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HydrogeochemicalanalysisofvolcanicandgeothermalfluidsintheAndesfromEcuadorusinghydrochemicalplots(Stif....

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Hydrogeochemical analysis of volcanic and geothermal fluids in the Andes from Ecuador

using hydrochemical plots (Stiff, Piper and Schoeller-Berkaloff diagrams)

View the table of contents for this issue, or go to the journal homepage for more

2016 IOP Conf. Ser.: Earth Environ. Sci. 39 012062

(http://iopscience.iop.org/1755-1315/39/1/012062)

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Hydrogeochemical analysis of volcanic and geothermal fluids

in the Andes from Ecuador using hydrochemical plots (Stiff,

Piper and Schoeller-Berkaloff diagrams)

D Carrera-Villacrés1, 2

, A Hidalgo1, P Guevara-García

1, M T Vivero

1 and V

Delgado-Rodríguez1

1Universidad 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

E-mail: dvcarrera@espe.edu.ec

Abstract. The formation of several sources of hot springs in the Andes from Ecuador was the

result of intense volcanic activity due to the subduction of the Nazca oceanic plate under the

South American continental plate. The aims of this study include the presentation of chemical

analysis in graphical form in order to describe the hidrogeochemistry water geothermal origins,

their chemical classification and their relationship to the complex geology of Ecuador using

different hydro chemical plots such as Stiff’s polygonal diagram, Piper’s trilinear diagram and

Schoeller-Berkaloff’s logarithmic vertical columns diagram. Geothermal waters can be divided

into two groups. The first group was associated with an extinct volcanic activity produced in

the Cenozoic and were qualified based on the type of water Na+-Cl- , while the second group

was associated with young Quaternary volcanic activity, and the types of water were Mg2+

-

HCO3-, Na

+-HCO3

-, Na

+-SO4

2-,Mg

2+-SO4

2-.

1. Introduction

Ecuador has various sources of geothermal water as a result of the strong magmatic activity produced

in the Quaternary by the subduction of the Nazca oceanic plate under the South American continental

plate [1]. These sources are located in the volcanic arc in Ecuador. The aims of this study include the

presentation of chemical analysis in graphical form in order to describe the hydro geochemistry from

hot springs used in spas located in the Andes of Ecuador, including their behavior and their

predominant ions, their chemical classifications and their relationship to the complex geology of

Ecuador according to different hydrochemical diagrams such Stiff’s polygonal diagram, Piper’s

trilinear diagram and Schoeller-Berkaloff’s logarithmic vertical columns diagram.

International Conference on Water Resource and Environment 2016 (WRE2016) IOP PublishingIOP Conf. Series: Earth and Environmental Science 39 (2016) 012062 doi:10.1088/1755-1315/39/1/012062

Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distributionof this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI.

Published under licence by IOP Publishing Ltd 1

2. Materials and methods

The samplings were taken from 34 locations along the Andes in Ecuador. The distance between

sampling sites was approximately 3215 kilometers. The sampling points are shown in figure 1.

Figure 1. Sampling points of hot springs in the Andes of Ecuador.

2.1. Determination of physico-chemical parameters

Any physic-chemical parameters were measured for all water samples. The first parameter was

water temperature as measured in-situ by a mercury thermometer. Sample pH values were analyzed at

the laboratory of the Universidad de las Fuerzas Armadas ESPE with a pH meter, Thermo Scientific

Orion 3-Star model, and the electrical conductivity (EC) was measured with a conductivity meter,

model HACH HQ14d. Finally, Total Dissolved Solids (TDS) and Waste Dry Calcined (WDC) were

measured with APHA support [2]. Anions and cations of the first 24 samples were sent Havoc

laboratory in Ecuador, accredited by the Accreditation Service Ecuadorian. The concentrations of Ca2+

and Mg2+

were obtained by colorimeter methods, the concentrations of Na+ and K

+ were measured

with an Ion Meter inoLab® pH / ION 7320, Cl- content was determined by colorimetry according to

NTE INEN 0976 [3], HCO3- was measured according to the volumetric method and SO4

2-, NO3

- and

PO43-

content were determined spectrophotometrically according to EPA guidelines [4].

Determination of the error rate in the variables was measured in the laboratory.

After obtaining the results of the analysis, a control is necessary to check any result discrepancies

according to the APHA [2] equation 1.

% 𝑀𝑖𝑠𝑡𝑎𝑘𝑒 = [∑

𝑚𝑒𝑞

𝐿 𝑐𝑎𝑡𝑖𝑜𝑛−∑

𝑚𝑒𝑞

𝐿 𝑎𝑛𝑖𝑜𝑛

∑𝑚𝑒𝑞

𝐿 𝑐𝑎𝑡𝑖𝑜𝑛+∑

𝑚𝑒𝑞

𝐿 𝑎𝑛𝑖𝑜𝑛

] ∗ 100 (1)

Table 1 shows the percentages of anions and cations admissible for each range.

International Conference on Water Resource and Environment 2016 (WRE2016) IOP PublishingIOP Conf. Series: Earth and Environmental Science 39 (2016) 012062 doi:10.1088/1755-1315/39/1/012062

2

Table 1. Percentage of allowable difference in analytical results.

Sum of cations (meq/L) % Acceptable difference

0.0 – 3.0 ± 0.2 %

3.0 – 10.0 ± 2 %

10 – 800 ± 2.5 % Source:[2]

It is necessary to check the results with the information the Table 1 to review the accuracy of

parameters.

2.2. Development of hydrochemical diagrams

The hydrochemical diagrams were developed with Diagrammes software versión 6.5, developed by

the laboratory of hydrogeology at the Université d’Avignon.

2.3. Mapping

The maps were produced using Arc GIS software with shape files obtained by the Instituto Geográfico

Militar of Ecuador (IGM) and geological mapping accomplished by the Instituto Nacional de

Investigación Geológico Minero Metalúrgico in Ecuador (INIGEMM). The maps were added to the

polygonal Stiff diagrams to analyze the variation between the cations and anions of the samples and

the spatial arrangement of the hydro geochemical families.

3. Results and discussions

To achieve better analysis and interpretation, the hydrogeochemical data was divided into three zones:

the northern zone (Carchi, Imbabura and Pichincha), central zone (Cotopaxi, Napo, Tungurahua and

Chimborazo) and the southern zone (Cañar, Azuay and El Oro).

In the northern zone, the greatest numbers of samples (20) were obtained due to the presence of

volcanoes with their bases in the Cordillera Occidental and the Andes Valley. The recorded

temperature values ranged from 18 to 60 ° C, with pH values between 4.96 to 7.65 and electrical

conductivity values ranging from 166 to 6795 µS / cm. Relative pH values <6 (Lloa and Aguas

Hediondas) indicated a possible interaction with acidic gases [5]. Table 2 shows the parameters

measured in Ecuador.

International Conference on Water Resource and Environment 2016 (WRE2016) IOP PublishingIOP Conf. Series: Earth and Environmental Science 39 (2016) 012062 doi:10.1088/1755-1315/39/1/012062

3

Table 2. Temperature, pH, EC, WDC, cation and anion in water samples in the Andes of Ecuador.

Total dissolved solid (TDS) content ranged from 208 to 4128 mg l-1

. Figure 2a represents the

associated Piper Diagram, and Map 1 depicts the related Stiff Diagram. Four water families were

determined in the Piper and Stiff diagrams: sodium bicarbonate, (Guachalá and El Tingo), sodium

Chloride (Chachimbiro y Nangulví), sulfated sodium (Aguas Hediondas) and bicarbonate magnesium,

while the remaining samples were characterized by their low salinity. The hot springs from Pichincha

Province are associated with the Caldera Chacana located in the volcanic center of the largest rhyolite

volcanic quaternary in Ecuador [6]. Carchi Province is associated with the Chiles volcanoes (Aguas

Hediondas) and the pyroclastic deposits of extinct volcanoes in Imbabura to the volcanic deposits of

the Yanahurco volcanoes (Chachimbiro) and Imbabura (Peguche).

K+

Na+

Ca+2

Mg+2

SO4-2

Cl-

HCO3-

CO3-2

1 Guachalá 39 6,4 2,6 1424,0 260,0 43,5 335,4 36,5 96,4 <2 340,0 980,0 0,0

2 Oyacachi 50 6,6 5,5 3184,0 2056,0 32,1 893,7 96,2 93,8 101,8 810,0 1701,9 0,0

3 Cununyacu 26 7,0 1,2 660,0 172,0 12,2 105,2 29,7 72,0 8,0 170,0 460,0 0,0

4 El Tingo 40 7,0 3,5 3848,0 972,0 22,7 445,0 24,8 135,9 10,0 380,0 1340,0 0,0

5 La Merced 35 6,5 1,2 1912,0 196,0 11,0 103,1 38,9 71,2 6,0 200,0 440,0 0,0

6 Lloa 29 6,0 1,9 1076,0 152,0 13,8 182,2 76,0 87,0 <2 250,0 680,0 0,0

7 Guapán 60 7,1 20,2 11308,0 10124,0 91,3 4462,0 76,2 95,7 <2 5857,5 2140,0 0,0

8 Agua Caliente - Portovelo 52 8,1 3,4 4012,0 1840,0 34,0 459,5 172,0 47,1 78,0 1099,1 120,0 0,0

9 Baños de Cuenca 62 7,2 4,6 4512,0 2028,0 54,3 637,5 85,0 41,1 72,0 1050,0 440,0 0,0

10 Los Elenes 21 6,9 2,3 1576,0 952,0 7,0 158,8 91,8 168,2 878,0 50,0 320,0 0,0

11 Cununyacu (Tungurahua) 47 8,3 5,1 3408,0 1816,0 4,7 690,0 253,3 94,0 96,0 1633,0 140,0 2,7

12 La Virgen (Baños) 53 6,5 5,9 4232,0 2712,0 59,8 409,9 14,6 481,9 965,0 790,0 920,0 0,0

13 El Salado VT (Baños) 40 6,3 7,2 6128,0 4156,0 56,0 361,3 281,4 490,1 856,8 1001,1 1421,9 0,0

14 El Salado Piscina (Baños) 45 6,6 9,0 7932,0 5476,0 69,1 478,2 306,2 641,3 3234,2 652,1 396,5 0,0

15 Guapante 25 7,2 1,2 1008,0 540,0 10,1 84,0 29,7 71,8 93,0 41,0 520,0 0,0

16 Nachehe 27 6,8 4,0 2616,0 1480,0 38,4 338,0 11,2 303,5 16,0 380,6 1781,0 0,0

17 Aluchán 43 7,0 1,5 1008,0 732,0 6,8 187,1 26,5 46,3 38,0 214,8 420,9 0,0

18 Jamanco 61 6,7 7,7 4772,0 4060,0 138,9 1239,0 256,8 38,9 297,0 2272,5 330,0 0,0

19 Santa Catalina (Papallacta) 56 7,1 2,1 1376,0 980,0 5,7 235,3 192,3 9,0 375,0 450,0 66,0 0,0

20 Nangulví 50 7,4 4,9 3016,0 2624,0 7,6 641,7 229,9 90,9 335,0 1466,9 72,0 0,0

21 Lagartijas 18 6,1 0,5 284,0 116,0 4,5 22,0 14,0 33,9 2,0 29,8 226,0 0,0

22 Peguche (Piscina Incaica) 23 6,5 1,9 1132,0 712,0 13,6 137,4 61,7 101,6 13,4 230,0 630,0 0,0

23 Peguche (Vertiente Sagrada) 23 6,6 2,2 1332,0 900,0 23,3 165,0 46,1 130,5 5,5 290,0 750,0 0,0

24 Chachimbiro 1 52 7,6 6,6 4128,0 3528,0 210,7 968,2 98,0 84,2 57,0 1880,5 500,0 0,0

25 Chachimbiro 2 60 6,4 6,8 4076,0 3432,0 183,2 964,0 83,8 82,2 56,0 1731,7 572,4 0,0

26 La Calera 34 6,3 1,3 852,0 552,0 29,1 73,4 74,2 85,5 31,0 64,3 737,4 0,0

27 Gruta de la Paz 40 6,9 2,6 1748,0 1232,0 74,6 156,1 27,7 215,1 3,5 159,1 1416,5 0,0

28 Paluz 21 6,2 1,1 764,0 508,0 4,7 32,9 68,1 69,9 3,5 38,9 576,5 0,0

29 Rumichaca 34 7,1 3,1 2032,0 1444,0 96,3 267,5 29,9 179,4 6,5 259,0 1490,8 0,0

30 Los 3 Chorros (Neptuno) 25 6,0 0,8 588,0 456,0 27,4 57,3 40,3 45,3 18,0 42,3 435,0 0,0

31 Complejo Turístico Tufiño 25 6,6 0,9 640,0 484,0 24,4 69,6 45,3 44,5 140,8 90,9 270,5 0,0

32 Aguas Hediondas 58 5,0 1,8 1572,0 1288,0 56,6 149,5 87,6 70,2 702,7 118,9 24,4 0,0

33 San Miguel de Car 23 6,2 0,4 376,0 240,0 10,6 26,5 18,0 24,2 37,4 32,0 151,3 0,0

34 El Puetate 18 6,7 0,2 208,0 128,0 1,3 7,1 8,6 12,1 4,4 11,4 83,5 0,0

18 4,96 0,1669 208 116 1,329 7,13 8,6 9,0425 2 11,36 24,4 0

38,7 6,7 3,7 2610,0 1716,1 43,5 457,2 89,2 128,1 275,5 708,5 663,4 0,1

62 8,3 20,2 11308,0 10124,0 210,7 4462,0 306,2 641,3 3234,2 5857,5 2140,0 2,7

Minimun

Average

Maximum

No. Location T°C pHEC

(dS/m)

TDS

(ppm)

WDC

(ppm)

CATION

(mg/l)

ANION

(mg/l)

International Conference on Water Resource and Environment 2016 (WRE2016) IOP PublishingIOP Conf. Series: Earth and Environmental Science 39 (2016) 012062 doi:10.1088/1755-1315/39/1/012062

4

Figure 2. (a) Piper diagram of sample points (b) Schoeller – Berkaloff diagram of sample points

in the northern zone. In the northern zone.

a b

Figure 3. Hydrogeochemical map of central zone via Stiff diagrams.

International Conference on Water Resource and Environment 2016 (WRE2016) IOP PublishingIOP Conf. Series: Earth and Environmental Science 39 (2016) 012062 doi:10.1088/1755-1315/39/1/012062

5

In the central zone, recorded temperature values ranged from 21 to 61 ° C, with pH values between

6.2 to 8.3 and EC values between 1150 to 8970 µS / cm.

The values from 1008 to 7932 mg l-1

were measured in TDS (El Salado). As shown in the Piper

diagram (figure 3a) and the Stiff diagrams (Map 2), four family types were determined. The first

family was bicarbonate magnesium (Guapante and Nagsiche), likely the result of shallow water areas

where sediment can accumulate [7] and matching its low mineralization and temperature. The second

family was sulphate magnesium (El Salado, La Virgen and Los Elenes). The third family was sodium

chloride (Papallacta, Cununyaku and Jamanco). The fourth family was sodium bicarbonate (Aluchán

and Oyacachi). The hot springs in this area are located within the Cordillera Real and associated with

volcanic activity produced in the Quaternary period by existing strata volcanoes as characterized by

their lava flows and pyroclastic basaltic to rhyolitic composition [8]).

Figure 4. (a) Piper diagram of samples points in (b) Schoeller – Berkaloff diagram of

central zone. sample points.

a b

International Conference on Water Resource and Environment 2016 (WRE2016) IOP PublishingIOP Conf. Series: Earth and Environmental Science 39 (2016) 012062 doi:10.1088/1755-1315/39/1/012062

6

Figure 5. Hydro geochemical map of central zone Stiff diagrams.

International Conference on Water Resource and Environment 2016 (WRE2016) IOP PublishingIOP Conf. Series: Earth and Environmental Science 39 (2016) 012062 doi:10.1088/1755-1315/39/1/012062

7

In the southern zone, the highest temperature and EC values were measured as follows: Baños de

Cuenca (62 °C) and Guapán (20,220 μS cm-1

). The pH values were neutral except for Portovelo (8.09)

which indicated a slightly basic value. Portovelo also indicated high TDS values greater than 4000 mg

l-1

, except for Guapán (11308 mg l-1

). This high salinity is the result of prolonged interaction with

rock-water and processes of evaporation [5]. As shown in the related Stiff diagrams (Map 3) and

Scholler-Berkaloff graph (figure 4b), the most abundant ions in these samples are Na+ and Cl

-.

The Piper diagram (figure 4a) identified a water family: sodium chloride characterized by deep

ancient aquifers and remaining geology of the extinct volcanic activity in the Miocene [9] in this area

of Ecuador. These waters are likely near or pass through salt diapirs [10].

Figure 6. (a) Piper diagram of sample points (b) Schoeller – Berkaloff diagram of sample points

in the southern zone. in the southern zone.

Figure 7. Hydrogeochemical map of south zone via Stiff diagrams.

a b

International Conference on Water Resource and Environment 2016 (WRE2016) IOP PublishingIOP Conf. Series: Earth and Environmental Science 39 (2016) 012062 doi:10.1088/1755-1315/39/1/012062

8

4. Conclusions

The hot springs in Ecuador can be divided into two groups. The first group was associated with extinct

volcanic activity produced in the Cenozoic (Oligocene, Miocene and Pliocene) and the second group

was associated with young volcanic activity in the Quaternary. The first group was characterized by

sodium chloride water (Guapán, Los Elenes, Baños de Cuenca, Cununyaku and Nagulví); these

samples were associated with higher recorded temperatures and higher mineralization than other

groups, and Stiff diagrams in "T" shapes. The water samples from the Quaternary were magnesium

bicarbonate and sodium bicarbonate, sodium sulfate and magnesium sulfate. These types of waters are

related to the complex geology of characteristic volcano deposits of igneous rocks (basalts and

rhyolites) and metamorphic rocks (schists) of the Cordillera Real and Inter-Andes Valley where they

were found, and characterized by Stiff diagrams shaped like arrowheads (Mg2+

- HCO3-Na

+ - HCO3

-)

and irregular polygons (Mg2+

-SO42-

, Na+ -SO4

2-).

References

[1] Lonsdale P and Klitgord 1978 Structure and tectonic history of the Eastern Panama Basin

Geological Society of America Bulletin 89: 981-99

[2] American public health association 1995 Standard methods for the examination of water and

wastewater 19th edition Publication office American public health association Washington

D.C. p 199 and 211

[3] NTE INEN 1984 Agua potable Determinación de Cloruros

[4] Environmental Protection Agency 1983 Methods for Chemical Analysis of Water and Wastes

Washington D.C.

[5] Inguagggiato S, Hidalgo S, Beate B and Bourquin J 2010 Geochemical and isotopic

characterization of volcanic and geothermal fluids discharged from the Ecuadorian volcanic

arc Geofluids 1-17

[6] Villares F 2010 Estudio geovulcanológico de la Zona sur de la Caldera Chacana Escuela

Politécnica Nacional

[7] Custodio E and Llamas M 2001 Hidrología Subterránea Tomo I. Ediciones Ortega. España

[8] Aspden J A and Litherland M 1992 The geology and Mesozoic Collisional history of the

Cordillera Real , Ecuador Tectonophysics 205: 187-204

[9] Beate B, Monzier M, Spikings R, Cotton J, Silva J, Bourdon E and Eissen J P 2001 Mio-

Pliocene adakite generation related to flat subduction in southern Ecuador: Quimsacocha

volcanic center Earth and Planetary Science Letters 192: 561-70

[10] Carrera D, Guevara P, Hidalgo A, Vivero M T and Maya M 2015 Removal of physical

information chemistry of spa that is utilizing geothermal water in Ecuador Procedia Earth

and Planetary Sciences 15: 367-73

International Conference on Water Resource and Environment 2016 (WRE2016) IOP PublishingIOP Conf. Series: Earth and Environmental Science 39 (2016) 012062 doi:10.1088/1755-1315/39/1/012062

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