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World Multidisciplinary Earth Sciences Symposium (WMESS 2016) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 44 (2016) 022027 doi:10.1088/1755-1315/44/2/022027
Hydrogeochemistry Characterization of Hot Springs Located
in The Andes of Ecuador
David Vinicio Carrera-Villacrés 1, Alexander Hidalgo-Hidalgo 1, Paulina
Guevara-García 1, María Vivero-Balarezo1, Vicente Delgado-Rodríguez 1
1
Universidad de las Fuerzas Armadas-ESPE, Departamento de Ciencias de la Tierra y
la Construcción, Grupo de Investigación en Contaminación ambiental (GICA), Av.
Gral. Rumiñahui S/N, Sangolquí, Ecuador
Abstract. The formation of several sources of hot springs in the Andes from Ecuador is the
result of an intense volcanic activity due to the subduction of the Nazca oceanic plate under the
South American continental plate. The aim of this study was to describe the
hydrogeochemistry water geothermal origin, its chemical classification and relationship with
the complex geology of Ecuador, using different hydro chemical diagrams (Stiff, Piper and
Schoeller-Berkaloff). Geothermal waters can be divided into two groups. The first group,
associated with an extinct volcanic activity produced in the Cenozoic, represents the Na+-Cl-
type. The second group is associated with a young Quaternary volcanic activity and its types of
water are Mg2+-HCO3-, Na+-HCO3-, Na+-SO42-, Mg2+-SO42-.
1. Introduction
Ecuador has various sources of geothermal water originating from a strong magmatic activity
produced in the Quaternary Period due to the subduction of the Nazca oceanic plate under the South
American continental plate [1] These sources are located in the called zone of volcanic arc of Ecuador.
The aim of this study is to describe the hydro geochemistry of the hot springs used in the spas located
in the Andes of Ecuador and also their behaviour, predominant ions, chemical classification and
relationship with the complex geology of Ecuador, using different hydrochemical diagrams, such as
Stiff, Piper and Schoeller-Berkaloff.
2. Materials and Methods
The samplings were taken in 34 places located along the Andes of Ecuador. The distance in sampling
was about 3215 kilometres. The Sampling points can be observed in the Figure 1.
2.1. Determination of physico-chemical parameters
Physico-chemical parameters were taken in situ for these samples. These samples were measured for
water temperature with a mercury thermometer. In the laboratory of the Universidad de las Fuerzas
Armadas ESPE, the pH was analysed with the usage of the pH meter model Thermo Scientific Orion
3-Star and the electrical conductivity (EC) was measured using a conductivity meter model HACH
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World Multidisciplinary Earth Sciences Symposium (WMESS 2016) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 44 (2016) 022027 doi:10.1088/1755-1315/44/2/022027
HQ14d. Finally, Total Dissolved Solids (TDS) and Waste dry calcined (RSC) were measured with the
support of APHA [2].
Figure 1. Samplings point of hot springs in the Andes from Ecuador
Anions and Cations of the first 24 samples were sent to Havoc, which is a laboratory in Ecuador, and
they are by the Ecuadorian Accreditation Service. In the laboratory of environmental work from
ESPE, 10 leftover samples were analysed. The concentrations of Ca2+ and Mg2+ were obtained by
colorimeter methods, the values of the concentrations of Na+ and K+ were measured with an Ion Meter
inoLab® pH / ION 7320, Cl- by colorimetry according to NTE INEN 0976 (1984), HCO3- by the
volumetric method and SO42-, NO3- and PO43- spectrophotometrically according to EPA [3].
2.2. Determination of the error rate in the variables measured in the laboratory
After obtaining the results of the analysis, a control was performed to check the error in the results by
calculating the percentage of error [1] existing in the sum of anions and cations, established by APHA
[2].
∑ ∑
% ∗ 100 (1)
∑ ∑
Table 1 shows the percentages admissible for each range of sum of anions and cations. It is
necessary to check the results with the information in the table 1 to review if the parameters measured
in laboratory are right.
Table 1. Percentage allowable difference in analytical results, [2]
Sum of cations (meq/L) % Acceptable difference
0.0 – 3.0 ± 0.2 %
3.0 – 10.0 ±2%
10 – 800 ± 2.5 %
2
World Multidisciplinary Earth Sciences Symposium (WMESS 2016) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 44 (2016) 022027 doi:10.1088/1755-1315/44/2/022027
2.3. Development of hydrochemical diagrams
The hydrochemical diagrams were made with the software Diagrammes versión 6.5 and developed by
the laboratory of the Hydrogeology of the Université d’Avignon. Piper diagrams triangular, polygonal
and Stiff logarithmic diagrams Berkaloff Schoeller vertical columns in order to chemically classify
water samples are plotted.
2.4. Mapping
The maps were produced using a software Arc GIS with the shape files of the Instituto Geográfico
Militar in Ecuador (IGM) and the geological mapping of the Instituto Nacional de Investigación
Geológico Minero Metalúrgico in Ecuador (INIGEMM). In these maps the polygonal diagrams of
Stiff were added to appreciate the variation between cations and anions of the samples and the spatial
arrangement of the Hydrogeochemical families.
3. Results and Discussions
For a better analysis and interpretation of hydrogeochemical data was divided in three zones: the
north zone (Carchi, Imbabura and Pichincha), the centre zone (Cotopaxi, Napo, Tungurahua and
Chimborazo) and the south zone (Cañar, Azuay and El Oro).
In the north zone the largest number of samples (20) was taken due to the presence of the volcanoes
that have their base in the Cordillera Occidental and the valley of the Andes. The temperature values
were recorded between 18 - 60 °C, having the pH values between 4.96 and 7.65 and the electrical
conductivity from 166 to 6795 µS / cm. Relatively pH values <6 (Lloa and Aguas Hediondas)
indicated a possible interaction with the acid gases [4].
The total dissolved solids (TDS) ranged from 208 to 4128 mg l-1. In the Figure 2A the Piper
Diagram is represented and Figure 3 shows the Stiff Diagram. Four water families were determined in
the Piper and Stiff diagrams: sodium bicarbonate, (Guachalá and El Tingo), sodium Chloride
(Chachimbiro y Nangulví), sulphated sodium (Aguas Hediondas) and bicarbonate magnesium, the rest
samples were characterized by their low salinity. The hot springs from Province of Pichincha are
associated with the Chacana caldera located in the volcanic centre of the largest rhyolite quaternary
volcanic complex of Ecuador [5]. In the province of Carchi is associated with volcanoes called Chiles
(Aguas Hediondas) and the pyroclastic deposits of extinct volcanoes that exist in the Province, in
Imbabura to volcanic deposits Yanahurco volcanoes (Chachimbiro) and Imbabura (Peguche).
Figure 2. (A)Piper diagram of samples points in North Zone. (B) Schoeller – Berkaloff diagram of
samples points in North Zone
3
World Multidisciplinary Earth Sciences Symposium (WMESS 2016) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 44 (2016) 022027 doi:10.1088/1755-1315/44/2/022027
Figure 3. Hydro-geochemical Map of north zone with Stiff diagrams
In the Central Zone, the recorded temperature values ranged from 21 to 61 °C, with the pH values
between 6.2 and 8.3 and EC between 1150 and 8970 µS / cm.
4
World Multidisciplinary Earth Sciences Symposium (WMESS 2016) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 44 (2016) 022027 doi:10.1088/1755-1315/44/2/022027
The values from 1008 to 7932 mg l-1 were measured in TDS (El Salado). As shown in the diagram
Piper (Figure 4a) and in the Stiff diagrams (Figure 5), there are four family types. The first family is
bicarbonate magnesium (Guapante and Nagsiche), probably because of the shallow water areas with a
sediment accumulation [6] and a low mineralization and temperature.
The second family is magnesium sulphate (El Salado, La Virgen and Los Elenes). The third one is
sodium chloride (Papallacta, Cununyaku and Jamanco).
The fourth one is bicarbonate sodium (Aluchán and Oyacachi). The hot springs in this area are
located within the Cordillera Real and they are associated with the Quaternary volcanic activity of the
existing stratovolcanoes characterized by their lava flows and pyroclastic basaltic to rhyolitic
composition [7]. In the case of SPAS called La Virgen and El Salado (Volcano Tungurahua),
Cununyaku (Chimborazo Volcano), Jamanco, Papallacta and Oyacachi (Volcanic Formation
Pisayambo).
Figure 4. (A) Piper diagram of samples points in Centre Zone. (B) Schoeller – Berkaloff diagram of
samples points
In the South Zone the highest temperature and EC values were measured: Baños de Cuenca (62°C)
and Guapán (20,220 μS cm-1). The pH values were neutral except for Portovelo, (8.09) showing a
slightly basic value and therefore also high values of TDS> 4000 mg l-1, and the special case of
Guapán (11308 mg l-1), whose high salinity is a result of the prolonged rock-water interaction and the
evaporation processes, [4]. As shown in the Stiff diagrams (Figure 7) and the Scholler Berkaloff graph
(Figure 6B), the most abundant ions in these samples are Na+ and Cl-.
The Piper diagram (Figure 6A) identified a family type of water: chloride sodium. This type of
water is characterized by ancient deep aquifers and the remaining geology of the extinct volcanic
activity of this area of Ecuador during the Miocene [8]. These waters are probably near or passing
through the salt diapers [9, 10].
5
World Multidisciplinary Earth Sciences Symposium (WMESS 2016) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 44 (2016) 022027 doi:10.1088/1755-1315/44/2/022027
Figure 5. Hydro-geochemical Map of centre zone with Stiff diagrams
6
World Multidisciplinary Earth Sciences Symposium (WMESS 2016) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 44 (2016) 022027 doi:10.1088/1755-1315/44/2/022027
Figure 6. (A) Piper diagram of samples points in South Zone. (B) Schoeller – Berkaloff diagram of
samples points in South Zone.
Figure 7. Hydro geochemical Map of south zone with Stiff diagrams
4. Conclusions
The hot springs in Ecuador can be divided into two groups. The first group is associated with the
extinct volcanic activity produced in the Cenozoic (Oligocene, Miocene and Pliocene) and the second
7
World Multidisciplinary Earth Sciences Symposium (WMESS 2016) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 44 (2016) 022027 doi:10.1088/1755-1315/44/2/022027
group is associated with the young Quaternary volcanic activity. The first group is characterized as
sodium chloride water (Guapán, Los Elenes, Baños de Cuenca, Cununyaku and Nagulví), which
recorded higher temperatures and higher mineralization than the other groups, and the Stiff diagrams
were in "T" form. The water samples from the Quaternary Era are: bicarbonate magnesium and
bicarbonate sodium, sulphate sodium and sulphate magnesium. These kinds of waters are related to the
complex geology of the characteristic volcano clastic deposits of igneous rocks (basalts and rhyolites)
and metamorphic rocks (schists) of the Cordillera Real and Inter-Andes Valley where they emerge.
Stiff diagrams are shaped as arrowhead (Mg2- HCO3-Na+ - HCO3) and irregular polygons (Mg2-SO42-,
Na+ -SO42-).
References
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[2] APHA. American public health association. 1995. Standard methods for the examination of
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[3] EPA, Enviromental Protection Agency. 1983. Methods for Chemical Analysis of Water and
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[4] Inguagggiato, S., Hidalgo, S,. Beate, B., Bourquin, J., 2010. Geochemical and isotopic
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[5] Villares, F., 2010. Estudio geovulcanológico de la Zona sur de la Caldera Chacana. Escuela
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[6] Custodio, E., Llamas, M., 2001. Hidrología Subterránea. Tomo I. Ediciones Ortega. España.
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[8] Beate, B., Monzier, M., Spikings, R., Cotton, J., Silva, J., Bourdon, E., Eissen, JP., 2001. Mio-
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[10] Hounslow, A., 1995. Water Quality Data. Lewis Publishers., United States of America, 71-125p
