Journal of Hydrology 540 (2016) 196206

Contents lists available at ScienceDirect

Journal of Hydrology
journal homepage: www.elsevier.com/locate/jhydrol

Hydrological modeling of a watershed affected by acid mine drainage

(Odiel River, SW Spain). Assessment of the pollutant contributing areas
L. Galvn a,, M. Olas b, C.R. Cnovas b, A.M. Sarmiento b, J.M. Nieto b
a
b

Department of Agroforestry Sciences, University of Huelva, Campus La Rbida, 21071 Huelva, CEI CAMBIO, Spain
Deparment of Earth Sciences, University of Huelva, Campus El Carmen, 21071 Huelva, Spain

a r t i c l e

i n f o

Article history:
Received 15 July 2015
Received in revised form 25 February 2016
Accepted 1 June 2016
Available online 7 June 2016
This manuscript was handled by Laurent
Charlet, Editor-in-Chief, with the assistance
of Prosun Bhattacharya, Associate Editor
Keywords:
Acidity
Metals
Mining pollution
Odiel
SWAT

s u m m a r y
The Odiel watershed drains materials belonging to the Iberian Pyrite Belt, where significant massive sulfide deposits have been mined historically. As a result, a huge amount of sulfide-rich wastes are deposited
in the watershed, which suffer from oxidation, releasing acidic lixiviates with high sulfate and metal concentrations. In order to reliably estimate the metal loadings along the watershed a complete series of discharge and hydrochemical data are essential. A hydrological model was performed with SWAT (Soil and
Water Assessment Tool) to solve the scarcity of gauge stations along the watershed. The model was calibrated and validated from daily discharge data (from 1980 to 2010) at the outlet of the watershed, river
inputs into an existent reservoir, and a flow gauge station close to the northern area of the watershed.
Discharge data obtained from the hydrological model, together with analytical data, allowed the estimation of the dissolved pollutant load delivered annually by the Odiel River (e.g. 9140 t of Al, 2760 t of Zn).
The pollutant load is influenced strongly by the rainfall regime, and can even double during extremely
rainy years. Around 50% of total pollution comes from the Riotinto Mining District, so the treatment of
Riotinto lixiviates reaching the Odiel watershed would reduce the AMD (Acid Mine Drainages) in a
remarkable way, improving the water quality downstream, especially in the reservoir of Alcolea, currently under construction. The information obtained in this study will allow the optimization of remediation efforts in the watershed, in order to improve its water quality.
2016 Elsevier B.V. All rights reserved.

1. Introduction
The Iberian Pyrite Belt (IPB) is one of the largest polymetallic
massive sulfide deposits in the world, with original reserves in
the order of 1700 million tons (Sez et al., 1999). Mining activities
of these resources commenced around 3000 BC (Nocete et al.,
2005), continuing intermittently throughout history until the second half of the nineteenth century, when large-scale exploitation
of these deposits developed until the end of the twentieth century
(Olas and Nieto, 2015). The legacy of this intense mining activity
has left large amounts of mining wastes deposited mainly in the
Odiel and Tinto watersheds. The exposure of these sulfide-rich
wastes to atmospheric conditions leads to the oxidation of sulfides,
releasing acidity, sulfate and toxic metals; a process commonly
known as Acid Mine Drainage (AMD), which causes the deterioration of receiving water bodies. This is one of the main causes of
water pollution worldwide (e.g. Bhattacharya et al., 2006; Routh
et al., 2007; S
anliyksel and Baba, 2013).
Corresponding author. Tel.: +34 959 219 872; fax: +34 959 219 440.
E-mail address: laura.galvan@dgyp.uhu.es (L. Galvn).
http://dx.doi.org/10.1016/j.jhydrol.2016.06.005
0022-1694/ 2016 Elsevier B.V. All rights reserved.

The most significant example of this type of pollution is the

Tinto River (Nieto et al., 2007). The Odiel River drains materials
mainly from the IPB and collects acidic lixiviates from several
mines: Tharsis, San Telmo, La Zarza, and Riotinto (Fig. 1), among
others. Although more extreme conditions are found in the Tinto
River, the length of AMD-affected water courses in the Odiel is
longer, and the pollutant load carried to the Ria of Huelva Estuary
and the Gulf of Cdiz is greater due to its higher discharges (Olas
et al., 2006). As a result of environmental concerns, much research
has been done in the last few years to characterize the level of mining pollution suffered by the Odiel watershed (Snchez-Espaa
et al., 2006; Olas et al., 2006; Cnovas et al., 2007, 2012;
Sarmiento et al., 2009; Grande et al., 2010; Galvn et al., 2013;
Nieto et al., 2013). Intense research has also focused on passivetreatment systems for highly metal-rich waters of AMD sources
(Macas et al., 2012a,b; Ayora et al., 2013), in order to accomplish
the goals proposed by the Water Framework Directive (WFD).
However, the main shortcoming of these studies is the lack of
complete discharge datasets, due to the shortage of gauge stations
in the Odiel watershed, and the malfunctioning of existing ones.
These data are essential to estimate reliably the relative

L. Galvn et al. / Journal of Hydrology 540 (2016) 196206

197

Fig. 1. Location map of the Odiel watershed, main mines and sampling points considered in this study (AMD-affected water courses marked in red). Right: different
sub-basins considered in the SWAT model. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

contribution of each sub-basin in the total pollutant load delivered

by the Odiel River, thus enabling cost-effective remediation measures in areas of high AMD pressure.
The main aim of this work is to develop an effective methodology to obtain discharge data, and estimate the pollutant contribution of each sub-basin of the Odiel River reliably, in order to
identify priority areas for remediation. This methodology has been
applied successfully in the Meca River Basin, which is considerably
smaller than the Odiel but is also affected by AMD (Galvn et al.,
2009). This is the first attempt to apply this methodology to a large
watershed deeply affected by mining pollution.
2. The Odiel River Basin
The Odiel River (SW, Spain) has a total length of 140 km and a
drainage basin of 2333 km2. However, this study only considers
the drainage area delimited by the Gibralen gauge station
(Fig. 1), with a surface of 2064 km2, just upstream from the point
where the river suffers from tidal influence up to where, with the
Tinto River, it forms a complex system of marshlands. The Odiel
watershed has a low population density of around 16 hab/km2,
and the main land use is forestry with low development of
agricultural and industrial activities (Galvn, 2011).

2.1. Geology
With the exception of the northernmost area, the Odiel River
Basin flows through materials from the IPB, which belongs to the
South Portuguese Zone of the Iberian Massif. The IPB includes three
units of different lithological characteristics (Sez et al., 1996). The
lower unit is the Phyllitic-Quartzitic (PQ) Group, consisting of a
thick sequence of phyllites and quartzites of Upper Devonian age.
The Volcano-Sedimentary Complex (VSC) is formed by shales,
greywakes and alternating episodes of felsic (dacites and rhyolites)
and mafic rocks (basaltic sills or small stocks) from the upper
Devonian to lower Carboniferous. Finally, the series ends up with
the Culm Group, a detrital unit of synorogenic turbidites, up to
3000 m thick, which basically consists of shales and conglomerates
of Carboniferous age (Tornos, 2006). In the northern part of the
watershed, the Odiel drains plutonic and metamorphic materials
from the Ossa-Morena Zone, mainly schists, quartzites, granites,
gneisses and marbles (upper Precambrian to Devonian age).
The VSC hosts numerous massive sulfide deposits. Among them
is the worlds largest deposit of polymetallic sulfides: the Riotinto
mining district with original reserves of 500 Mt (Sez et al., 1999).
Pyrite is the most abundant mineral (>90%) with variable amounts
of sphalerite, chalchopyrite and galena. Other minor minerals are

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L. Galvn et al. / Journal of Hydrology 540 (2016) 196206

arsenopyrite, tetrahedritetennantite, cassiterite and pyrrhotite.

According to geochemical classifications of volcanic-hosted massive sulfides, the IPB deposits correspond to the ZnPbCu type
(Tornos, 2006).
2.2. Hydrology
The average rainfall in the Odiel watershed is close to 740 mm,
displaying high intra- and inter-annual variability. The average
temperature is 17.4 C, with average minimum and maximum values of 11.4 and 23.4 C, respectively. The watershed has an average
altitude of 261 m, with a maximum elevation of 926 m in the
northern mountainous area. Around 60% of the watershed is found
between 100 and 200 m and less than 1% shows altitudes higher
than 700 m.
The main tributaries of the Odiel River (Fig. 1) are the Oraque
River (with a drainage basin of 607 km2), Olivargas (183 km2)
and the Meca River (316 km2). The materials constituting the basin
have a low permeability. The only aquifers are formed by dispersed
outcrops of marbles from the Ossa-Morena Zone in the northern
part of the basin, with a total surface of 63 km2. These small aquifers are unconfined and receive recharge directly from rainfall
(Galvn, 2011).
The average streamflow of the Odiel River at Gibralen is
17.5 m3/s (Galvn, 2011). The main reservoirs in its basin are the
Olivargas (storage capacity of 28.5 hm3), Odiel (7.4 hm3) and Sancho (58 hm3), which is strongly affected by mining pollution
(Galvn et al., 2009; Torres et al., 2013). There are other reservoirs
in the watershed, such as Gossan-Cobre (Fig. 1), aimed at storing
tailings produced by hydrometallurgical mineral processing from
Riotinto. The construction of a new reservoir (Alcolea, 246 hm3)
has recently commenced, which will be the largest of the watershed and may store acidic waters if remediation measures are
not put into practice to reduce the AMD load (Olas et al., 2011).
3. Methods
The methodology applied in this study relies on a hydrological
modeling of the Odiel watershed to obtain a complete discharge
dataset for each sub-basin, coupled with synoptic samplings in
the whole watershed to obtain detailed hydrochemistry information. These data will be used to establish relationships between
discharge and pollutant concentrations and thus to estimate the
pollutant fluxes along the watershed. This will be explained in
more detail in the following sections.
3.1. Hydrological modeling
A hydrological modeling of the Odiel River was performed using
the SWAT code (Soil and Water Assessment Tool; Neitsch et al.,
2005a,b). SWAT is a semidistributed hydrological model, with an
ArcGIS interface called ArcSWAT, which delimits the river watershed and network using the Digital Elevation Model (DEM), and
calculates the daily water balance, based on soil type, slope, land
use and weather data, by the following equation:

SWt SW0

X
Rday  Q surf  Ea  W seep  Q gw

where SWt is the final soil water content, SW0 is the initial soil
water content, t is the time, Rday is the rainfall, Qsurf is the surface
runoff, Ea is the amount of evapotranspiration, Wseep is the water
input into the vadose zone from the soil profile, and Qgw is the
amount of water returning to the rivers as base flow.
The model represents spatial variability in the watershed, by
discretizing it into smaller units in two steps. First, a division into
sub-basins is made and the water network is calculated. Second,

each sub-basin is divided into several Hydrologic Response Units

(HRUs), with homogeneous characteristics of use, coverage and soil
type. To calculate the surface runoff, the SCS (Soil Conservation
Service) curve number procedure was used (Arnold et al., 1995).
The estimation of each sub-basin runoff is made by adding those
of the HRU that make up the sub-basin, and is routed into the associated channel up to its mouth, along the drainage network. Discharge data generated for each sub-basin is considered in further
calculations for downstream sub-basins, using the variable storage
routing method (Neitsch et al., 2005b).
The portion of rainfall that does not turn into surface runoff is
removed from the soil by percolation and evapotranspiration.
The Hargreaves method was used to calculate potential evapotranspiration because only needs daily values for minimum and maximum temperatures and geographical location (Hargreaves and
Samani, 1985) and gives similar results than other more complex
methods as the PenmanMonteith (Galvn, 2011). The water that
percolates into the ground can go back to surface streams, either
by lateral flow through soil profile, or as base flow coming from
the aquifer. The groundwater system is divided into two aquifers:
one unconfined (which contributes to surface water flow); and a
deep, confined aquifer where infiltrated water does not return to
the system.
A gauge station placed at the watershed outlet was considered
for model calibration and validation purposes (Gibralen; Fig. 1).
For the same aim, simulated Meca River contributions to the Sancho Reservoir (Fig. 1) were compared to experimental reservoir
storage levels. There is another gauge station located in the middle
course of the river. However, its use was rejected due to the high
number of missing data, and the anomalous values observed in
the existent dataset. The absence of gauge stations in the northern
part of the watershed was compensated by using the adjacent
gauge station at the Mrtigas River (sub-basin of 35.2 km2),
located outside the Odiel River watershed. The hydrogeological
parameters of the southern part of the watershed were obtained
from the Meca sub-basin (315 km2), after calibration and validation with water level from the Sancho Reservoir, located just at
the outlet of this sub-basin. Finally, the calibration and validation
of the middle area of the watershed was performed using discharge
data from the outlet Odiel River gauge station at Gibralen (Fig. 1).
Calibration of parameters with a higher weight in the calibration
process was performed using the SWAT-CUP program
(Abbaspour et al., 2007).
In order to assess the simulations performed during the calibration and validation steps, hydrographs obtained by SWAT were
compared visually to those obtained by the gauge stations. In addition, the following statistic parameters were calculated: Pearsons
correlation coefficient (r); NashSutcliffes efficiency parameter
(NSE; Nash and Sutcliffe, 1970); root mean square error (RMS in
m3/s; Hogue et al., 2006); and runoff volume deviation (DV;
Boyle et al., 2000).
3.2. Water samplings and analytical techniques
Several synoptic samplings were performed along the watershed (Fig. 1) from May 2009 to June 2010, with an approximate
monthly frequency. The number of samples collected at each point
ranged from 9 to 16. Hydrochemical data obtained from Sarmiento
(2007) was also used in the model. Electrical conductivity (EC), pH
and redox potential (Eh) were measured in situ with portable
meters. All samples were collected in 100 mL pre-cleaned highdensity polyethylene containers. Water samples were filtered
immediately after collection through 0.45 lm Millipore filters.
Samples for major cations and metal analysis were acidified in
the field to pH < 2 with HNO3 (2%) Merk Suprapur. Then, they were
stored in the dark at 4 C in polyethylene bottles until analysis.

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Concentrations of dissolved Al, As, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li,
Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Si, Se, Sn, Sr and Zn were determined by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES Jobin-Yvon Ultima2), although only the most
relevant will be discussed in this study. Multi-elemental standards
solutions prepared from single certified standards, supplied by SCP
SCIENCE, were used for calibration. They were run at the beginning
and at the end of each analytical series. Certified Reference Material SRM-1640 NIST fresh-water-type and inter-laboratory standard IRNM-N3 waste-water test material (European Commission
Institute for Reference Materials and Measurements) were also
analyzed. Detection limits were calculated by average and standard deviations from ten blanks. Detection limit was below
0.1 mg/L for Al, Ca, Cu, Fe, Mg, Mn, Na, S, Si, K, and Zn, and 3 lg/
L for Sr, Li, Ni, P, Sb, Se, Sn, Mo, As, Cd, Cr, Pb, Be and Co. Samples
were analyzed in triplicate to evaluate the precision, and differences were below 5% for all elements.
3.3. Estimation of contaminant loads
There are different methods to estimate the pollutant load
carried by a river (Preston et al., 1989). Regression methods, which
use an empirical linear relationship between concentration and log
Q values to calculate unknown concentrations of known flows, are
the most suitable when concentration and flow show high values
of correlation (Robertson and Roerish, 1999; Quilb et al., 2006;
Olas et al., 2006). This is the only reliable methodology to estimate
element loads in Mediterranean rivers, when synoptic samplings
fail to capture floods (when highest flow rates and pollutant loads
are reached) and the number of samples is limited (Galvn et al.,
2013). The accuracy of this method relies mainly on the quality
of correlation between flow and concentration. Only relationships
with determination coefficients (R2) higher than 0.60, equivalent
to a correlation coefficient (r) of 0.77, were accepted for
calculations.
4. Results and discussion
4.1. Hydrological modeling
The topography was obtained from the Digital Elevation Model
(DEM) of the Andalusian Regional Government, with an accuracy of
10  10 m. An outlet (the point that defines the creation of a subbasin) was created for each sampling point with available hydrochemical data, as well as for the junction of the main tributaries.
Thus, 53 sub-basins were created (Fig. 1). The land-use map was
obtained from aerial photo-interpretation data, acquired by the
Andalusian Environmental Agency in 1999. The main land use is

forestry, with large extensions of Eucaliptus globulus (28.7% of

the watershed), scrubland (26.9%), and grassland (15%). Soil data
were obtained from a field survey in the watershed. Eleven soil
types were defined; their main characteristics are shown in Table 1
and Fig. 2. Soils are generally poorly developed, prevailing the
Inceptisol order (code 9, 24% of the surface) according to the classification of the USDA Soil Taxonomy. The available water capacity
was calculated using the formula of Saxton et al. (1986). Once landuse and soil-type data were entered into the model, the second
level of subdivision into HRUs was carried out, taking into account
a 10% threshold for land use and a 5% threshold for soil type. As a
result, the final number of HRUs was 1699.
Weather data (daily rainfall and maximum and minimum temperatures) were obtained from 23 rainfall stations and 12 temperature stations, respectively. The series of daily data underwent
quality control. Anomalous values were corrected, and missing
data were replaced with interpolated values from linear regression
with nearby gauges, in order to have a homogeneous and complete
data series available. As SWAT does not reflect adequately the spatial distribution of rainfall with orographic variations in the basin, a
more reliable methodology was applied to estimate the rainfall
distribution (Galvn et al., 2014): the daily precipitation was calculated by multiplying the recorded precipitation by a factor depending on the difference between the center of the elevation band and
the altitude of the rain gauge, instead of adding a constant amount,
as performed by SWAT.
The first step was the calibration and validation of the Mrtigas
and Meca sub-basins, in order to obtain the hydrogeological
parameters in the northern and southern parts, respectively, of
the watershed. The calibration and validation of the model for
the whole watershed was performed subsequently using discharge
data from the Gibralen gauge station (Fig. 1).
The available dataset of daily water inputs to the Sancho Reservoir comprises the periods 1982 to 2002, and the hydrological year
2009/10. The calibration period for the Meca River was from 1982
to 2000, devoting the rest of data for validation purposes. Some
variables were modified initially by manual calibration, and afterwards using the SWAT-CUP program, in order to minimize
observed differences between simulated and measured flow: baseflow recession constant of the aquifer (ALPHA_BF); groundwater
revap coefficient (GW_REVAP), which controls the evapotranspiration from the aquifer when the saturated zone is close to the surface or where deep-rooted plants are growing; initial depth of
water in the shallow aquifer (SHALLST); threshold depth of water
in the shallow aquifer required for base flow to occur (GWQMN);
threshold depth of water in the shallow aquifer for revap to occur
(REVAPMN); groundwater delay time for aquifer recharge
(GW_DELAY); percolation fraction to deep aquifer (RCHRG_DP);
SCS curve number (CN2); soil evaporation compensation factor

Table 1
Main characteristics of considered soil types (AWC: available water capacity, SHC: saturated hydraulic conductivity).
Soil code

10

11

Basin surface (%)

Depth (cm)
AWC (% vol.)
Rock fragment (%)
Clay (% fine fraction)
Silt (% fine fraction)
Sand (% fine fraction)
Organic content (% weight)
SHC at 10 cm (cm/h)
SHC at 50 cm (cm/h)
Bulk density (g/cm3)
Soil hydrologic group

4.8
90.1
0.14
43.0
21.5
42.9
35.5
1.6
2.9
0.7
1.3
C

6.5
59.9
0.15
36.1
29.7
40.4
29.9
2.7
2.2
0.6
1.3
C

9.8
34.0
0.14
39.0
18.4
40.2
41.4
1.7
1.6
1.3
1.3
B

7.9
53.8
0.16
39.1
19.3
51.0
29.6
2.0
1.3
0.6
1.2
C

9.9
55.0
0.15
35.6
16.9
48.32
34.8
2.0
1.8
0.8
1.2
C

4.8
63.5
0.14
38.9
20.8
40.0
39.2
2.2
2.7
1.2
1.3
C

8.1
55.
0.13
74.3
15.1
37.3
47.6
1.0
1.7
1.7
1.4
C

5.3
97.5
0.11
10.3
13.1
27.1
59.7
1.6
8.0
1.8
1.4
C

23.8
48.0
0.14
43.7
23.6
41.7
34.7
3.2
1.4
1.0
1.2
C

16.6
58.4
0.15
39.3
26.8
41.2
31.9
2.4
1.5
0.4
1.3
C

2.4
92.5
0.14
7.60
16.3
41.0
42.6
1.5
1.7
0.2
1.4
D

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L. Galvn et al. / Journal of Hydrology 540 (2016) 196206

Fig. 2. Soils map of the Odiel watershed (see Table 1 for description).

(ESCO) which regulates the direct evaporation from soil water; and
the available water capacity of the soil (SOL_AWC).
Parameters values after the calibration step are shown in
Table 2. A NashSutcliffes efficiency parameter (NSE) value of
0.89 was obtained after calibration, which is considered to be a
very good value according to Moriasi et al. (2007) (Table 3). A
slight overestimation of monthly discharge values (around 5%)

Table 2
Main parameter values after calibration model of the Odiel watershed (see text for
explanation).
Parameters

Subbasins: 1, 2, 6,
9, 14 y 21

Subbasins: 41, 42, 43, 45,

46, 47, 50 y 51

Other
subbasins

ALPHA_BF
GW_REVAP
SHALLST
GWQMN
REVAPMN
GW_DELAY
RCHRG_DP
CN2
ESCO
SOL_AWC

0.2
0.055

150
30
41

25%

20%

1
0.1055
0
292.5
442.5
0.025
0.2
30%
0.01
+0.04 ud.

0.95
0.02

423
383
0.27
0

0.31

was observed. Fig. 3 compares monthly discharge values simulated

using those recorded for the calibration and validation periods. The
monthly NSE values obtained (0.75) during the validation step are
considered as good by Moriasi et al. (2007). The value for runoff
volume deviation (DV) in the validation step increased notably
with respect to the calibration period, which is attributed to the
inaccuracy of water inputs into the reservoir at low stages, and
the existence of some anomalous values recorded at the reservoir
in 2001/02 (Galvn et al., 2009).
In order to obtain the hydrological characteristics for the northern sub-basins, a manual calibration was performed in the Mrtigas River using the following variables: ALPHA_BF, GW_REVAP;
GWQMN, REVAPMN; GW_DELAY; CN2; and SOL_AWC. The values
of the parameters linked to groundwater (Table 2), as the lower
baseflow recession constant in relation to de Meca River, evidence
the existence of dispersed aquifers (marbles from the Ossa-Morena
Zone) in the northern part of the watershed. The runoff volume
deviation between observed and modeled discharges during the
calibration step was close to 1, and the monthly NSE value was
0.61, considered as satisfactory by Moriasi et al. (2007). Fig. 4
shows the fit between modeled and observed monthly discharges
for the calibration and validation periods.

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L. Galvn et al. / Journal of Hydrology 540 (2016) 196206

Table 3
Monthly and daily statistical indices for calibration and validation model of Meca, Mrtigas and Odiel Rivers (r: correlation coefficient; NSE: NashSutcliffes efficiency; RMS: root
mean square error; and DV: runoff volume deviation).
Meca

Mrtigas

Calibration

r
NSE
RMS
DV

Validation

Odiel

Calibration

Validation

Calibration

Validation

Daily

Monthly

Daily

Monthly

Daily

Monthly

Daily

Monthly

Daily

Monthly

Daily

Monthly

0.82
0.68
6.22
1.05

0.94
0.89
1.71
1.05

0.91
0.72
6.67
1.48

0.97
0.75
2.26
1.48

0.56
0.28
1.06
1.04

0.81
0.61
0.34
1.05

0.61
0.19
1.26
0.92

0.84
0.69
0.44
0.92

0.86
0.73
46.64
1.10

0.93
0.83
20.55
1.10

0.76
0.57
42.37
1.10

0.87
0.70
24.28
1.10

Fig. 3. Monthly discharges of the Meca River for the calibration (1982/2000) and validation (2001/02 and 2009/10) periods.

Once the main parameters of the northern and southern parts of

the watershed were obtained, the model for the whole Odiel
watershed was performed. Parameters obtained from the Mrtigas
River were utilized for the northern sub-basins (1, 2, 6, 9, 14 and
21, Fig. 1); while those obtained from the Meca River model were
used in the southern ones (41, 42, 43, 45, 46, 47, 50, and 51; Fig. 1).
The remaining sub-basins were calibrated with SWAT-CUP, by
modifying the following variables: ALPHA_BF; GW_REVAP;
GWQMN; REVAPMN; GW_DELAY; RCHRG_DP; and ESCO (Table 2).
The monthly NSE value for the whole watershed was 0.83; a very
good value according to Moriasi et al. (2007). An overestimation of
around 10% of observed discharges was observed due to the water
consumption in the watershed not being considered in the model.
This overestimation remained for the validation period, while
monthly NSE values can be considered as good. The highest differences between observed and modeled values were recorded during
dry seasons (Fig. 5) and are probably due to the inexistence of a
channeled section in the Gibralen gauge station. The river section
in this point is wide (almost 80 m) and the discharge during these
periods very low (generally < 10 L/s), which implies a high uncertainty in the observed values.
Considering the whole modeled period (from 1982 to 2010), the
Odiel River had an average contribution of 550 hm3 (average

discharge of 17.5 m3/s), of which 9% is delivered by the Olivargas

watershed, 27% by the Oraque, and 10% by the Meca (Fig. 1).
4.2. Pollutant load estimation
Table 4 shows main physicochemical parameters and element
concentrations at some representative points in the watershed
(Fig. 1). The Agrio Creek (point 14) collects the acidic lixiviates
from the Riotinto Mining District, showing a high level of AMD pollution, with maximum values of 1140 mg/L of Al, 554 mg/L of Fe,
269 mg/L of Zn, etc. As a result of this significant AMD input,
together with others of lesser relevance (Fig. 1), the Odiel River
at point 15 show a high level of pollution, with pH values ranging
from 2.3 to 4.5, and average concentrations of 65 mg/L of Fe,
231 mg/L of Al, etc. (Table 4). In the middle reach of the Odiel River
(points 34 and 45), the level of pollution is slightly lower than
upstream (average concentrations of Al between 88 and 96 mg/L;
Table 4) despite the confluence of several AMD inputs, due to the
higher contribution of AMD unaffected waters that cause a dilution
effect in toxic metal concentrations (Sarmiento et al., 2009).
The Oraque headwaters receive the acidic lixiviates from the
San Telmo, Lomero-Poyatos, Confesionarios, and Perrunal mines
(Fig. 1), while significant AMD inputs from the Tharsis mines join

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L. Galvn et al. / Journal of Hydrology 540 (2016) 196206

Fig. 4. Monthly discharges of the Mrtigas River for the calibration (1980/88) and validation (1989/94) periods.

Fig. 5. Monthly discharges of the Odiel River at Gibralen gauge station for the calibration (1982/2000) and validation (2001/10) periods.

203

L. Galvn et al. / Journal of Hydrology 540 (2016) 196206

Table 4
Summary statistics for pH, redox potential (Eh), specific conductivity (SC) and dissolved concentrations of pollutant elements at the most representative points of the Odiel basin.
pH

Eh
mV

SC
mS/cm

Al
mg/L

Be

Cd

lg/L

lg/L

Cu
mg/L

Fe
mg/L

Mn
mg/L

lg/L

Ni

Pb
lg/L

SO4
mg/L

Zn
mg/L

Ayo. Agrio (14)

Mean
Median
Min.
Max.
Sta. Dev.

n = 10
2.813
2.805
2.58
3.18
0.206

686
679
632
744
220

6.82
5.85
3.25
13.0
3.11

402
314
133
1140
281

23
17
20
7.0
20

499
384
146
1210
315

55
41
17
140
37

254
191
57
554
169

80
59
20
190
54

1399
1132
290
3298
911

246
177
70
537
182

6762
4600
1794
16932
4608

117
79
28
269
81

Odiel (15)
Mean
Median
Min.
Max.
Sta. Dev.

n = 30
3.1
3.0
2.3
4.5
0.6

559
551
364
757
198

3.56
1.79
0.54
12.6
3.53

231
79
12
1086
289

15
7.2
0.4
54
16

212
82
18
868
257

23
9
1.5
95
28

65
21
1.9
271
80

37
13
2.3
156
47

581
230
37
2260
718

79
42
8.4
375
100

2924
1136
229
11134
3405

47
17
3.9
209
61

Odiel (34)
Mean
Median
Min.
Max.
Sta. Dev.

n = 13
3.6
3.7
2.7
4.7
0.6

636
630
509
745
192

1.79
1.19
0.59
4.54
1.32

88
41
17
280
84

92
48
38
296
78

10
6.7
3.1
33
8.2

11
7.3
2.1
35
10

16
8.2
3.7
60
17

264
140
75
1010
268

62
26
6.1
294
88

1314
754
385
4284
1177

21
12
6
69
19

Odiel (45)
Mean
Median
Min.
Max.
Sta. Dev.

n = 29
3.2
3.0
2.2
4.7
0.6

554
534
330
781
186

1.96
1.43
0.26
5.73
1.38

96
67
8
498
106

87
59
6.9
398
83

10
7.2
1.0
40
8.3

20
9.1
1.5
106
26

18
10
1.2
76
18

265
176
17
1094
252

134
55
18.2
571
146

1414
908
147
5823
1278

25
16
2.3
99
23

Oraque (77)
Mean
Median
Min.
Max.
Sta. Dev.

n = 12
2.7
2.6
1.9
4.0
0.6

456
455
284
558
91

2.96
1.65
0.20
8.25
2.94

144
45
2.2
476
180

8.6
4.5
0.1
22
9.1

151
69
7.1
445
161

10
6.0
0.4
38
11

60
41
1.0
224
62

24
7.0
0.4
72
29

628
173
9.2
2048
793

85
98
21
143
46

2371
818
77
7032
2711

52
18
1.5
172
63

Meca (88)
Mean
Median
Min.
Max.
Sta. Dev.

n = 29
2.9
2.8
1.7
4.4
0.6

554
532
429
735
104

2.11
2.21
0.48
5.39
1.09

88
88
8.8
305
63

4.8
5.2
0.4
13
3.0

62
66
4.5
198
39

10
9.7
1.6
43
7.8

36
12
1.7
311
68

16
16
1.3
41
10

437
481
32
1086
257

127
104
7.0
969
189

1379
1459
177
5440
1004

27
28
4.3
108
21

Odiel (91)
Mean
Median
Min.
Max.
Sta. Dev.

n = 29
3.4
3.4
2.6
4.7
0.5

517
511
346
726
105

1.28
1.05
0.35
2.93
0.71

39
38
4.9
121
25

2.6
2.6
0.3
7.4
1.7

41
42
4.4
91
22

3.9
3.7
0.7
11
2.1

6.6
3.4
0.9
36
8.4

9.0
6.3
1.2
19
6.3

137
103
11
274
83

70
46
15
179
53

798
647
124
1697
476

12
11
2.1
26
6.5

the river in its lower course. As a consequence of this AMD pressure, the Oraque River (point 77) shows an average pH value of
2.7 and high pollutant concentrations (60 mg/L of Fe, 144 mg/L of
Al and 52 mg/L of Zn; Table 4).
The Meca River (point 88) is also affected by acidic lixiviates
coming from the Tharsis mines, showing a high level of AMD pollution (average values of 88 mg/L of Al, 36 mg/L of Fe and 27 mg/L
of Zn; Table 4). This river is regulated by the Sancho Reservoir,
which removes a significant fraction of the incoming pollutant load
(50% of Al, 45% of Cu and 27% of Zn; Galvn et al., 2009), giving rise
to a water quality improvement downstream.
The Odiel River (point 91), just before the confluence with the
estuary, shows lower metal concentrations than those recorded
upstream (e.g. 39 mg/L of Al, 6.6 mg/L of Fe and 12 mg/L of Zn),
due to the dilution effect exerted by freshwaters streams. This is
especially significant for Fe owing to intense precipitation
processes along the river course. The saturation indices (SI) for Fe
minerals forming from AMD waters were calculated with PHREEQC
(Parkhurst and Appelo, 1999) with the database of MINTEQ2.
For schwertmannite, the data of Yu et al. (1999) were used. The
most probable phases precipitating in the Odiel River are
K-Jarosite (KFe3(SO4)2(OH)6) and schwertmannite (Fe8O8(OH)6
(SO4) (Cnovas et al., 2007). For K-Jarosite the SI values show

oversaturation (from 1.9 to 5.1) at points 14, 15, 34 and 45, located
in the middle and northern part of the basin, while in the southern
points (77, 88 and 91) the values were close to equilibrium (2.3 to
1.3). In relation to schwertmannite, the middle and northern
samples show conditions close to equilibrium (SI from 1.1 to
3.2) while those in the south were undersaturated (7.4 to
9.1). These data coincide with a more intense precipitation of iron
in the river reaches closer to the AMD sources.
The dissolved pollutant load delivered by the Odiel River was
estimated for the period 1982/2010, by establishing relationships
among discharges obtained with SWAT and metal concentrations
at several control points. Fig. 6 shows some examples of these relationships; metal loads have only been calculated using relationships displaying values of R2 > 0.60.
The outstanding main contributors of pollutants to the Odiel
River are the lixiviates originated in the Riotinto Mining District,
delivered by the Agrio Creek (point 14), with an annual load of
4400 t of Al, 2140 t of Fe, 958 t of Zn, and high amounts of other
metals, such as Cd, Ni, etc. (Table 5). These values represent about
4060% (depending on the element) of the pollutant load in the
watershed outlet. Sanchez-Espaa et al. (2005) estimated the contaminant load for the sub-basins of the Odiel River from two samplings corresponding to different hydrological conditions (winter

204

L. Galvn et al. / Journal of Hydrology 540 (2016) 196206

Fig. 6. Examples of relationships between modeled discharges and dissolved element concentrations at different sampling points considered in this study: (a) Odiel River at
Santa Rosa (point 34); (b) Meca River (point 88); and (c) Odiel River at Gibralen (point 91).

Table 5
Annual pollutant loads delivered by the main water courses of the Odiel watershed for the period 1982/2010.
Al

Cu

Fe

Zn

SO4

ton
Agrio Creek (Point. 14)
Odiel after Agrio Creek (Point. 15)
Odiel after Olivargas (Point 34)
Odiel at Sotiel (Point 45)
Oraque River (Point 77)
Meca River (Point 88)
Odiel at Gibralen (Point 91)

4398
6296
6556

1615
418
9138

Be

Cd

Ni

5226
6364
9200

1906
263
8931

12250
15630
18151
22754
5718
1652
25060

kg
559
723
1127

212
69

2141
1585
997

1485

and summer). According to their results, the Agrio River contributes between 27 and 81% of the total contaminant load of sulfates, Al, Cd, Cu, Fe, Mn, and Zn, showing a higher range than that
found by us.
The Odiel at its upper course (point 15) carry a high pollutant
load (6300 t/yr of Al, 1376 of Zn, etc.) after receiving the acidic lixiviates from several mines, such as Concepcin, San Platn, Esperanza, and Poderosa, and the confluence of the above-mentioned
Agrio Creek. However, the Fe load diminishes with respect to the
latter, due to the intense Fe precipitation during mixing between
the Odiel and Agrio waters. Recently, an AMD passive-treatment
plant, based on dispersed alkaline substrate (DAS) technology,
was implemented in the Esperanza Mine with successful results
(Macas et al., 2012a,b). The operation of this plant, together with

958
1376
1878

713
150
2764

62904
88802
118703
138397
34784
7397
158378

338

103
16
431

other projected in the Concepcin Mine (Fig. 1), will improve the
water quality in this river reach in the short term.
In the middle course of the Odiel River (point 34) a significant
increase in Zn, Cd and Ni loads (Table 5) was observed, due principally to the acidic lixiviates from La Zarza mine, while the Fe load
continued to decrease in relation to upstream values. Pollutant
loads downstream (point 45) could not be estimated for some elements owing to poor correlations between discharges and element
concentration (R2 < 60). However, an increment in sulfate and Ni
loads was observed (Table 5).
The pollutant load carried by the Oraque River before the confluence with the Odiel was of 1600 t/yr of Al, 710 t/yr of Zn, etc.
(Table 5), which represents between 18 and 32% of the pollutant
load carried by the Odiel River at Gibralen. Just at the confluence

L. Galvn et al. / Journal of Hydrology 540 (2016) 196206

of the Oraque and Odiel Rivers, the construction of the Alcolea

Reservoir (246 Mm3) has commenced; the pollutant load estimated at this point strengthens the doubts about the final quality
of the water stored in this reservoir (Olas et al., 2011).
The Meca River (point 88), the last tributary of the Odiel before
the confluence with the estuary, carries a high pollutant load into
the Sancho Reservoir, standing at 420 t/yr of Al and 150 t/yr of Zn
(Table 5). This pollutant load causes the acidification of reservoir
waters (pH close to 4), and significant concentrations of toxic metals. The Odiel River at Gibralon, just before the confluence with
the estuary (point 91), carries 9140 t/yr of Al, 2760 t/yr of Zn,
25 t/yr of Ni, etc. (Table 5), which constitutes an extreme case of
pollution worldwide. According to previous studies (Olas et al.,
2006; Nieto et al., 2007), most toxic metals (Al, Cd, Co, Ni, Zn,
etc.) are carried in the dissolved fraction. However, the transport
of Fe, As, Cr and Pb by particulate matter can be very significant,
especially during flood events (Cnovas et al., 2007, 2008, 2010).
Sanchez-Espaa et al. (2005) found that most of dissolved contaminants (99% Fe, 7274% of Al, 73% Zn, 6872% of SO4, etc.) are
retained in the Odiel basin by precipitation in the water courses.
Adding the contaminant load of points 45, 77 and 88 (Table 5)
and comparing the results with that of the basin outlet (point
91), we obtain that only 13% of SO4 and 17% de Zn are retained
in the basin (for the rest of elements there is no values at point
45). These high differences are probably due to the samplings of
Sanchez-Espaa et al. (2005) were carried out in different dates
(e.g. the winter sampling was carried out through February and
November of 2003 and March of 2004) and, therefore, the characteristics (discharges and dissolved concentrations) of the AMD and
river samples are not homogeneous.
Comparing the results obtained in this study with those estimated by Olas et al. (2006) for the period 1995/2003, based on
weekly sampling, similar loads for most elements are observed
except for Al (Table 6). However, Olas et al. (2006) recognize a
high uncertainty in the Al load estimation, due to the lower number of analytical data used, which suggests that the Al loads estimated in this study are more reliable.
A comparison with estimations from Galvn et al. (2013) for the
hydrological year 2009/10, which was unusually wet, was also performed (Table 7). The results obtained in the present study for this
year, considering the whole watershed, are slightly lower (between
20 and 30%) than those obtained by Galvn et al. (2013), except for
Cd. It may be noted that the determination coefficient (R2) used for
Cd in our study is 0.60, and therefore, subject to a higher
uncertainty. On the other hand, an exhaustive study of
Table 6
Comparison of average pollutant loads estimated in this study with those obtained by
Olas et al. (2006).

Al
Zn
SO4
Cd
Ni

t/yr
t/yr
t/yr
t/yr
t/yr

Calculated values

Olas et al. (2006)

9138
2764
158376
8.9
25.1

4557
2612
147213
7.1
33.9

Table 7
Comparison of average pollutant loads estimated in this study for the year 2009/10
with those obtained by Galvn et al. (2013).

Al
Zn
SO4
Cd
Ni

t/yr
t/yr
t/yr
t/yr
t/yr

Calculated values

Galvn et al. (2013)

18935
5695
320775
18.4
50.4

13259 1071
4265 242
257534 13464
11.2 0.7
38.9 2.1

205

discharge-concentration relationships showed the existence of

intra- and inter-annual variations (Olas et al., 2006). The present
study did not take into account these variations and average values
of these relationships were obtained (and thus, average values of
pollutant loads) without considering extreme rainy conditions,
such as those obtained by Galvn et al. (2013).

5. Conclusions
The SWAT model is a useful tool to reproduce a historical discharge data series, and to infer discharge data when missing gaps
are recorded at gauge stations. The reliability of the model relies
logically on the quality of input data. The calibration with experimental data at selected points of the watershed, and otherwise
in watersheds of similar characteristics, is of paramount importance to obtain reliable results. In the Odiel River a good fit
between simulated and measured discharges was observed for all
sub-basins considered during the calibration and validation steps.
The highest differences were observed at low stages during the
dry season, due to the high uncertainty of measurements under
those conditions at the Gibralen gauge station, which does not
have a channeled section.
Concerning the average loads of dissolved elements, the Agrio
Creek, which receives the acidic lixiviates from the Riotinto Mining
District, is by far the main pollutant contributor of the Odiel watershed (around 4060%). Other areas of high AMD pressure are the
Odiel upper course, where the effluents from the Concepcin, San
Platn, Esperanza, and Poderosa mines join the river before its
junction with the Agrio Creek, and the Olivargas sub-basin, which
collects the drainages coming from La Zarza mine. Contrary to
other contaminants, the Fe dissolved load decreases in some areas
downstream of the mining zones, due to intense precipitation
along the riverbed.
The Oraque River, affected by several mines located in its headwaters and by the Tharsis mines downstream, also contributes to
the pollutant load delivered by the Odiel River; around 18 and
32% of the total load. Recently, the construction of a new reservoir
in the watershed has commenced, just at the confluence of the Oraque and Odiel Rivers. The pollutant load into the projected reservoir calculated in this study supports previous estimations that
forecast the acidic composition of stored waters if remediation
measures on AMD sources are not put into practice. The Tharsis
mines also release a high pollutant load into the Meca River
(418 t/yr of Al, 150 t/y of Zn, among others), which is the cause
of the current acidification of the Sancho Reservoir.
It has been estimated that the average dissolved pollutant loads
delivered by the Odiel River for Al (9138 t/yr), Zn (2764 t/yr) and
other toxic metals (e.g. Cd, Cu, Ni) are quite similar to those
obtained in previous studies. These pollutant loads increase notably during rainy years. This study provides essential information
to decision-makers; the collection and treatment of Riotinto lixiviates reaching the Odiel watershed would reduce the AMD pressure
by around 4060%, notably improving the water quality downstream, especially in the forthcoming Alcolea Reservoir.

Acknowledgements
This work has been financed by the projects CGL-2010-21956C02-2 and CGL-2013-48460-C2-1-R from the Spanish Ministry of
Economy and Competitiveness. L. Galvn has been financially supported by the Postdoctoral Program for the Strengthening of R+D+I
capacities from Huelva University. C.R Cnovas was supported
with a Grant from the Andalusian Regional Government
(P11-RNM-7199). We thank two anonymous reviewers for their

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L. Galvn et al. / Journal of Hydrology 540 (2016) 196206

constructive comments, which helped us to improve the original

manuscript. We also thank the support of CEI CAMBIO.
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