Atmospheric Research 80 (2006) 67 – 85

www.elsevier.com/locate/atmos

Rainwater chemical composition at two sites in

Central Mexico
A.P. Báez *, R.D. Belmont, R.M. Garcı́a, M.C.B. Torres, H.G. Padilla
Laboratorio de Quı́mica Atmosférica, Centro de Ciencias de la Atmósfera,
Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, México D.F. 04510, Mexico
Received 28 February 2004; received in revised form 30 March 2005; accepted 24 June 2005

Abstract

Chemical analyses were performed on rainwater samples collected at the National Autonomous
University of Mexico (UNAM) in Mexico City and at a wooded site, Rancho Viejo (RV) in the State of
Mexico, for the periods 1994–2000 and 1994–1999, respectively. At UNAM, rainwater was collected for the
entire rainy season period each year, while at RV, technical considerations limited collection to weekends
only. The results showed large variations in rainwater chemical composition in most years, mainly because of
the variability of meteorological conditions and also because of changes in source emissions. Sulfates and
NH4+ showed higher annual volume-weighted mean concentrations (VWMC) in both sites. At UNAM, the
maximum annual VWMC for SO42 occurred in March and the minimum in July and August. Lower
concentrations of almost all ions were found at RV; however, the H+ concentration was higher at this site. The
pH in Mexico City, calculated from the annual VWMC of H+, was 4.95, which is a little higher than pH
values reported in some other countries. Despite the fact that sulfate and NO3 concentrations were lower at
RV, the pH was lower. Air-mass back trajectories were calculated for individual concentrations of SO42, H+,
NH4+, Ca2+, and Mg2+, observed at each sampling site for weekend data. At RV, sulfate concentrations were
higher when air-mass back trajectories indicated a wind flow from Mexico City and Toluca at 1000 MAGL
(meters above ground level) and 3000 MAGL. The hydrogen ion exhibited the same behavior. Calcium and
Mg2+ concentrations were also higher when the wind blew from urban areas at 1000 and 3000 MAGL. At
UNAM, H+ concentration was lower and Ca2+ and Mg2+ were higher when wind blew from the northern
sector of the city at 1000 and 3000 MAGL. In UNAM, the NO3/SO42 and NH4+/SO42 ratios were 0.5 and
1.09 in 1994 and 0.86 and 1.64 in 2000, respectively, indicating a decrease in SO2 emissions resulting from
the change of fuel oil to gas fuel. The SO42/Ca2+ ratio was significantly lower at the UNAM site (1.82)
compared to RV (5.36), and the SO42/H+ ratio was significantly higher at the UNAM site (6.77) compared to
RV (2.01). The Spearman’s rho correlation between ionic concentrations indicated a positive correlation in
most cases ( p b 0.05) for data from UNAM and RV. The multiple regression correlation analysis to predict

* Corresponding author. Tel.: +52 55 5622 4071; fax: +52 55 5622 4050.
E-mail address: barmando@atmosfera.unam.mx (A.P. Báez).

0169-8095/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.atmosres.2005.06.008
68 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85

H+ concentration in Mexico City showed that NO3, NH4+, SO42, and Ca2+ contributed 23.2%, 20.9%, 8.0%,
and 6.1%, respectively, to the H+ prediction, while Cl plus Na+ plus K+ only contributed 2.2%, and Mg2+
did not contribute. Sea-salt contribution to rainwater chemical composition was negligible with any wind
direction at both levels. Excess sulfate (non-sea-salt sulfate) represented 98.7% of the total sulfate in
rainwater collected during weekends at RV and 98.6% for weekend and annual rain samples at UNAM.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Rainwater chemistry; Annual variations; Acidity in forests; Central Mexico

1. Introduction

Although the chemical composition of wet precipitation has been studied in many countries for
more than 30 years, such investigations remain important because anthropogenic emissions of
some gases and aerosols in the atmosphere are continuously increasing. Air pollutant emissions are
increasing rapidly in Asia, and the opposite is the case in Europe and North America (Higashino et
al., 1997). Lee et al. (2000) reached the same conclusion, stating that the fast-growing economy in
East Asia resulted in increased emissions of SO2 and NOx . According to Galloway (1995), future
emissions of these pollutants in Asia will be equal to or even greater than the combined emissions
of Europe and North America by 2020. Emissions from fossil fuel combustion have produced an
environmental acidification of rain (Higashino et al., 1997; Lee et al., 2000; Terada et al., 2002). As
a consequence, there has been damage to terrestrial, aquatic, and biological systems. Regarding
ammonia, its concentration has increased substantially over the past years (Walker et al., 2000).
The geographical extent to which precipitation chemistry is affected by industrial emissions has
produced transboundary pollution with the associated ecological and political problems (Lee,
1993; Tuncer et al., 2001). Herut et al. (2000) performed chemical analyses of rain samples
collected during five winter seasons and studied the variation of rain chemistry in relation to
natural and anthropogenic sources and transport of the constituents. Civerolo and Rao (2001)
reported a space–time analysis of precipitation-weighted SO42 concentration data across the USA.
Several studies of temporal trends in precipitation chemistry in different regions have been
published. Dillon et al. (1988) reported a 10-year trend for sulfate, nitrate, and hydrogen
deposition in Central Ontario. Fay et al. (1989) published observed and modeled trends of sulfate
and nitrate in precipitation in eastern North America. Puxbaum et al. (1998) concluded that
sulfate and hydrogen concentrations have decreased with well-defined significant trends in
central Austria in a 10-year trend study of the precipitation chemistry. Other studies of trends for
nitrate and ammonium concentrations have been conducted (Erisman et al., 1989; Lynch et al.,
1995; Avila, 1996). In the present study, the chemical composition of precipitation and temporal
variability were determined in a highly polluted urban area and in a rural area from 1994 to
2000. The aim was to examine the long-term temporal variability of rainwater chemical
composition in Mexico City and Rancho Viejo and its relationship to governmental policies of
anthropogenic gas emissions.

2. Materials and methods

2.1. Sampling sites

One sampling site was chosen in Mexico City (Fig. 1). The rain collector was located on the
roof of the Atmospheric Sciences Center building at the campus of the National Autonomous
 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85
Fig. 1. Sampling site locations; M.C.M.Z. stands for Mexico City Metropolitan Zone.

69
70 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85

University of Mexico (UNAM), at an elevation of 2250 m above sea level (masl). The mean
annual rainfall is 860 mm. Rancho Viejo (RV) is located in a mountainous wooded region about
80 km southwest of Mexico City (Fig. 1). It is a small place with scattered houses mainly used
on weekends and holidays. It is situated at 2700 masl surrounded by mountains covered with
pine forests. This site was included for comparison of the results with those obtained at UNAM.
It was also included because it lies beyond Mexico City limits with no nearby air-polluting
sources but is also downwind of Mexico City, especially during the rainy season. Therefore, it is
only responsive to regional emission sources and consequently is ideal for evaluating the impact
that Mexico City has on rainwater chemical composition in forest ecosystems.

2.2. Sample collection

Daily wet-only rainwater samples were collected at the UNAM site from 1994 to 2000 with
an automatic wet/dry precipitation collector (Andersen Metal Works, Inc.) and transferred into
standard high-density polyethylene buckets (29.5 cm diameter). The total rainfall amount
collected was 4363 mm.
In RV, unfortunately, it was only possible to collect rain samples on weekends because of
technical limitations. The primary consideration was lack of personnel able to remain
continuously at this isolated place during the entire rainy season. Rain samples were collected
from 1994 to 1999 also with an automatic wet/dry precipitation collector (Andersen Metal
Works, Inc.). The total rainfall amount collected was 1205 mm.
After collection, rainwater from the bucket was poured out into a high-density polyethylene
bottle, sealed with its respective cap, and refrigerated until chemical analyses were performed.
Buckets were cleaned thoroughly with deionized water just after rain sample collection.

2.3. Statistical analysis

The Kruskal–Wallis ANOVA Ranks Test was used to compare sulfate and calcium
concentrations among the different wind sectors, obtained from air-mass back trajectory
analysis for 1000 and 3000 m above ground level (MAGL). If this test detected a statistically
significant difference, the Mann–Whitney Rank Sum Test was applied to identify the pair of
wind sectors producing the significant difference observed in the Kruskal–Wallis Test.

2.4. Chemical analysis

The samples were analyzed for pH, SO42, NO3, Cl, alkalinity (HCO3), Ca2+, Mg2+, Na+,
+
K , and NH4+. Rain samples were filtered through Millipore 0.45-Am membrane filters leached
with deionized water before chemical analyses. Rainwater pH was measured within 24 h after
collection of samples by using an Orion 960 autochemistry system. Calibration was performed
by means of buffer solutions at pH 4 and 7. Sulfates, NO3, and Cl were determined by non-
suppressed ion chromatography, and ammonium was determined by suppressed chromatography
with a Perkin Elmer chromatograph, using an isocratic LC pump 250 and a conductivity
detector. Sodium, K+, Ca2+, and Mg2+ were analyzed by flame atomic absorption spectrometry
with a GBC 932AA instrument. Conductance was determined with a YSI 3200 conductivity
instrument. Alkalinity was determined using the Gran’s titration method with an Orion 960
autochemistry system, and HCO3 concentrations were computed using the equation described
for Stumm and Morgan (1981).
 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85 71

The detection limits (DLs), in Aeq l 1, were 4.58, 2.74, 1.13, and 2.33 for SO42, NO3, Cl,
and NH4+, respectively. DLs for Na+, K+, Ca2+, and Mg2+ were 0.074, 0.16, 0.5, and 0.13,
respectively.

2.5. Data quality

Precision of methods was determined by analysis of standards from 10 replicate

measurements at different concentrations. The results showed that the precision for SO42,
NH4+, NO3, Ca2+, and Mg2+ was b 5% RSD (relative standard deviations).
The quality of analysis of each sample was checked for ion balance and specific conductance
calculations, defined by Peden et al. (1986) as: Ion Percent Difference = [(Cations  Anions) /
Cations + Anions)]  100 and Conductance Percent Difference = [(Calculated  Measured Con-
ductance) / (Measured Conductance)]  100, respectively.

3. Results and discussion

3.1. Annual and monthly variations

Annual and monthly volume-weighted mean concentrations (VWMC) and standard

deviations of VWMC of the analyzed ions for UNAM are shown in Figs. 2 and 3, respectively.
Fig. 4 shows the weekend VWMC of the main analyzed ions for UNAM and RV.
The rainy season extends from about May to mid-October, depending on synoptic conditions.
Rains are scarce or even absent from November to April in central Mexico. On some occasions,
the rainy season starts in late June, as happened in 1998 during the strong 1997–1998 El Niño
event. Consequently, there are large and systematic variations in rainwater chemical composition
in most of the years.
These large variations during the course of a single year, solely the result of variability in
meteorological conditions, render a trend analysis of rainwater chemical composition
meaningless. The large variations produced by meteorological conditions would mask the
change in rainwater chemical composition that could be produced throughout a long period.
In general, monthly ionic concentrations at the UNAM site were higher at the beginning of
the rainy season in May. H+ and Cl were exceptions, decreasing significantly as the rainy
season advanced. Sulfates and NH4+ showed a higher annual VWMC, followed by NO3 2+
, Ca ,
 + 2+ + 2  +
Cl , Na , Mg , and K . The maximum annual VWMC for SO4 , NO3 , and NH4 occurred in
1996. The maximum monthly VWMC of SO42 occurred in March, and the minimum
concentration was observed in July and August. Maximum VWMC of NO3 occurred in April
and May, and minimum concentrations occurred in June and July. Regarding weekend VWMC,
the concentration of SO42 was slightly higher than that of NH4+.
Sulfate, NO3 2+  + +
, Ca , Cl , NH4 , Na , and Mg
2+
concentrations were lower in RV, as was
+
expected. However, the H concentration was higher in RV than at the UNAM site. Potassium
concentrations were also higher than at the UNAM site. These differences were significant at
p b 0.05, according to the Mann–Whitney test (Table 1).
The pH in the UNAM site, calculated from annual VWMC of H+, was 4.95 (ranging from
4.71 to 5.43); these are slightly acidic values but a little less so than those reported for southern
China, the Korean peninsula, Japan, Central Eastern Europe, and Albany, New York (Table 2).
It is important to note that despite the fact that the VWMC of sulfate and nitrate ions in
rainwater was lower at RV than at the UNAM site, the VWMC of H+ was higher at RV (Fig. 4)
72 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85

120
SO4 NO3

80
eq L-1

40

0
30
Cl H
20
eq l-1

10

0
12
Na K Mg

8
eq L-1

0
150
Ca NH4
100
eq L-1

50

0
1000
Rain amount
mm

500

0
1994 1995 1996 1997 1998 1999 2000
Samping year

Fig. 2. Annual volume-weighted mean concentrations (VWMC) and standard deviations of the VWMC (bars on lines) of
analyzed ions in wet precipitation collected at the Autonomous University of Mexico (UNAM).
 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85 73

160
SO4 NO3

120
eq L-1

80

40

0
25
Cl H
20

15
eq l-1

10

0
30
Na K Mg

20
eq L -1

10

0
180
Ca NH4

120
eq L -1

60

0
Mar Apr May Jun Jul Aug Sep Oct Nov
Month

Fig. 3. Monthly volume-weighted mean concentrations (VWMC) and standard deviations of the VWMC (bars on lines)
of analyzed ions in wet precipitation collected at the Autonomous University of Mexico (UNAM).

because the extensive pine forests and higher rain levels prevent alkaline soil particles from
being blown by the wind.
It is difficult to relate rainwater chemical composition to a complex phenomenon like the
1997–1998 El Niño event. Even more, the way El Niño affects the rain amount depends on the
geographical situation of a specific region (Avila, 2002, cited by Gay et al., 2004). This outcome
was also observed in the precipitation data from UNAM and RV; the rain amount increased 38%
at the UNAM site from 1997 to 1998, whereas in RV, the rain amount in 1998 was only 7%
74 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85

120 20
(SO42-) (Cl-)
80

-1
-1

10
40

0 0
1994 1995 1996 1997 1998 1999 1994 1995 1996 1997 1998 1999
University Rancho Viejo University Rancho Viejo

60 10
(NO3-) (Na+)
40
-1

-1
5
20

0 0
1994 1995 1996 1997 1998 1999 1994 1995 1996 1997 1998 1999
University Rancho Viejo University Rancho Viejo

10 60
(K+) (Ca2+)
40
-1

-1

5
20

0 0
1994 1995 1996 1997 1998 1999 1994 1995 1996 1997 1998 1999
University Rancho Viejo University Rancho Viejo

8 120
(Mg2+) (NH4+)
6
80
-1

-1

4
40
2

0 0
1994 1995 1996 1997 1998 1999 1994 1995 1996 1997 1998 1999
University Rancho Viejo University Rancho Viejo

80 500
(H+) (Rain amount)
-1

mm

40 250

0 0
1994 1995 1996 1997 1998 1999 1994 1995 1996 1997 1998 1999
University Rancho Viejo University Rancho Viejo

Fig. 4. Annual volume-weighted mean concentrations (VWMC) of analyzed ions in wet precipitation collected at the
Autonomous University of Mexico (UNAM) and Rancho Viejo (RV) on weekends.

higher than in 1997. The increase in precipitation from 1997 to 1998 was enhanced by the fact
that the summer of 1997 was characterized by a negative precipitation anomaly (Magaña and
Vázquez, 2003). There does not seem to be a direct relationship between rain amount and
rainwater chemical composition. On one hand, the increase in precipitation in 1998 was
 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85 75

Table 1
Comparison of ion concentrations in Aeq l 1 between Mexico City and Rancho Viejo using the Mann–Whitney test for
weekend data from 1994 to 1999
Median T statistica
Mexico City (N = 83) Rancho Viejo (N = 82)
SO2
4 76.667 44.144 5227y
Cl 9.296 4.198 5002y
NO3 42.857 20.633 4701y
Na+ 4.522 1.022 4304y
K+ 2.046 3.033 7703y
Ca2+ 34.600 7.743 4122y
Mg2+ 3.689 1.885 5095y
NH+4 95.000 38.106 4012y
H+ 1.148 14.986 8356y
N is the number of samples.
a
The T statistic is the sum of the ranks in the smaller sample group. This value is compared to the population of all
possible rankings to determine the possibility of T occurring.
y
There is a statistically significant difference at p b 0.05 (two-tailed test).

accompanied by a decrease in ionic species concentration in rainwater at the UNAM site. The
increase in the amount of precipitation in 1998 produced a lesser content of soil particles
containing alkaline metals in rainwater, therefore, the hydrogen ion concentration increased. On
the other hand, despite below-normal rains in the summer of 1997, the concentration of ionic
species in rainwater was not noticeably higher than in any other year throughout the whole
studied period because of a concentration effect. In contrast, the outcome was different at RV,
where despite higher levels of rain in 1998, the concentration of alkaline metals did not decrease
that year, as it did at the UNAM site. This difference may possibly be a result of the perennial
forests that prevent soil particles from being easily blown off by the wind, regardless of whether
it is a rainy year or not. At this site, rainwater chemistry appeared to depend on wind direction
rather than on El Niño, based on the analysis of air-mass back trajectories at 1000 and 3000
MAGL (meters above ground level), which are discussed in the next section.

3.2. Air-mass back trajectories

The VWMC in relation to wind directions obtained by air-mass back trajectory analysis are
presented in Tables 3 and 4. The individual concentrations of sulfate (as a chemical tracer of
anthropogenic pollution) and calcium (as a chemical tracer of crustal particles) were associated
with the corresponding air-mass back trajectories calculated by the NOAA HYSPLIT model
(Hybrid Single-Particle Lagrangian Integrated Trajectory Model) (Draxler and Rolph, 2003).

Table 2
Average pH in Mexico City and other locations
Site pH References
Albany, New York 4.2 Khwaja and Husain (1990)
Central Eastern Europe 4.4 to 4.5 Hjellbrekke et al. (1995)
Southern China 4.7 Wang and Wang (1996)
Japan 4.8 Hara (1998)
Korean peninsula 4.7 Lee et al. (2000)
Mexico City 4.95 (4.71 to 5.43) This study
76 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85

Table 3
Volume-weighted mean concentrations in Aeq l 1 for three wind direction sectors (sector 1, 0–908; sector 2, 91–1358; and
sector 3, 136–3608) at the Rancho Viejo for weekend data from 1997 to 1999
Ion Air-mass trajectory sector at 1000 MAGLa Air-mass trajectory sector at 3000 MAGL
Sector 1 Sector 2 Sector 3 Sector 1 Sector 2 Sector 3
N 30 3 17 32 3 15
SO2
4 54.09 68.88 15.85 51.80 19.60 20.48
Cl 6.98 7.21 3.60 7.13 2.49 2.86
NO3 25.48 11.94 11.95 23.87 9.21 11.41
Na+ 1.57 1.00 0.88 1.18 1.37 1.28
K+ 4.97 2.40 3.71 4.24 1.94 5.72
Ca2+ 10.01 3.69 4.05 8.79 4.91 5.47
Mg2+ 2.76 0.45 1.56 2.40 1.08 1.99
NH+4 47.74 26.81 20.65 41.28 27.22 29.31
H+ 23.17 36.64 4.16 23.60 5.46 3.14
N is the number of samples.
a
Meters above ground level.

Hydrogen ion, NH4+, and Mg2+ were also associated with back trajectories as a complementary
analysis. Air-mass back trajectories were calculated for 1000 and 3000 MAGL, and NOAA
trajectories were calculated from 1997. The level 1000 MAGL was considered because storm
cloud bases frequently lie around 1000 MAGL. The level 3000 MAGL is about 1200 m higher
than the highest mountain summit that lies between Mexico City and Toluca and RV; at the same
time, it is close to the height of the 500 millibars (mb) isobaric surface (one of the mandatory
levels in meteorological analysis). The calculated air-mass back trajectories were grouped into
three wind direction sectors: sector 1 from 18 to 908; sector 2 from 918 to 1358; and sector 3 from
1368 to 3608. The criteria to select these sectors in the study of rainwater chemical composition
at RV were based on the geographical direction of large urban and industrial areas, in relation to
this site, and on the direction of prevailing winds during the rainy season. Therefore, the large
urban and industrial areas are located in sector 1, and the prevailing winds also blow from this
sector, which corresponds to the direction of trade winds. Sector 2 corresponds to the wind
direction frequently observed at the rear sector of easterly waves. Also, although there are no
important urban areas in sector 2, it is plausible that the complex local wind patterns and wind

Table 4
Volume-weighted mean concentrations of (Aeq l 1) for four wind direction sectors (sector 1, 1–908; sector 2, 91–1808;
sector 3, 181–2708; and sector 4, 271–3608) at the University of Mexico for 1997–2000 data
Ion Air-mass trajectory sector at 1000 MAGLa Air-mass trajectory sector at 3000 MAGL
Sector 1 Sector 2 Sector 3 Sector 4 Sector 1 Sector 2 Sector 3 Sector 4
N 95 44 10 10 74 59 12 14
SO2
4 62.3 76.2 55.5 67.5 56.4 73.9 60.6 75.6
Cl 11.0 10.4 10.5 6.9 10.3 10.8 7.4 12.0
NO3 40.8 55.4 27.8 56.5 34.6 55.5 44.9 45.3
Na+ 7.4 5.3 2.5 5.4 7.5 5.2 4.6 4.8
K+ 3-0 2.4 2.9 2.4 2.9 2.3 3.2 3.7
Ca2+ 44.4 33.6 15.2 25.5 42.7 34.1 30.4 27.5
Mg2+ 5.1 3.8 1.7 2.7 4.7 3.8 3.5 3.9
NH+4 93.9 106 74.5 88.8 90.4 104 96.1 79.1
H+ 7.3 17.5 9.1 19.2 3.9 16.8 7.9 21.1
a
Meters above ground level.
 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85 77

shear in mountainous areas produce a horizontal interchange of air between sectors 1 and 2.
Sector 3 is the largest sector because there are only wooded areas up to several hundreds of
kilometers around RV. Therefore, if this sector had been subdivided into smaller sectors, it would
have resulted in more air-mass back trajectories with similar air-mass origins from the point-of-
view of rainwater chemical composition. Regarding the UNAM site, because it is surrounded by
intense anthropogenic emission sources, the air-mass back trajectory sectors were subdivided
into four equally sized sectors: 18 to 908, 918 to 1808, 1818 to 2708, and 2718 to 3608. Fig. 5
shows some examples of air-mass back trajectories observed during the rainy season.

(a) (b)

(c) (d)

(e) (f)

Fig. 5. Some air-mass back trajectories observed during the rainy season for different years. Backward trajectories ending
at: (a) 00 UTC 04 Aug 97, (b) 04 UTC 12 Oct 97, (c) 22 UTC 20 Jun 98, (d) 23 UTC 29 May 99, (e) 21 UTC 06 Jul 99,
and (f) 06 UTC 19 Sep 99.
78 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85

At RV, volume-weighted mean sulfate concentrations (Table 3) were higher when air-mass
back trajectories at 1000 MAGL came from 18 to 908 (54.1 Aeq l 1) and from 918 to 1358 (68.9
Aeq l 1) in relation to trajectories between 1368 and 3608 (15.8 Aeq l 1). The higher VWMC of
sulfate observed when wind direction came from these sectors is an evidence of the interchange
of air mentioned above. This implication seems emphasized by the fact that hydrogen
concentrations were also higher when wind was blowing from sectors 1 and 2 (23.2 and 36.6 Aeq
l 1), respectively, and lower when air was blowing from sector 3 (4.16 Aeq l 1). The results for
sulfate and hydrogen confirm that sulfuric acid was transported from these sectors and rained out
over the mountainous area where RV is located. A similar result was obtained for ammonium,
although the difference between its concentrations for sector 2 and 3 was much less (47.7, 26.8,
and 20.6 Aeq l 1 for sectors 1, 2, and 3, respectively). At 3000 MAGL, the sulfate concentration
was higher only for sector 1 (51.8 Aeq l 1) versus 19.6 and 20.5 Aeq l 1 for sectors 2 and 3,
respectively. The hydrogen concentration was also higher for sector 1 (23.6, 5.46, and 3.14 Aeq
l 1 for sectors 1, 2, and 3, respectively). The previous results observed at RV also agreed with
the geographic position of RV in relation to Mexico City and Toluca. These results strongly
suggest that air-mass back trajectories from 08 to 1358 at 1000 MAGL were associated with
lower pH and higher sulfate concentrations, whereas these parameters were associated only with
air-mass back trajectories at 3000 MAGL from 08 to 908. This finding agreed or matched with
the orographic characteristics of the studied region. The horizontal dispersion of air pollutants
like sulfuric acid, transported from urban and industrial areas to downwind wooded areas where
RV is, covered broader areas at low levels than at high levels simply because air currents are
forced to flow around and over mountains, especially at low levels, and because light aerosols
such as sulfuric acid do not settle down.
Calcium concentrations were higher only for sector 1 at both levels: 10 Aeq l 1, versus 3.7
and 4 Aeq l 1 for sectors 2 and 3, respectively, at 1000 MAGL; and 8.8 Aeq l 1 versus 4.9 and
5.5 Aeq l 1 for sectors 2 and 3, respectively, at 3000 MAGL.
Magnesium behaved similarly to calcium; its concentrations were 2.8, 0.45, and 1.6 Aeq l 1
for sectors 1, 2, and 3, respectively, at 1000 MAGL; and 2.4, 1.1, and 2 Aeq l 1 for sectors 1, 2,
and 3, respectively, at 3000 MAGL. These results also agreed with the actual distribution of the
most important sources of calcium and magnesium, which lie precisely northeast of RV. The
higher Ca2+ and Mg2+ concentrations associated only with air-mass back trajectories from 08 to
908 at both levels are consistent with the fact that heavier dust particles settle down during the
winding airflow around mountains at low levels. Obviously, these particles also settle down at
higher levels; therefore, the maximum concentrations of Ca2+ and Mg2+ were also associated
with air-mass back trajectories from 08 to 908.
At the UNAM site, the concentrations of sulfate among the four sectors (Table 4) presented a
lesser variation than at RV at 1000 and 3000 MAGL; they were 62.3, 76.2, 55.5, and 67.5 Aeq
l 1 for sectors 1, 2, 3, and 4, respectively, at 1000 MAGL; and 56.4, 73.9, 60.6, and 75.6 Aeq
l 1 for the sectors, respectively, at 3000 MAGL. This finding is consistent with the fact that the
UNAM site is surrounded by numerous pollution sources. Ammonium ion concentrations had a
pattern similar to sulfate (93.9, 106, 74.5, and 88.8 Aeq l 1 at 1000 MAGL, and 90.4, 104, 96.1
and 79.1 Aeq l 1 at 3000 MAGL, for sectors 1, 2, 3, and 4, respectively).
The concentrations of hydrogen ion were lower for sector 1 at both levels: 7.3, 17.5, 9.1, and
19.2 Aeq l 1 for sectors 1, 2, 3, and 4, respectively, at 1000 MAGL; and 3.9, 16.8, 7.9, and 21.1
Aeq l 1 at 3000 MAGL. The lower concentrations of hydrogen ion when air-mass back
trajectory indicated a flow from sector 1 could have resulted from neutralization reactions mainly
between sulfuric acid and dust particles. The main sources of these components are situated in
 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85 79

Table 5
Ion ratios (calculated from volume-weighted mean concentrations in Aeq l 1) for four wind direction sectors (sector 1, 1–
908; sector 2, 91–1808; sector 3, 181–2708; and sector 4, 271–3608) at the National Autonomous University of Mexico
for the period 1997–2000
Ion ratio Sea Air-mass trajectory sector at 1000 MAGLb Air-mass trajectory sector at 3000 MAGLb
salt ratioa Sector 1 Sector 2 Sector 3 Sector 4 Sector 1 Sector 2 Sector 3 Sector 4
NO3 /SO4
2
– 0.7 0.7 0.5 0.8 0.6 0.8 0.7 0.6
NH4+/SO2 4 – 1.5 1.4 1.3 1.3 1.6 1.4 1.6 1.0
SO2
4 /Ca
2+
2.44 1.4 2.3 3.6 2.6 1.3 2.2 2.0 2.8
SO2
4 /H
+
– 8.5 4.4 1 3.5 14.6 4.4 7.7 3.6
2+ 2+
Ca /Mg 0.19 8.7 8.8 9.1 9.3 9.1 8.9 8.6 7.1
Cl/Na+ 1.16 1.5 2.0 4.2 1.3 1.4 2.1 1.6 2.5
N is the number of samples.
a
Calculated using Aeq.
b
Meters above ground level.

sector 1, as shown by the higher concentration of calcium and magnesium and by the lower
concentrations of hydrogen when air-mass back trajectories at 1000 and 3000 MAGL showed
that the wind blew from this sector (Table 4).

3.3. Sea salt contribution, ion ratios, and correlations

Excess sulfate (non-sea-salt sulfate) represented 98.7% of the total sulfate in rainwater
collected at RV and 98.6% for weekend and annual rain samples at the UNAM site. The
quantification of sea-salt contribution was based on chloride. The SO42/Ca2+ ratio in rainwater
was closer to the ratio in sea salt (2.44) at the UNAM site compared to RV for all the sectors
(Tables 5 and 6). However, this finding does not suggest that Mexico City is much closer to the
seashore, but simply that calcium concentration was much higher at the UNAM site than at RV.
The Ca2+/Mg2+ ratio was much higher than in sea salt (0.195) at both sampling sites for all the
sectors because of the continental character of these sites. The Ca2+/Mg2+ ratio in the crust is
higher than unity, where the magnesium content is lower than that of calcium; however, it is
lower than unity in sea salt, where the magnesium content is higher than that of calcium. This
ratio was higher at the UNAM site than at RV because calcium concentration was much higher at
the UNAM site than at RV, as was the case with the SO42/Ca2+ ratio. The Cl/Na+ ratio was
higher than in sea salt (1.16) at both sampling sites because there are other sources of chloride in

Table 6
Ion ratios (calculated from volume-weighted mean concentrations in Aeq l 1) for three wind direction sectors (sector 1,
0–908, sector 2, 91–1358, and sector 3, 136–3608) for weekend data from 1997 to 1999 in the Rancho Viejo
Ion ratio Sea Air-mass trajectory at 1000 MAGLa Air-mass trajectory at 3000 MAGL
salt ratioa Sector 1 Sector 2 Sector 3 Sector 1 Sector 2 Sector 3
NO3/SO2
4 – 0.47 0.17 0.75 0.46 0.47 0.56
NH4+/SO24 – 0.88 0.39 1.30 0.80 1.39 1.43
SO2
4 /Ca
2+
2.44 5.30 18.68 3.91 5.90 3.99 3.74
SO2
4 /H
+
– 2.33 1.88 3.81 2.19 3.59 6.52
2+ 2+
Ca /Mg 0.19 3.70 8.24 2.59 3.66 4.55 2.74
Cl/Na+ 1.16 4.44 7.20 4.08 5.20 3.01 2.23
a
Meters above ground level.
80 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85

continental regions. The main reason this ratio was noticeably higher at RV than at the UNAM
site is that the concentration of sodium was higher at the UNAM site, where the content of dust
particles was also higher. All the sectors showed clear continental characteristics for SO42/Ca2+,
Ca2+/Mg2+, and Cl/Na+ ratios corresponding to the obvious continental characteristics of the
sampling sites, where the main components in rainwater come from sources other than sea salt.
For instance, Mexico City is situated at more than 300 km from the closest shoreline; even more,
high mountains surround it. Also, the Sierra Madre Oriental with mountains above 4000 masl
lies close to the Gulf of Mexico coast. The heavy rains that occur in these mountains (several
thousands millimeters per year) are another factor that scavenges sea-salt aerosols even further.
Therefore, the concentration of sea-salt aerosols is depleted rapidly, as tropical maritime air
masses invade central Mexico during the rainy season. These environmental conditions make the
quantification of sea-salt contribution highly uncertain.
The Spearman’s rho correlation was applied to identify relationships between annual ionic
concentrations at UNAM and in both sites on weekend data (Tables 7 and 8). It must be noted
that a significant statistical association between variables should be interpreted with care. For
example, sulfate and nitrate concentrations commonly show a significant correlation; however,
this correlation is related to common emissions sources and transport processes rather than to
chemical reactions between precursor species (Lee, 1993). The Spearman’s rho correlation
analysis between ionic concentrations indicates a positive correlation in most cases at the
significance level of 0.05.
At the UNAM site, considering annual VWMC of SO42, NO3, and NH4+, the NO3/SO42
and NH4+/SO42 ratios were 0.5 and 1.09 in 1994 and 0.86 and 1.64 in 2000, respectively (Fig.
6). According to Fig. 2, the increase of NO3/SO42 and NH4+/SO42 ratios resulted mainly from a
decrease in SO42 concentration (34% from 1994 to 2000). The SO42 and NO3 correlation can
also be a consequence of their common source origin. For weekend data, the NO3/SO42
increased from 0.58 to 0.85 and from 0.41 to 0.71 at the UNAM site and at RV, respectively. The
correlation between NH4+ and SO42 indicates that ammonium sulfate is a common constituent in
the atmosphere in central Mexico, consistent with the fact that ammonium and sulfate were
present in high concentrations in rainwater. The NH4+/SO42 ratio increased from 0.98 to 1.68 and
from 0.87 to 1.38 at the UNAM site and at RV, respectively. A decrease for sulfates has also been
observed in other countries (Fay et al., 1989; Puxbaum et al., 1998). In Mexico City, the
decrease of SO42 can be explained by the SO2 reduction in industrial emissions and by the

Table 7
Spearman’s rho correlation between ion concentrations in wet precipitation collected at Mexico City from 1994 to 2000
(N = 303a)
Cl NO
3 Na+ K+ Ca2+ Mg2+ NH+4 H+ HCO
3
y y y y y y y y
SO4 0.524 0.663 0.463 0.546 0.628 0.623 0.657 0.158 0.0754
Cl 0.449y 0.621y 0.569y 0.521y 0.554y 0.512y 0.117y 0.177y
NO3 0.482y 0.510y 0.558y 0.565y 0.711y 0.136y 0.0242
Na+ 0.874y 0.840y 0.861y 0.621y 0.484y 0.551y
K+ 0.787y 0.843y 0.619y 0.367y 0.442y
Ca2+ 0.955y 0.696y 0.414y 0.505y
Mg2+ 0.660y 0.360y 0.450y
NH+4 0.269y 0.385y
H+ 0.885y
a
Number of samples.
y
Correlation is significant at p V 0.05 (two-tailed).
 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85 81

Table 8
Spearman’s rho correlation among ion concentrations in wet precipitation collected in Mexico City and Rancho Viejo on
weekends from 1994 to 1999
Cl NO
3 Na+ K+ Ca2+ Mg2+ NH+4 H+ HCO
3 Rain amount
Mexico City (N = 83)§
SO2
4 0.557* 0.737* 0.518* 0.586* 0.735* 0.712* 0.737* 0.224* 0.076 0.486*
Cl 0.451* 0.724* 0.658* 0.589* 0.618* 0.562* 0.0987 0.177 0.368*
NO3 0.522* 0.580* 0.624* 0.626* 0.737* 0.175 0.010 0.466*
Na+ 0.893* 0.821* 0.824* 0.701* 0.419* 0.508* 0.328*
K+ 0.794* 0.828* 0.717* 0.288* 0.415* 0.440*
Ca2+ 0.952* 0.796* 0.267* 0.394* 0.401*
Mg2+ 0.757* 0.225* 0.372* 0.422*
NH+4 0.225* 0.377* 0.492*
H+ 0.909* 0.057
HCO 3 0.089

Rancho Viejo (N = 82) a

SO2
4 0.673** 0.765** 0.427** 0.264** 0.621** 0.537** 0.673** 0.729** 0.289** 0.078
Cl 0.551** 0.555** 0.211 0.564** 0.490** 0.496** 0.504 0.148 0.088
NO3 0.477** 0.261** 0.785** 0.632** 0.736** 0.471** 0.179 0.143
Na+ 0.451** 0.638** 0.675** 0.588** 0.0495 0.0079 0.170
K+ 0.399** 0.650** 0.441** 0.116 0.172 0.192
Ca2+ 0.859** 0.745** 0.225** 0.0182 0.135
Mg2+ 0.695** 0.107 0.0114 0.098
NH+4 0.173 0.170 0.075
H+ 0.625** 0.199
HCO 3 0.198
a
Number of samples.
* Correlation is significant at p V 0.05 (two-tailed).
** Correlation is significant at p b 0.05 (two-tailed).

reduction of sulfur content in fuel oil. Besides other SO2 control strategies applied in 1986,
1989, 1991, and 1993, industrial diesel oil with a sulfur content of 1% replaced fuel with a sulfur
content of 2% in 1997. The result of the measurements of ambient SO2 by the government
monitoring network, operating in the metropolitan area of Mexico City, indicated that the
concentration of SO2 in the last 6 years has been below the air quality standard (0.13 ppm per
hour and 0.03 ppm annually).
The increase of NH4+/SO42 ratio from 1994 to 2000 (Fig. 6) is a consequence of the decrease
in rainwater sulfate concentration. In contrast, ammonium ion did not present significant
variations throughout the 7-year sampling period. In Mexico City Valley, there are numerous
sources of ammonium that have not yet been reliably inventoried. However, some ammonium
sources are agricultural, including manure handling (around Mexico City there are still several
agricultural areas); cleansing-product manufacturing and domestic use; and hair-coloring
products.
The SO42/Ca2+ ratio was significantly lower at the UNAM site (1.8 for overall data and 1.82
for weekend data) than at RV (5.36 for weekend data), primarily because calcium concentration
at RV was much less as a result of a much lower concentration of crustal particles.
The SO42/H+ ratio was significantly lower at the UNAM site (6.34 for overall data and 6.77
for weekend data) than at RV (2.01 for weekend data) because the sulfate concentration was
lower at RV, but most of all because hydrogen concentration is higher at RV. This concentration
is not higher as a result of greater air pollution but as a result of fewer acid-neutralizing soil
82 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85

1.0
(a)
NO3/SO4 ratio

0.5

R = 0.848, p = 0.016
0.0

2
(b)
NH4/SO4 ratio

R = 0.850, p = 0.015
0

12
(c)
9
Ca/Mg ratio

R = - 0.0823, p = 0.861
0
1994 1995 1996 1997 1998 1999 2000
Years

Fig. 6. Trends of ionic concentration ratios for the period 1994–2000 at the Autonomous University of Mexico (UNAM):
a) NO3/SO2 + 2 2+ 2
4 , b) NH4 /SO4 , and c) Ca /Mg . The line represents the trend or regression line.

particles at this site. Hydrogen ion correlated positively with SO42 and NO3, indicating the
presence of nitric and sulfuric acids as H+ donor species. Although there was a good correlation
between H+ and SO42 at the UNAM site, it is meaningful that this correlation was much higher
at RV (Table 3). The correlation between H+ and NO3 was not significant at the UNAM site but
significant at RV. These results indicate a greater relationship between H+ and SO42 and NO3
ions at RV because neutralization reactions between soil particles and acids in rainwater are less
important at this location than at the UNAM site. The high rainwater acidity observed at RV
demonstrates the large impact of Mexico City emissions on air and rainwater quality in
downwind wooded areas, with the possible acidification of the forest soil. Deposition of the
 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85 83

Table 9
Multiple linear regression analysis using H+ concentration as the dependent variable in Mexico City (N = 303a)
Model Coefficient Standard error t-value VIFb F-ratio ANOVAc R
y
Constant 8.133 2.121 3.835 0.000 90.810y 0.690
NO3 0.536 0.034 15.842y 2.025
Ca2+ 0.195 0.023 8.504y 1.767
NH+4 0.140 0.026 5.360y 2.237
a
Number of samples.
b
Variance inflation factor.
c
Analysis of variance for the variables included in the model.
y
Significant at p b 0.05.

different ions was not calculated for RV because rainwater samplings were made only on
weekends.
In contrast, hydrogen ion correlated negatively with Ca2+, Mg2+, Na+, K+, and NH4+, as a
result of neutralizing reactions between hydrogen ion and alkaline particles and ammonia.
Chloride correlated negatively to H+ at a significance level of 0.05.
The correlation between the alkaline ions Ca2+, Mg2+, Na+, and K+, and the poorly defined
trend of the Ca2+/Mg2+ ratio from 1994 to 2000 for overall data at the UNAM site and weekend
data at the UNAM and RV sites, suggest a common crustal origin of these metals. The Cl/Na+
ratio was significantly lower at the UNAM site (1.71 for overall data and 1.8 for weekend data)
than at RV (4.84 for weekend data) because the sodium concentration was much lower as a result
of a lesser content of crustal particles at RV.
A multiple regression correlation analysis (MRC) was performed to predict H+ concentration,
and the hierarchical MRC analysis used by Cohen and Cohen (1975) was applied to select the
variables included in the final model (Table 9). The MRC analysis showed that NO3, NH4+, SO42,
and Ca2+ contributed 23.2%, 20.9%, 8.0%, and 6.1%, respectively, to the H+ prediction, while
Cl plus Na+ plus K+ only contributed 2.2%, and Mg2+ did not contribute. The fact that nitrate
contributed 23.2% and sulfate contributed only 8.0% is possibly the result of the sulfur-dioxide
control emissions and the slight increase of nitrate concentration in rainwater.

4. Conclusions

Because of the large variations in rainwater chemical composition observed in most of the
years at both sampling sites, it was difficult to evaluate changes in rainwater chemical
composition during a long period based solely on changes in source emission characteristics.
Also, the variability of meteorological conditions during a single year produces large variations
in rainwater composition capable of masking changes resulting from pollution sources
characteristics.
The VWMC of sulfate decreased during the study period as a consequence of the reduction of
SO2 in industrial emissions and the replacement of fuel oil by natural gas in thermoelectric
power plants.
The ionic ratios of nitrate and ammonium to sulfate concentration in rainwater at the UNAM
increased from 1994 to 2000 because of a decrease in sulfate concentration.
The concentrations of all ions, except H+, in rainwater collected during weekends were higher
at the UNAM site than in the wooded area (RV) (downwind of Mexico City), as was expected,
mainly because of the highly polluted atmosphere of Mexico City. The higher hydrogen ion
concentration in RV was a consequence of the lower concentration of wind-blown dust at this
84 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85

place; this decreased dust concentration resulted from the higher humidity and vegetation cover
at this location and in the surrounding mountains, and not from a higher concentration of sulfate
in rainwater.
The presence of acid rain at RV indicates a possible harmful impact of Mexico City and other
upwind anthropogenic sources on forested downwind regions.
The analysis of the chemical composition of rainwater in relation to the analysis of air-mass
back trajectories seemed to perform reasonably well for the two levels. However, it is not easy
to know the level at which this analysis performed best; thus, a multilevel air-mass back
trajectory analysis is mandatory in mountainous regions. More-extensive studies are necessary
to identify the best level for this kind of analysis for the region studied in this work. Also,
despite the fact that the air-mass back trajectory analysis seemed to perform reasonably well, it
must be stressed that air-mass back trajectory analyses cannot be completely reliable and must
be interpreted with caution in regions with very complex terrain and wind patterns, such as
those in this study. A costly network of numerous meteorological stations and atmospheric
soundings must be carefully situated for study of the actual transport mechanism of air
pollutants.

Acknowledgments

The authors gratefully acknowledge the NOAA Air Resources Laboratory (ARL) for
providing the HYSPLIT transport and dispersion model and/or READY website (http://
www.arl.noaa.gov/ready.html) used in this publication. The authors are indebted to Delibes
Flores Roman, Rosa Marı́a Ayala, and Carlos Contreras for their support in computation and also
grateful to Jorge Escalante, Wilfrido Gutiérrez, and Alfredo Rodrı́guez for the maintenance of
the sampling equipment and to Calixto Cuevas for his assistance in the laboratory.

References

Avila, A., 1996. Time trends in the precipitation chemistry at a mountain site in northeastern Spain for the period 1983–
1994. Atmos. Environ. 30, 1363 – 1373.
Civerolo, K., Rao, S.T., 2001. Space–time analysis of precipitation-weighted sulfate concentrations over the eastern US.
Atmos. Environ. 35, 5657 – 5661.
Cohen, J., Cohen, P., 1975. Applied Multiple Regression Correlation Analysis for the Behavioral Sciences. Lawrence
Erlbaum Associates, Hillsdale, NJ.
Dillon, P.J., Lusis, M., Reid, R., Yap, D., 1988. Ten-year trends in sulfate, nitrate and hydrogen deposition in Central
Ontario. Atmos. Environ. 22, 901 – 905.
Draxler, R.R., Rolph, G.D., 2003. HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model access via
NOAA ARL READY Website (http://www.arl.noaa.gov/ready/hysplit4.html). NOAA Air Resources Laboratory,
Silver Spring, MD.
Erisman, J.W., Frank, A.A., De Leeuw, M., Van Aalst, R.M., 1989. Deposition of the most acidifying components in
Netherlands during the period 1980–1986. Atmos. Environ. 23, 1051 – 1066.
Fay, J.A., Golomb, D., Zemba, S.G., 1989. Observed and modeled trend of sulfate and nitrate in Eastern North America.
Atmos. Environ. 23, 1863 – 1866.
Gay, C., Hernández, M., Jiménez, J., Lezama, J., Magaña, V., Morales, T., Orozco, S., 2004. Evaluation of climatic
forecasts of rainfall for the Tlaxcala State (México): 1998–2002. Atmosfera 17, 127 – 150.
Galloway, J.N., 1995. Acid deposition: perspectives in time and space. Water Air Soil Pollut. 85, 15 – 24.
Hara, H., 1998. Acid deposition chemistry in Asia, Europe, and North America. Prog. Nucl. Energy 32, 331 – 338.
Herut, B., Starinsky, A., Katz, A., Rosenfeld, D., 2000. Relationship between the acidity and chemical composition of
rainwater and climatological conditions along a transition zone between large deserts and Mediterranean climate,
Israel. Atmos. Environ. 34, 1281 – 1292.
 A.P. Báez et al. / Atmospheric Research 80 (2006) 67–85 85

Higashino, H., Tonooka, Y., Yanagisawa, Y., Ikeda, Y., 1997. Emission inventory of SO2 and NOx in East Asia with grid
data system. In: Murano, K. (Ed.), Proceedings of the International Workshop on Unification of Monitoring Protocol
of Acid Deposition and Standardization of Emission Inventory. Tsukuba, Japan, pp. 124 – 144.
Hjellbrekke, A.G., Lövblad, G., Sjöberg, K., Schaug, J., Skjelmoen, J.E., 1995. Data report 1993: Part 1. Annual
summaries. EMEP/CCC-Report 7/95, Norwegian Institute for Air Research, pp. 4–18.
Khwaja, H.A., Husain, L., 1990. Chemical characterization of acid precipitation in Albany, New York. Atmos. Environ.
24A, 1869 – 1882.
Lee, S.D., 1993. Spatial variability of urban precipitation chemistry and deposition: statistical associations between
constituents and potential removal processes of precursor species. Atmos. Environ. 27B, 321 – 337.
Lee, B.K., Hong, S.H., Lee, D.S., 2000. Chemical composition of precipitation and wet deposition of major ions on the
Korean peninsula. Atmos. Environ. 34, 563 – 575.
Lynch, J.A., Grimm, J.W., Bowersox, V.C., 1995. Trends in precipitation chemistry in the United States: a national
perspective, 1980–1992. Atmos. Environ. 29, 1231 – 1246.
Magaña, V., Vázquez, J., Pérez, J.L., Pérez, J., 2003. Impact of El Niño on precipitation in Mexico. Geofı́s. Int. 42,
313 – 330.
Peden, M.E., Bachman, S.R., Brennan, C.J., Demir, B., James, K.O., Kaiser, B.W., Lockard, J.M, Rothert, J.E., Sauer, J.,
Skowron, L.M., Slater, M.J., 1986. Development of standard methods for the collection and analysis of precipitation.
Contract CR810780-01. Illinois State Water Survey, Analytical Chemistry Unit, Champaign, IL.
Puxbaum, H., Simeonov, V., Kalina, F.M., 1998. Ten years trends (1984–1993) in the precipitation chemistry in Central
Austria. Atmos. Environ. 32, 193 – 202.
Stumm, W, Morgan, J.J., 1981. Aquatic Chemistry: An Introduction Emphasizing Chemical Equilibria in Natural Waters,
second edition. A Wiley-Interscience Publication, John Wiley and Sons, New York, Chichester, Brisbane, Toronto,
Singapore, pp 226–228.
Terada, H., Ueda, H., Wang, Z., 2002. Trend of acid rain and neutralization by yellow sand in east Asia—a numerical
study. Atmos. Environ. 36, 503 – 509.
Tuncer, B., Bayar, B., Yesilyurt, C., Tuncel, G., 2001. Ionic composition of precipitation at the Central Anatolia (Turkey).
Atmos. Environ. 35, 5989 – 6002.
Walker, J.T., Aneja, V.P., Dickey, D.A., 2000. Atmospheric transport and wet deposition of ammonium in North Carolina.
Atmos. Environ. 34, 3407 – 3418.
Wang, W., Wang, T., 1996. On acid rain formation in China. Atmos. Environ. 30, 4091 – 4093.