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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv
Centro de Tecnologas Ambientales, Universidad Tcnica Federico Santa Mara, Av. de Espaa, Valparaso, Chile
Departamento de Qumica Analtica, Facultad de Ciencias, Universidad de Extremadura, Av. de Elvas, s/n. 06006 Badajoz, Spain
Departamento de Fsica Aplicada, Universidad de Extremadura, Campus Universitario, Cceres, Spain
Winter snow precipitation in the Central Andes mountain range reects urban atmospheric emissions of Santiago de Chile by signicant
enrichment of anthropogenic elements. The preliminary results obtained in this study are promising for assignment and tracking of pollution
sources by exploiting chemical information collected in the snow.
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 5 July 2011
Received in revised form
2 November 2011
Accepted 16 November 2011
Seasonal snow precipitation in the Andes mountain range is evaluated as an environmental indicator of
the composition of atmospheric emissions in Santiago de Chile metropolitan area, by measuring a set of
representative trace elements in snow samples by ICP-MS. Three late winter sampling campaigns (2003,
2008 and 2009) were conducted in three sampling areas around Cerro Colorado, a Central Andes
mountain range sector NE of Santiago (36 km). Nevados de Chilln, a sector in The Andes located about
500 km south from the metropolitan area, was selected as a reference area. The experimental results at
Cerro Colorado and Nevados de Chilln were compared with previously published data of fresh snow
from remote and urban background sites. High snow concentrations of a range of anthropogenic marker
elements were found at Cerro Colorado, probably derived from Santiago urban aerosol transport and
deposition combined with the effect of mining and smelting activities in the area, whereas Nevados de
Chilln levels roughly correspond to urban background areas. Enhanced concentrations in surface snow
respect to deeper samples are discussed. Signicant differences found between the 2003, 2008 and 2009
anthropogenic source markers proles at Cerro Colorado sampling points were correlated with changes
in emission sources at the city. The preliminary results obtained in this study, the rst of this kind in the
southern hemisphere, show promising use of snow precipitation in the Central Andes as a suitable
matrix for receptor model studies aimed at identifying and quantifying pollution sources in Santiago
de Chile.
2011 Elsevier Ltd. All rights reserved.
Keywords:
Trace elements
Atmospheric pollution
Snow
Santiago de Chile
Central Andes
1. Introduction
Trace elemental proles are key data sets for the assessment of
potential aerosol toxicity and also for pollution sources identication
and quantication (Watson et al., 2002; Viana et al., 2008, and
references therein). Urban aerosol elemental proles are usually
evaluated on aerosol samples obtained at particular city locations or
closely around, but these samples can be potentially affected by
analytical noise due to rapid temporal changes of pollution sources,
and also by the intrinsic heterogeneity of the urban areas. In contrast,
remote sampling may provide clearer information, aside of data
* Corresponding author. Tel.: 34 924 289389; fax: 34 924 274244.
E-mail address: epinilla@unex.es (E. Pinilla Gil).
1
Present address: Departamento de Biologa y Qumica, Facultad de Ciencias
Bsicas, Universidad Catlica del Maule. Avenida San Miguel, 3605. Talca, Chile.
1352-2310/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2011.11.045
52
Fig. 1. Map of Central Chile showing the Cerro Colorado (CC) sampling area close to Santiago de Chile and the Nevados de Chilln (NCH) reference sampling area.
53
wind. The sampling sites were selected so that they were as far as
possible from local contamination sources such as ski trails, cable
car stations, trees or exposed rocks.
2.3. Analytical procedure
The samples were melted at room temperature under hood
extraction and acidied with subboiled nitric acid to make 5%
solutions. A complete set of trace elements was determined by
ICP-MS using a PerkinElmer ELAN 9000 instrument placed in a clean
room. Analytical determinations were carried out in triplicate on raw
aqueous samples without any preconcentration or pretreatment step
to minimize contamination. Some elements were under the instrument detection limit and other gave no relevant environmental
information, so As, Pb, Cd, Ni, V, Cr, Mn, Co, Ba, Cu, Zn, Mo and Sb
were selected for discussion after screening the data base for relevant results. These elements are classied in the literature as tracers
of diverse anthropogenic activities (Viana et al., 2008 and references
therein). The precision ranged from 10 to 20% depending on the
elements and the concentration levels. Detection limits were calculated according to the IUPAC denition as three times the standard
Fig. 2. Map showing the location of the sampling sites Cerro Colorado (a) and Nevados
de Chilln (b).
54
Table 1
Limits of detection (LOD) calculated from 3s of 10 replicates of blank solution and
analytical results of certied reference material SPS-SW2 Reference material for
measurements of elements in surface waters. All data in mg kg1.
Element
LOD
SPS-SW2 measured
SPS-SW2 certied
As
Pb
Cd
Ni
V
Cr
Mn
Co
Ba
Cu
Zn
Mo
Sb
0.007
0.613
0.013
0.115
0.004
0.025
0.091
0.007
0.714
0.119
0.045
0.025
0.008
5.03 0.83
2.47 0.28
0.25 0.02
4.84 0.30
4.81 0.33
1.02 0.06
4.74 0.53
1.00 0.07
25.06 2.89
10.41 0.75
9.74 1.69
4.92 0.36
1.53 0.51
5.0 0.3
2.5 0.1
0.26 0.02
5.0 0.3
5.0 0.3
1.00 0.05
5.0 0.3
1.00 0.05
25.0 1.0
10.0 1.0
10.0 2.0
5.0 0.3
Not certied
deviation of concentrations estimated after ten repetitive measurement of the blank solution (5% HNO3 in ultrapure water) are reported
in Table 1. The obtained values were low enough for measuring the
expected concentrations in the real samples. A certied reference
material (SPS-SW2 Reference material for measurements of
elements in surface waters, Spectrapure Standards, Oslo, Norway)
was used for quality control of the data. A good agreement between
measured and certied values was observed for most elements
assayed (Table 1). Enrichment of elements in the real snow samples
were calculated as mean element concentration at location 1/mean
element concentration at location 2.
3. Results and discussion
3.1. General overview and comparison with reference areas
Trace element concentrations measured in the surface snow at
the sampling locations Cerro Colorado (CC) and Nevados de Chilln
(NCH) are given in Table 2, aside with literature data about previously reported values of trace elements in fresh snow from locations
that can be considered relatively remote in their regional context
(Pyrenees, Alps, and Alaska). For each area, the quoted values are the
median values and the range (minimum and maximum) of the
whole set of samples obtained during the sampling campaigns. Most
anthropogenic elemental concentrations measured at Cerro
Colorado are higher than corresponding literature values. The
differences were especially signicant in the cases of As, Pb, Cd, Mn,
Co, Ba, Cu, Zn and Mo, whereas Ni and V concentrations were only
slightly higher. Cr and Sb concentrations in Cerro Colorado snow
samples were similar or lower than previously reported values in
regional background areas. These results are in support of a signicant impact of emission sources from Santiago de Chile in the area,
but the data can also reect the impact of miningesmelting activities. The proximity of copper strip mining operations at Los Bronces
(40 km NW of the Cerro Colorado sampling area) is probably related
with the high Cu values observed. The giant El Teniente (mine) e
Caletones (smelter) copper complex (95 km SW), can be also related
with enhanced levels of some elements in the snow of Cerro Colorado as a result of particulate matter transport. Elevated levels of Cu,
Zn and As were measured by Romo-Krger et al. (1994) in particulate
matter around El Teniente e Caletones. Snow samples taken at
Nevados de Chilln presented similar concentration ranges for
anthropogenic elements than literature values for most elements,
except for somewhat elevated values of Pb, Cd, Cu, and Mo. Whereas
Nevados de Chilln has been selected as a regional reference in our
study, the experimental data shown that a signicant degree of
anthropogenic impact is detected in the area. This can be due to
nearby sporting activities, but transport from regional sources can be
implied, including emissions from Chilln (60 km NW) and Concepcin (130 km W). Also, altered composition of particulate matter
in the regional scale, due to geological abnormalities and surface
coverage mobilization by weathering and mining activities is typical
in Chile, and also the regional dispersion of smelting particulate
emissions (Kavouras et al., 2001; De Gregori et al., 2002; Gidhagen
et al., 2002). The regional air dynamics conguration contributes to
this phenomenon, with SW air masses traveling from the coast to the
high slope, west face mountainsides in The Andes.
Anthropogenic elements concentrations at Cerro Colorado and
Nevados de Chilln samples were then compared with previously
reported values for Cu, Zn, Pb and Cd levels in snow sampled from
urban background areas around Cincinnati, OH, USA (Glenn and
Sansalone, 2002), Lulea and Sundsvall in Sweden (Reinosdotter
and Viklander, 2005), and Innsbruck in Austria (Engelhard et al.,
2007). The results are summarized in Table 3. The most notable
feature is probably the very high Cu levels measured at Cerro
Colorado snow samples, with maximum values exceeding one
order of magnitude Nevados de Chilln values and previously
published urban background data. Cu levels at Nevados de Chilln
samples were similar to those reported in the literature. Zn
concentrations in snow samples from Cerro Colorado are in the
Table 2
Element concentration ranges measured values in Cerro Colorado (CC) and Nevados de Chilln (NCH) and comparison with literature values about trace elements in fresh snow
from regional background locations. Concentrations are given in median values and range in brackets. All data in mg kg1.
Element
CC
As
Pb
Cd
Ni
V
Cr
Mn
Co
Ba
Cu
Zn
Mo
Sb
0.55
19.48
0.72
0.70
0.33
0.01
12.25
0.42
5.90
33.29
29.59
0.27
0.03
a
b
c
d
e
NCH
(0.03e3.33)
(2.36e74.86)
(0.13e2.18)
(0.22e4.92)
(0.01e4.94)
(0.01e4.69)
(1.61e133.82)
(0.11e5.34)
(0.64e77.84)
(4.97e386.68)
(10.14e114.46)
(0.06e1.68)
(0.01e0.20)
Veschambre (2006).
Bacardit and Camarero (2010).
Veysseyre et al. (2001).
Gabrielli et al. (2008).
Douglas and Sturm (2004).
0.01 (0.01e0.16)
9.21 (1.85e13.55)
0.18 (0.14e0.83)
0.21 (0.06e0.56)
0.01 (0.01e0.02)
<LOD
0.12 (0.05e2.24)
0.03 (0.02e0.50)
0.42 (0.36e1.75)
3.59 (1.08e17.83)
14.93 (13.20e16.59)
0.01 (0.01e0.39)
0.02 (0.01e0.08)
Atlantic pyreneesa
Central pyreneesb
0.11 (0.07e0.47)
0.05 (0.02e0.07)
0.93 (0.04e9.14)
Chamonix alpsc
Eastern alpsd
0.23 (0.07e1.76)
0.02 (0.008e0.06)
0.87 (0.02e33.70)
0.05 (0.02e0.22)
0.02 (0.004e0.11)
0.13 (0.003e4.6)
0.04 (0.003e3)
1.20 (0.01e173)
0.02 (0.002e0.97)
0.5 (0.009e36.5)
0.28 (0.08e29.1)
1.7 (0.02e63.1)
0.04 (0.01e0.72)
0.03 (0.002e6.2)
0.37 (<LODe1.35)
0.04 (0.02e0.09)
0.04 (0.02e0.09)
0.13 (0.06e0.29)
0.30 (0.06e1.08)
0.11 (0.08e0.30)
0.17 (0.01e3.07)
0.02 (<LODe0.39)
2.30 (0.07e6.57)
0.03 (0.02e0.05)
0.20
0.005
0.15
0.03
0.28
0.02
0.03
(0.06e1.13)
(0.001e0.007)
(0.06e0.57)
(0.01e0.23)
(0.10e0.75)
(0.01e0.03)
(0.009e0.08)
NW Alaskae
0.06
0.26
0.006
0.14
0.27
(0.009e0.19)
(0.03e0.59)
(0.001e0.02)
(0.07e0.62)
(0.01e1.06)
2.79 (0.19e9.20)
1.07 (0.12e4.00)
Zn
Cd
Pb
Cincinnati
5e35
0.2e0.35
0.5e10
Lulea
Sundsvall
Innsbruck
CC
NCH
2e10
Source
55
Fig. 3. Box and whisker plots showing the distribution of selected anthropogenic elements concentrations in the snow from sampling areas at Cerro Colorado (CC) and Nevados de
Chilln (NCH).
56
Table 4
Enrichment of anthropogenic tracer elements concentrations measured in the
snow samples collected during the sampling campaigns at Cerro Colorado (CC) vs
reference values at Nevados de Chilln (NCH). Sources traced: trafc (1); smelting
(2); biomass and coal burning (3); waste incineration (4).
Element
Sources traced
Cerro Colorado
mean (mg kg1)
Nevados de Chilln
mean (mg kg1)
Conc. ratio
CC/NCH
As
Pb
Cd
Ni
V
Cr
Mn
Co
Ba
Cu
Zn
Mo
Sb
2,
1,
1,
2
1,
1,
1,
2
1
1,
1,
1,
1,
1.50
28.66
0.74
1.92
1.36
1.36
46.06
1.35
27.36
105.51
51.07
0.71
0.11
0.04
8.21
0.33
0.26
0.01
<LOD
0.52
0.18
0.68
6.24
15.05
0.09
0.04
37.5
3.5
2.2
7.3
108.1
3
2, 4
2
2, 3
2
2
2,
2,
2,
2,
3, 4
3, 4
3
3, 4
88.4
7.6
40.0
16.9
3.4
7.8
3.1
including sampling of individual snowing events would be necessary to fully characterize elements distribution in the snow during
the winter season.
Table 5
Temporal evolution of the concentration of anthropogenic elements in the surface
snow taken at Cerro Colorado during the 2003, 2008 and 2009 sampling campaigns.
All concentrations in mg kg1.
Element 2003
As
Pb
Cd
Ni
V
Cr
Mn
Co
Ba
Cu
Zn
Mo
Sb
0.76
3.99
0.15
2.99
1.02
2.97
61.46
1.08
38.87
97.89
75.33
0.27
0.02
2008
(0.33e1.26)
2.01 (0.55e3.33)
(2.63e5.98)
61.47 (38.90e74.86)
(0.13e0.19)
1.37 (0.84e2.18)
(1.84e4.92)
2.24 (0.49e3.75)
(0.79e1.47)
2.75 (0.47e4.94)
(1.82e4.69)
1.12 (0.25e1.76)
(17.15e123.35) 74.66 (15.49e133.82)
(0.38e1.56)
2.52 (0.26e5.34)
(12.82e70.42)
37.28 (4.61e77.84)
(42.66e162.43) 189.46 (26.05e386.68)
(31.83e114.46) 49.63 (18.55e72.37)
(0.21e0.36)
1.27 (0.73e1.68)
(0.01e0.04)
0.18 (0.15e0.20)
2009
1.74 (1.65e1.87)
20.54 (13.02e31.26)
0.70 (0.67e0.72)
0.52 (0.37e0.81)
0.31 (0.13e0.46)
0.01
11.60 (5.52e16.96)
0.47 (0.11e0.66)
5.93 (1.97e9.80)
29.19 (12.21e38.44)
28.26 (18.76e37.07)
0.61 (0.27e0.91)
0.13 (0.13e0.15)
the concentrations of As, Pb, Cd, V, Mn, Co, Cu, Mo and Sb were
maximum, probably reecting the impact of signicant changes in
the energy sources distribution at Santiago de Chile during the
studied period. Ni, Cr, Ba (no biomass or coal burning tracers) and
Zn showed a different trend with decreasing values from 2003 to
2009. These preliminary results support the potential use of snow
analysis at Cerro Colorado for indicating changes in the urban
atmosphere of Santiago.
4. Conclusions
This work has demonstrated that anthropogenic trace element
levels in snow precipitation at sampling locations in Cerro Colorado,
Central Andes, about 40 km NE from the metropolitan area are
affected by urban atmospheric emissions from Santiago de Chile. A
simple methodological approach consisting in surface snow
sampling and analysis by a standardized ICP-MS method (including
proper precautions to avoid sample contamination), provide information about spatial distribution and temporal evolution of the
atmospheric precipitation at the selected sampling locations.
Signicant enrichments for a variety of trace element markers,
related to trafc, smelting and biomass burning were found in
Cerro Colorado, by comparison with relatively undisturbed locations at Nevados de Chilln, 500 km S. Temporal evolution of trace
element levels at Cerro Colorado, between 2003 and 2009, were
correlated with changes in Santiago de Chile urban atmospheric
emissions in the same period.
Our preliminary results have shown that snow precipitation in
the Central Andes could be a suitable matrix for receptor model
studies aimed at identifying and quantifying pollution sources at
Santiago de Chile, as a simple and affordable methodology to
complement the information of urban atmospheric surveillance
networks.
Acknowledgements
This work was supported by Agencia Espaola de Cooperacin
Internacional al Desarrollo (AECID), project D/031258/10. Additional support from projects CONICYT: FONDEF D05-I-10054,
FONDECYT 1070500; DGIP-USM N 13.09.57 and Junta de Extremadura (Spain) is also acknowledged.
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57