rain represented less than 10% of total rainfall (Avila and
Alarcon, 1999). In southern Korea, the higher formate and acetate 2.1. Site sampling
ions concentration were associated with air masses trajectories
from the continental area, and lower concentrations with oceanic The State of São Paulo occupies 2.9% of the Brazilian territory and
air masses (Hong et al., 2011). is responsible for over 31% of Brazilian Gross Domestic Product
The wind sector analysis and trajectory models have been used (GDP). The state has over 41 million inhabitants and the largest
to assess the impact of air masses in the chemical composition of vehicle fleet in the country with over 19 million units. Besides
dry and wet deposition (Fleming et al., 2012). In the last years there hosting the largest number of different sectors industries, the state
have been an increasing number of studies about the air pollution of São Paulo centralizes over 50% (3.6 million hectares of cultivated
evaluation through HYSPLIT (Hybrid Single Particle Lagrangian In- area) of the Brazilian production of sugar cane. Many regions (cen-
tegrated Trajectory) model, specifically connecting the backward tral, north and northwest) in the state suffer serious problems of air
trajectories with analyzed wet deposition concentrations. For pollution during the harvest period due to the practice of burning
instance, Morselli et al. (2008) showed the presence of Sahara dust sugar cane manual harvesting (CETESB, 2011). The MASP is located
in particulate matter samples from Bologna, Italy. Báez et al. (2007) in the eastern region of the state of São Paulo (23.5 S and 46.7 W),
evaluated the transport of trace metals to the Central Mexico City with an average altitude of 800 m and w50 km from the shore.
region. The effect of air masses transport in rainwater ionic From 2002 to 2005, MASP had an inhabitant/vehicle ratio around
composition has also been discussed in urban centers with heavy 2.8, with a total of 6 million vehicles. According to CETESB, around
vehicular fleet and industries (Garcia et al., 2006; Strayer et al., 90% of air pollutants emissions were due the transport sector, which
2007). burns a complex mixture of different fuel types: gasohol (78%
The relations between ionic species in rainwater samples are gasoline þ 22% anhydrous ethanol), hydrous ethanol (95% v/v) and
usually applied to identify potential sources for atmospheric diesel. In the period of study the use of ethanol ranged from 34 to
pollution. Traditionally, the sodium ion has been used to identify 44%, gasoline 50e60% and diesel decreases from 6.5 to 5.6% of the
marine influence by the presence of sea-salts in rainwater or in the total fuel burned. This change could be attributed to the beginning of
particulate matter soluble phase. Keene et al. (1986) applied con- the flex fuel vehicles popularization process; this engine repre-
centration ratios to estimate the sea-salt fractions in atmospheric sented 3% of 2005’s vehicular fleet (CETESB, 2005). Samples were
samples, and also emphasized that the sodium ion may not always collected at Mackenzie University campus, in the central area of the
be appropriate. Thus, the evaluation criteria must be carefully MASP, which is a densely urbanized region, surrounded by large
analyzed for the region under study. Recently, Dos Santos et al. avenues with intense traffic of buses and light vehicles.
(2012) discussed the influence of the South Atlantic Ocean on sea
salt mass concentrations in aerosol from urban atmosphere of 2.2. Rainwater sampling
Buenos Aires and highlighted the episodes of high Naþ concen-
trations when onshore winds speed were higher than 4.3 m s1. On The wet-only samples were collected with an automatic rain-
the other hand, the potassium ion was identified as indicator of water collector G. K. Walter Eigenbrodt model (Königsmoor, Ger-
biomass burning processes and biogenic sources (such as leaf many) inside the campus of Mackenzie University (23 320 S,
fragments, pollen, log, etc.), in both wet and dry deposition (Forti 46 390 W), in the central area of MASP, from July 2002 to December
et al., 2000; Pauliquevis et al., 2007). 2005. The high density polyethylene flasks were maintained with
In Brazil, the agriculture activities involving sugar cane har- deionized water until the time of use, in addition to receiving pe-
vesting period, deforestation process and pasture maintenance riodical maintenance for cleaning. After the end of the rainfall
fires in the Amazon are important sources of air pollution (Allen event, or in the early morning (for evening events), the sampling
et al., 2004; Pauliquevis et al., 2007; Honório et al., 2010). High flask was transferred to the laboratory where the sample volume
potassium concentrations in rainwater and particulate matter were was determined. Afterward, fractions of w50 mL were separated
associated with events in some regions with these characteristics. for different analytical determinations (pH, conductivity and major
Also it is important to highlight that the period of fires always co- ions). For ionic chromatography analysis, the sample fraction was
incides with drought or low rainfall seasons, mostly in June through filtered with Millex membrane (pore 0.22 mm) and frozen (18 C)
November (Cavicchioli et al., 2010). until analysis.
In a site such as the Metropolitan Area of São Paulo (MASP), the
local anthropogenic sources of sodium and potassium are signifi- 2.3. Reagents and solutions
cant and could mask these ions origins. In this study, the influence
of mesoscale phenomena, such as the entry of sea breeze (wind All reagents were of analytical grade (>99% purity, Merck) and
speed and direction analysis) and transport of air masses (HYSPLIT were used without further purification. Ultra-pure water used to
model) of the Naþ and/or Kþ in rainwater was evaluated. To identify prepare the solution was obtained from a Barnstead Nanopure
events with excess of sodium and potassium species in rainwater system (resistivity >18 MU cm). The stock standard solutions
samples, ratios between Kþ and/or Naþ ions and anthropogenic (100 mmol L1) were prepared by dissolution of their salts in
ions (NO 2
3 and SO4 ) were calculated. For the MASP, the environ- deionized water and stored at 4 C in the dark. The multi-element
mental agency of São Paulo State (CETESB) attributes more than standard solutions at 5.0, 10, 25 or 50 mmol L1 concentrations
80% of NOx to vehicular emissions and around 60% of SOx to fixed which were used for ion-chromatography measurements were
sources. Moreover, the precursors of Naþ and Kþ in the atmosphere prepared daily by dilution in deionized water of stock standard
are related with land-use activities, marine air masses and other solutions just before use (Leal et al., 2004).
M.S. Vieira-Filho et al. / Atmospheric Environment 79 (2013) 299e307 301
2.4. Instrumentation average value, and only 9 samples out of those had pH values 4.5.
The results of the ionic balance (Allan, 2004) indicate a good dis-
The pH direct measurements were carried out by a potentiom- tribution around the ideal model (y ¼ x), with linear coefficient of
eter Digimed model DM-20. The glass electrode and potentiometer 0.98 (R2 ¼ 0.95) (Fig. 1a). In order to avoid misleading conclusions,
were calibrated with pH 7.00 and 4.00 buffers solutions. Conduc- the ionic balance for rainwater samples with ratios Kþ/NO þ
3 and K /
2 þ þ 2
tivity measurements were made with a conductivimeter Digimed SO4 or Na /NO3 and Na /SO4 above 1.5 was calculated separately
Model DM-31. The measurements of conductivity and pH were to ensure that these samples are representative of the total data set
done with samples at 25 0.2 C. The analyses of major ionic (Fig. 1b).
species were carried out by a chromatographic system Metrohm The potassium and sodium monthly average concentration
761 model with conductivity detection. The detection limits for and monthly rainfall are presented in Fig. 2. The annual climato-
Mg2þ and Ca2þ ions were 2.4 and 1.3 mmol L1, respectively, while logical rainfall from 1939 to 2007 was 1400 mm, with correspon-
for all other evaluated species (CH3COO, HCOO, Cl, NO
2 , NO3 , dent rainy period from December to March with rainfall
þ þ þ
SO2 2
4 , C2O4 , Na , K and NH4 ), the detection limits were lower >150 mm month1 and drought period from May to August with
than 1.0 mmol L1. The details for these determinations were dis- rainfall <50 mm month1. Winter (dry) and summer (rainy) tem-
cussed previously (Leal et al., 2004). peratures range from moderate (average 16 C in July) to high
(average 28 C in February). The total rainwater volume studied
2.5. Meteorological data (3960 mm) represented 70% of the rainfall for the period in the
MASP, and was also well distributed in all months. The potassium
The hourly wind data at ground level were obtained from the maximum monthly concentration was usually observed in the dry
Center for Weather Forecasting and Climate Studies (CPTEC/INPE), period (shaded regions) while sodium did not show a clear pattern
and meteorological data station from Institute of Astronomy, with some relative maximums in both seasons.
Geophysics and Atmospheric Sciences, University of São Paulo (IAG/ Fig. 3 shows potassium, sodium, chloride, sulfate and nitrate
USP) were evaluated for the events of sodium and potassium excess. concentrations variability, with extreme, mean and median values.
Backward trajectories were generated with 72 h from HYSPLIT Nitrate and sulfate were the dominant species, exceeding all other
model (Draxler and Hess, 1997; Draxler and Rolph, 2012; HYSPLIT e ions due to the expressive anthropogenic emission processes in a
http://ready.arl.noaa.gov/HYSPLIT.php) obtained through the metropolitan area like São Paulo. The potassium arithmetic mean
READY (Real-time Environmental Applications and Display System) concentration (4.89 10.5 mmol L1) was 5.8 times lower than the
platform from NOAA (National Oceanic and Atmospheric Admin- nitrate (28.5 27.5 mmol L1) and 3.4 times lower than the sulfate
istration). Meteorological data (Reanalysis) - products of NOAA/ (16.7 17.7 mmol L1). Regarding the sodium ion, the average
OAR/ESRL PSD, Boulder, Colorado, USA e from the global atmo- concentration (17.6 30.3 mmol L1) to the set of samples was
spheric model for the years 2002e2005 were used as input data substantially equal to sulfate (Fig. 3). However, the median value for
(http://www.esrl.noaa.gov/psd/, accessed in November, 2012). sodium was 1.4 times lower than sulfate (10.9 mmol L1).
Backward trajectories of each excess event end at 23.55 S and Within the total set of samples evaluated, samples with sodium
46.64 W, the last 24 h of integration represent the sample collec- and potassium concentrations higher than nitrate and sulfate
tion date. The vertical velocities from the Reanalysis were used for concentrations were identified. In order to characterize these
all potassium events. The height levels trajectories used were 500, events, the adopted criteria based on ratios [Kþ]/[NO þ
3 ] and [K ]/
2 þ þ 2
1500 and 3000 m above ground level (AGL) to avoid complicated [SO4 ] or [Na ]/[NO3 ] and [Na ]/[SO4 ] > 1.5 were used to evaluate
local topography. the possible long-range transport influence to the rainwater ionic
composition in MASP. From this restriction, only 7 samples fol-
3. Results and discussion lowed this condition for potassium, <3%, and 31 for sodium, w10%.
The volume weight mean (VWM) concentrations of some rain-
3.1. Ionic composition water ions from MASP are compared with other sites sampling on
Table 1. While the cations concentrations presented little differ-
Regarding the acidity evaluation, the total of 315 rainwater ences between the dry and rainy seasons, sodium (32.4 mmol L1)
samples can be considered neutral, characterized by a 5.3 pH and potassium (10.9 mmol L1) excess events were significantly
Fig. 1. a) Ionic balance in rainwater samples collected from July 2002 to December 2005 (n ¼ 315) in downtown MASP. b) Ionic balance in rainwater samples with ratios of sodium
(n ¼ 31) and potassium (n ¼ 7) exceeding 1.5 in relation with sulfate and nitrate concentrations.
302 M.S. Vieira-Filho et al. / Atmospheric Environment 79 (2013) 299e307
differences among dry and rainy seasons. The nitrate and sulfate
concentrations in São Paulo from the dry period were at least two
times lower than those evaluated in Mexico City (Báez et al., 2007).
Table 1
Comparison of the volume weight mean (VWM) ions concentrations in MASP and other sites in Brazil and worldwide.
São Paulo (rainy)a 07/2002e12/2005 231 10.9 3.0 8.5 19.9 11.1 a
São Paulo (dry)b 84 8.8 3.8 9.2 20.3 12.2
São Paulo (Kþ excess) 7 15.9 10.9** 5.2 6.1 5.6
São Paulo (Naþ excess) 31 32.4* 6.4 20.9 13.0 8.8
Sugar cane non-harvestc 01/2003e07/2007 264 0.9 1 1.1 8.1 1.8 b
Sugar cane harvestc 2.5 5.7 4.5 17.5 5.3
Central Amazonia (rainy) 04/1998e12/2001 87 2.4 1.1 3.3 3.7 2.0 c
Central Amazonia (dry) 5.6 1.9 7.4 7.5 5.1
Northern India (rainy) 06/1999e09/2001 57 8.4 2.4 9.9 7.7 4.6 d
Northern India (dry) 11 17.3 4.2 15.9 13.4 7.1
Mexico City (rainy season) 2001e2002 71 7.0 2.2 9.6 42.6 30.9 e
Taiwan 01/1999e12/2000 79 75 6 90 22 29 f
Hong Kong 152 37 4 43 27 37
The p-values from t-test for both set of samples are indicated in bold. For sodium (*p-value < 105) and potassium (**p-value < 0.06). References: a) this study; b) Coelho et al.,
2011; c) Pauliquevis et al., 2007; d) Khare et al., 2004; e) Báez et al., 2007; f) Wai et al., 2007.
a
VWM for the months with rainfall >100 mm: OctobereMarch.
b
VWM for the months with rainfall <100 mm.
c
Central region of São Paulo State: AprileSeptember.
Fig. 4. Spatial distribution of the number of monthly fire spots (28 km 28 km) in Brazil based on data from satellite NASA GSFC, calculated by INPE (Instituto Nacional de Pesquisas
Espaciais). The statistics for maximum, minimum and mean fire spots per square area are presented as well. Accessed in August 07, 2012: http://www.inpe.br/queimadas.
304 M.S. Vieira-Filho et al. / Atmospheric Environment 79 (2013) 299e307
Fig. 5. Backward trajectories plots (72 h) from HYSPLIT model for the days when excess potassium concentrations were registered in the rainwater samples in MASP. The above
ground levels are 500 m (red), 1500 m (blue) and 3000 m (green).
for pizzerias and steakhouses in 2003 (BESP, 2004). This total Regarding to the surface winds, the sea breeze in São Paulo can
firewood can be expressed as 7.5 ha of eucalyptus forest per month be characterized by the intensification or change to quadrant Easte
(considering the wood density of 390 kg m3). These sources are South, and these changes may be preceded by quadrant NortheEast
usually not considered in atmosphere chemical balances and winds (Oliveira and Dias, 1982; Oliveira et al., 2003). From the total
contribute to potassium concentrations. of our rainwater samples, only 31, were identified as sodium excess
events by calculating the ratios ([Naþ]/[NO 3 ] and [Na ]/
þ
2
3.3. Sodium excess events [SO4 ] > 1.5). The surface wind speed and direction (Fig. 6) were
analyzed for all these days. The maximum scale for velocity is
The land use changes and urbanization could cause alteration on indicated in the upper right corner, and the vector absence corre-
atmospheric circulations, changing surface fluxes and dispersion of sponds to calm winds condition (<1 m s1). The wind intensity
pollutants (Morris et al., 2001; Freitas et al., 2007). The MASP is distribution indicates a predominance of calm conditions (47%),
located at a distance of w50 km from the coastline, and there is a while only 10% reaches values higher than 6 m s1. Based on these
mountain range (Serra do Mar) with ridges up to 1000 m, between observations it is possible to confirm the light wind speed char-
this region and the sea coast, which imposes a natural barrier to the acteristic of MASP as previously discussed by Rodriguez et al.
air masses from the Atlantic Ocean. The sea breeze circulation is (2010). For the 31 days with sodium excess, 45% of them exhibit
considered important mesoscale circulation to MASP, which is the sea breeze wind direction pattern for MASP. In these 14 days,
characterized by an intensification of southeast winds at the sur- the wind maximum intensity occurred during the mid-afternoon,
face at 13e14 h (local time) in 50% of year days (Oliveira and Dias, where the shaded areas (Fig. 6) indicate the largest period of the
1982; Oliveira et al., 2003). In order to observe the phenomenon of sea breeze occurrence (Pereira Filho et al., 2005; Vemado, 2012).
the incoming sea breeze, data from IAG/USP weather station, Regarding the classification by surface winds, the sea breeze was
located in the path of the incoming breeze toward the MASP were absent in 55% of the days analyzed. Therefore, the influence of the
analyzed. ocean is not mandatory for high relative sodium concentrations in
M.S. Vieira-Filho et al. / Atmospheric Environment 79 (2013) 299e307 305
Fig. 6. Hourly wind variation for the events with higher sodium concentrations in rainwater samples in MASP. The events are separated by year: a) 2002. b) 2003. c) 2004 and d)
2005. Data were from Weather Station of IAG/USP. The shaded hours represent the sea-breeze occurrence period.
MASP. In the earth’s crust the sodium has a mixing ratio of implies that one of these ions, usually the sodium, is not consumed
22,700 ppm (2.27%), ranking it as the seventh most abundant or produced by other processes. In other words, no local sources are
element and the fifth most abundant metal. There are unlimited considered in this evaluation. The reported ratios between chloride
supplies of sodium chloride in ocean waters and natural brines, and sodium in seawater from the literature vary 20% around the
besides the incorporation in basic industries for inorganic matter value found by Wilson (1975). This variability is due to difference in
manufacturing (Greenwood and Earnshaw, 1984). Thus, these re- local sampling sites, since particles from the soil dust are also added
sults highlight the importance of local sources for sodium ion in to the rainwater, changing this ratio.
MASP. Another aspect of sodium chloride in atmospheric samples,
Several studies showed that the ions ratios in seawater indicated particularly aerosol and fogs (i.e., low liquid water content), it is the
the influence of sea spray in the atmospheric samples; this possibility of Cl loss due to the incorporation of nitric acid (HNO3),
connection was deeply evaluated by Keene et al. (1986). Analyses of nitrogen dioxide (NO2), sulfuric acid (H2SO4) or sulfur dioxide (SO2)
aerosols composition in remote coastal regions indicated Naþ and in the droplets, which volatilizes hydrochloric acid (HCl) to atmo-
Mg2þ concentrations similar to seawater samples. Therefore, these sphere due to the increase in acidity (Martens et al., 1973). The loss
species retain oceanic properties and could be considered tracers of Cl is dependent on the acidity, and statistically significant
(Talbot et al., 1986). It is important to note that these assumptions (w89%) under high acidity conditions, pH < 3 (Keene et al., 1998). It
have been systematically used for rainwater samples (Lara et al., is important to note that the chloride depletion phenomenon was
2001; Mello, 2001; Teixeira et al., 2004; Khare et al., 2004; reported in dry deposition of coastal regions, and part of this HCl
Zhuang et al., 2008; Huneau et al., 2009). However, using this can reincorporate in wet deposition regardless of the mechanism.
relation to quantify the sea salt fraction on aerosol or rainwater So the loss of Cl is lower or even not observed in rainwater
Table 2
Pearson correlation among sodium, chloride and potassium ions identified in the São Paulo rainwater samples, also the chloride and sodium ratios are presented. The values
were classified by dry and rainy seasons.
Fig. 7. Ratio Cl/Naþ concentrations in function of: (a) Naþ concentration and (b) pH values in rainwater samples in MASP from July 2002 to December 2005. The shaded ratio
represents the values reported in Keene et al. (1986) for seawater samples plus a deviation of 20%. The bold dots represent the samples with ratios that exceeded 1.5 in relation with
sulfate and nitrate concentrations.
samples (Andreae et al., 1990; Wai et al., 2007). Other potential ocean influence did not play an important role in the occurrence of
sources of sodium or magnesium, such as soil dust, represent the excess concentrations, considering that less than half of these
important aspect to be evaluated in coastal regions (Ayears et al., events were preceded by the sea breeze. This high concentration
1999). implies a considerable bias in the estimate of non-sea salt fraction
To evaluate the presence of the sodium chloride in rainwater for atmospheric deposition, if it is considered that the sodium only
samples, the ratios between these ions were calculated and dis- originated from oceanic processes. From 2002 to 2005, the sodium
cussed as follows. The Pearson correlation for rainy and dry seasons and potassium excess events were circumstantial and indicate that
was evaluated for potassium, sodium and chloride (Table 2). The binding these ions concentrations with only external sources could
corresponding p-values indicated a high significant level for so- lead to underestimation and/or equivocal findings in MASP.
dium and chloride correlations, and the association was also
stronger in the rainy season (0.88). This value implies that these Acknowledgments
species could have originated from similar sources, for instance, the
sea-spray. However, the ratio between these species was closer to This research has been supported by FAPESP (03/01194). The
the seawater value (1.17) in the dry season, which mixes the hy- authors are grateful to the NOAA for the provision of the HYSPLIT
pothesis about the similarity of the sources and suggests a Cl trajectories model used in this publication, and also thanks to the
depleted state during the rainy season. To evaluate the Cl loss Meteorological Station (IAG/USP), CPTEC/INPE and INMET for the
effect, Cl/Naþ ratios as a function of sodium concentration and pH other atmospheric data. We also thank to CAPES and CNPq for the
were evaluated (Fig. 7); the shaded region represents the seawater student grants provided. We thank Dr. E. Abrantes for the English
ratios (20% standard deviations) reported in the literature. The revision.
samples with sodium excess (n ¼ 31), predominantly presented
chloride deficiency. As no significant pH effect on Cl/Naþ ratios
References
(Fig. 7b) was observed, it is not reasonable to evaluate the sodium
excess due to the HCl volatilization (chloride loss). Considering the Allan, M.A. (Ed.), 2004. Manual for the GAW Precipitation Chemistry Programme e
above discussion, it is possible to consider other sodium com- Guidelines, Data Quality Objectives and Standard Operating Procedures GAW-
pounds sources, rather than only the sea-spray sodium chloride for 160. WMO GAW-World Meteorological Organization Global Atmosphere Watch.
Allen, A.G., Cardoso, A.A., da Rocha, G.O., 2004. Influence of sugar cane burning on
the MASP. aerosol soluble ion composition in Southeastern Brazil. Atmospheric Environ-
ment 38, 5025e5038.
4. Conclusions Andreae, M.O., Talbot, R.W., Berresheim, H., Beecher, K.M., 1990. Precipitation
chemistry in central Amazonia. Journal Geophysical Research 95 (D10), 16987e
16999.
In this study the wet deposition was measured continuously at a Avila, A., Alarcon, M., 1999. Relationship between precipitation chemistry and
highly urbanized site with rainfall representativeness higher than meteorological situations at a rural site in NE Spain. Atmospheric Environment
33, 1663e1677.
70%. As a result, 7 samples were classified as potassium excess Ayears, G.P., Gillett, R.W., Cainey, J.M., Dick, A.L., 1999. Chloride and bromide loss
samples with a VWM concentration of 10 mmol L1, and 31 for the from sea-salt particles in Southern Ocean air. Journal of Atmospheric Chemistry
sodium with 32 mmol L1, while for the total samples these ions 33, 299e319.
VWM concentrations were 4 and 15 mmol L1, respectively. From
Báez, A., Belmont, R., García, R., Padilla, H., Torres, M.C., 2007. Chemical composition
of rainwater collected at a southwest site of Mexico City, Mexico. Atmospheric
backward trajectories analyses, we observed that half out of these Research 86, 61e75.
potassium excess events, presented concentrations directly pro- BESP, 2004. Balanço Energético do Estado de São Paulo Ano Base 2003. Secretaria de
Energia, Recursos Hídricos e Saneamento, São Paulo (Estado), p. 205. (Série
portional to fire spot numbers, which means that some maximum
Informações Energéticas, 002).
potassium concentrations in rainwater samples could be associated Beverland, I.J., Crowther, J.M., Srinivas, M.S.N., Heal, M.R., 1998. The influence of
with biomass burning activities. However, it was not possible to meteorology and atmospheric transport patterns on the chemical composition
distinguish the sugar cane management from the long-range of rainfall in south-east England. Atmospheric Environment 32 (6), 1039e1048.
Cavicchioli, A., Morrone, E.P., Marques, R., Fornaro, A., 2010. Impactos atmosféricos
transport from forest biomass burning in Brazilian central- das transformações territoriais e do crescimento do agronegócio na Amazônia
northern regions. For the sodium events it was observed that the matogrossense. Confins (Online), 10/2010, URL: http://confins.revues.org/6646.
M.S. Vieira-Filho et al. / Atmospheric Environment 79 (2013) 299e307 307
CETESB, 2005. Relatório de qualidade do ar no Estado de São Paulo 2004. Série Leal, T.F.M., Fontenele, A.P.G., Pedrotti, J.J., Fornaro, A., 2004. Composição iônica
Relatórios/Secretaria do Estado do Meio Ambiente, São Paulo. ISSN 0103e4103. majoritária de águas de chuva no centro da cidade de São Paulo. Quimica Nova
http://www.cetesb.sp.gov.br/ar/qualidade-do-ar/31-publicacoes-e-relatorios. 27 (6), 855e861.
CETESB, 2011. Relatório de qualidade do ar no Estado de São Paulo 2010. Série Martens, C.S., Wesolowski, J.J., Harris, R.C., Kaifer, R., 1973. Chlorine loss from Puerto
Relatórios/Secretaria do Estado do Meio Ambiente, São Paulo. ISSN 0103e4103. Rican and San Francisco Bay area marine aerosols. Journal of Geophysical
http://www.cetesb.sp.gov.br/ar/qualidade-do-ar/31-publicacoes-e-relatorios. Research 78, 36.
Coelho, C.H., Allen, A.G., Fornaro, A., Orlando, E.A., Grigoletto, T.L.B., Mello, W.Z., 2001. Precipitation chemistry in the coast of the Metropolitan Region of
Campos, M.L.A.M., 2011. Wet deposition of major ions in a rural area impacted Rio de Janeiro, Brazil. Environmental Pollution 114, 235e242.
by biomass burning emissions. Atmospheric Environment 45, 5260e5265. Morris, C.J.G., Simmonds, I., Plummer, N., 2001. Quantification of the influences of
Cuadra, S.V., Costa, M.H., Kucharic, C.J., da Rocha, H.R., Tatsch, J.D., Inman- wind and cloud on the nocturnal urban heat island of a large city. Journal
Bamber, G., da Rocha, R.P., Leite, C.C., Cabral, O.M.R., 2012. A biophysical model Applied Meteorology 40, 169e182.
of sugar cane growth. GCB Bioenergy 4, 36e48. Morselli, L., Bernardi, E., Vassura, I., Passarini, F., Tesini, E., 2008. Chemical
Dayan, U., Lamb, O., 2003. Meteorological indicators of summer precipitation composition of wet and dry atmospheric depositions in an urban environment:
chemistry in central Pennsylvania. Atmospheric Environment 37, 1045e1055. local, regional and long-range influences. Journal Atmospheric Chemistry 59,
Dos Santos, M., Dawidowski, L., Smichowski, P., Ulke, A.G., Gómez, D., 2012. Factors 151e170. http://dx.doi.org/10.1007/s10874-008-9099-9.
controlling sea salt abundances in the urban atmosphere of coastal South Oliveira, A.P., Dias, P.L.S., 1982. Aspectos observacionais da brisa marítima em São
American megacity. Atmospheric Environment 59, 483e491. Paulo. In: Anais do II Congresso Brasileiro de Meteorologia, Pelotas, Rio Grande
Draxler, R.R., Rolph, G.D., 2012. HYSPLIT (HYbrid Single-particle Lagrangian Inte- do Sul, Brasil, pp. 129e161.
grated Trajectory). Model Access via NOAA ARL READY Website. NOAA Air Re- Oliveira, A.P., Bonstein, R.D., Soares, K., 2003. Annual and diurnal wind patterns in
sources Laboratory, Silver Spring, MD. http://ready.arl.noaa.gov/HYSPLIT.php. the city of São Paulo. Water Air Soil Pollution Focus 3, 3e15.
Draxler, R.R., Hess, G.D., 1997. Description of the Hysplit_4 Modeling System. NOAA Pauliquevis, T., Lara, L.L., Antunes, M.L., Artaxo, P., 2007. Aerosol and precipitation
Technical Memorandum ERL ARL-224, December, p. 24. chemistry in a remote site in Central Amazonia: the role of biogenic contri-
Fleming, Z.L., Monks, P.S., Manning, A.J., 2012. Untangling the influence of air-mass bution. Atmospheric Chemistry and Physics Discussions 7, 11465e11509.
history in interpreting observed atmospheric composition. Atmospheric Pereira Filho, A.J., Massambani, O., Hallak, R., Karam, H., 2005.
Research 104-105, 1e39. http://dx.doi.org/10.1016/j.atmosres.2011.09.009. A hidrometeorological forecast system for the Metropolitan Area of Sao Paulo.
Forti, M.C., Melfi, A.J., Astolfo, R., Fostier, A.H., 2000. Rainfall chemistry composition In: World Weather Research Program Symposium on Nowcasting and Very
in two ecosystems in the northeastern Brazilian Amazon (Amapa State). Journal Short Range Forecasting e Toulouse, France, Meteofrance (CDROM).
of Geophysical Research 105 (D23), 28,895e28,905. Rodriguez, C.A.M., da Rocha, R.,P., Bombardi, R., 2010. On the development of
Freitas, E.D., Rozoff, C.M., Cotton, W.R., Silva Dias, P.L., 2007. Interactions of an urban summer thunderstorms in the city of São Paulo: mean meteorological charac-
heat island and sea-breeze circulations during winter over the metropolitan teristics and pollution effect. Atmospheric Research 96 (2e3), 477e488.
area of São Paulo, Brazil. Boundary-Layer Meteorology 122, 43e46. Samara, C., Tsitouridou, R., Balafoutis, C.H., 1992. Chemical composition of rain in
Garcia, R., Torres-Ma, C., del, Padilha, H., Belmont, R., Azpra, E., Arcega-Cabrera, F., Thessaloniki, Greece, in relation to meteorological conditions. Atmospheric
Báez, A., 2006. Measurement of chemical elements in rain from Rancho Viejo, a Environment 26B (3), 359e367.
rural wooded area in the State of Mexico, Mexico. Atmospheric Environment Seinfeld, J.H., Pandis, S.N., 1998. Atmospheric Chemistry and Physics of Air Pollution,
40, 6088e6100. 2o ed. John Wiley, New York.
Gonçalves, C., Santos, M.A., Fornaro, A., Pedrotti, J.J., 2010. Hydrogen peroxide in the Setzer, A.W., 1993. Operational satellite monitoring of fires in Brasil. International
rainwater of Sao Paulo megacity: measurements and controlling factors. Journal Forest Fire News, FAO-UN 9, 8e11. http://queimadas.cptec.inpe.br/wrqueimadas/
of Brazilian Chemical Society 21, 331e339. documentos/1993_Setzer_Operational_Monitoring_FAO.pdf.
Greenwood, N.N., Earnshaw, A., 1984. Chemistry of Elements, 1 ed. Pergamon Press. Strayer, H., Smith, R., Mizak, C., Poor, N., 2007. Influence of air mass origin on the
Hong, S.B., Kim, W.H., Ko, H.J., Lee, S.B., Lee, D.E., Kang, C.H., 2011. Characteristics of wet deposition of nitrogen to Tampa Bay, Florida e an eight-year study. At-
formate and acetate concentrations in precipitation at Jeju Island, Korea. At- mospheric Environment 41, 4310e4322.
mospheric Research 101, 427e437. Talbot, R.W., Harris, R.C., Browell, E.V., Gregory, G.I., Sebacher, D.I., Beck, S.M., 1986.
Honório, B.A.D., Horbe, A.M.C., Seyler, P., 2010. Chemical composition of rainwater Distribution and geochemistry of aerosols on tropical North Atlantic tropo-
in western Amazonia d Brazil. Atmospheric Research 98, 416e425. sphere: relationship to Saharan dust. Journal of Geophysical Research 91 (D4),
Huneau, F., Celle-Jeanton, H., Travi, Y., Loye-Pilot, M.D., Bertrand, G., 2009. Rain- 5173e5182. http://dx.doi.org/10.1029/JD091iD04p05173.
water chemistry at a Mediterranean inland station (Avignon, France): local Teixeira, E.C., Migliavacca, D., Pires, M., Fachel, J., 2004. Study of chemical elements
contribution versus long-range supply. Atmospheric Research 91, 118e126. in atmospheric precipitation in South Brazil. Atmospheric Environment 38,
Keene, W.C., Sander, R., Pszenny, A.A.P., Vogt, R., Crutzen, P.J., Galloway, J.H., 1998. 1641e1656.
Aerosol pH in the marine boundary layer: a review and model evaluation. Vemado, F., 2012. Sea Breeze Circulation Analysis and Its Impacts over Metro-
Journal of Aerosol Science 29 (3), 339e356. politan Area of São Paulo Precipitation Using ARPS Model (M.S. thesis).
Keene, W.C., Pszenny, A.A.P., Galloway, J.N., Hawley, M.E., 1986. Sea-salt corrections Institute of Astronomy, Geophysics and Atmospheric Sciences, University of
and interpretation of constituent ratios in marine precipitation. Journal of São Paulo.
Geophysical Research 91 (D6), 6647e6657. Wai, K.M., Wang, S.H., Tanner, P.A., Lin, N.H., 2007. A dual study of the rainwater
Khare, P., Goel, A., Patel, D., Bejari, J., 2004. Chemical characterization of rainwater at a chemistry within the western Pacific region. Journal Atmospheric Chemistry 57,
developing urban habitat of Northern India. Atmospheric Research 69, 135e145. 85e103.
Lara, L.B.L.S., Artaxo, P., Martinelli, L.A., Victoria, R.L., Camargo, P.B., Krusche, A., Wilson, T.R.S., 1975. Salinity and the Major Elements of Sea Water. In: Chemical
Ayers, G.P., Ferraz, E.S.B., Ballester, M.V., 2001. Chemical composition of rain- Oceanography, vol. 1. Academic, Orlando, pp. 364e413.
water and anthropogenic influences in the Piracicaba River Basin, Southeast Zhuang, G., Huang, K., Xu, C., Wang, Y., Tang, A., 2008. The chemistry of the severe
Brazil. Atmospheric Environment 35, 4937e4945. acidic precipitation in Shanghai, China. Atmospheric Research 89, 149e160.