Hydrological Sciences Journal Journal des Sciences Hydrologiques, 59 (6) 2014 1213

http://dx.doi.org/10.1080/02626667.2013.834341

Hydrochemical characterization of an acid mine drainage-affected

reservoir: the Sancho Reservoir, Huelva, southwest Spain
J.C. Cern1, J.A. Grande1, M.L. de la Torre1, J. Borrego1, M. Santisteban1 and T. Valente1,2
1
Centro de Investigacin para la Ingeniera en Minera Sostenible (CIPMS), Escuela Tcnica Superior de Ingeniera, Universidad de
Huelva, Ctra. Palos de la Frontera s/n, ES-21218 Palos de la Frontera, Huelva, Spain
grangil@uhu.es
2
Centro de Investigao Geolgica, Ordenamento e Valorizao de Recursos, Departamento de Cincias da Terra, Universidade do
Minho, Campus de Gualtar, P-4710-057 Braga, Portugal

Received 25 October 2012; accepted 9 July 2013; open for discussion until 1 December 2014
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014

Editor D. Koutsoyiannis; Associate editor M.D. Fidelibus

Citation Cern, J.C., Grande, J.A., de la Torre, M.L., Borrego, J., Santisteban, M., and Valente, T., 2014. Hydrochemical character-
ization of an acid mine drainage-affected reservoir: the Sancho Reservoir, Huelva, southwest Spain. Hydrological Sciences Journal,
59 (6), 12131224. http://dx.doi.org/10.1080/02626667.2013.834341

Abstract The objectives of this study were to discover the relationship between variables in a water reservoir and
the hydrochemical variations related to acid mine drainage (AMD), and to describe the horizontal stratification
related to vertical salinity and variations in metals present in the region. The information obtained may be
used for establishing risk evaluation criteria and to design future remediation strategies, which could be useful for
new dams. The hydrochemical characterization was based on a sampling campaign performed in October 2011. A
total of 28 samples, at 1-m-deep intervals, were obtained. The hydrogeochemical study of the polluted reservoir
shows that the dilution effect is not sufficient to neutralize AMD contributions from mining activity. Sampling
carried out from the surface water to the deepest points reveals stratification of the reservoir that allows it to be
included in the group of monomictic and holomitic lakes.
Key words acid mine drainage; water reservoir; natural attenuations; factor analysis; Iberian Pyrite Belt; stratification;
hydrological characterization; pollution; surface waters; remediation

Caractrisation hydrochimique dun rservoir affect par un drainage de mine acide: le rservoir
de Sancho, Huelva, Sud-Ouest espagnol
Rsum Les objectifs de cette tude taient de dcouvrir la relation entre les variables qualitatives dun rservoir
et les variations hydrochimiques lis au drainage minier acide (DMA), et de dcrire la stratification horizontale
lie la salinit verticale ainsi que les variations des mtaux prsents dans la rgion. Linformation obtenue peut
tre utilise pour tablir des critres dvaluation des risques et pour laborer des stratgies dassainissement
futures, qui pourraient tre utiles pour de nouveaux barrages. La caractrisation hydrochimique a t base sur
une campagne dchantillonnage effectue en octobre 2011. Un total de 28 chantillons, des intervalles de 1 m
de profondeur, a t obtenu. Ltude hydrogochimique du rservoir pollu montre que leffet de dilution nest
pas suffisant pour neutraliser les contributions du DMA de lactivit minire. Lchantillonnage effectu partir
de leau de surface pour les points les plus profonds rvle une stratification du rservoir qui lui permet dtre
inclus dans le groupe de lacs monomictiques et holomictiques.
Mots clefs drainage minier acide ; rservoir deau ; attnuations naturelles ; analyse factorielle ; ceinture de pyrite ibrique ;
stratification ; caractrisation hydrologique, pollution, eaux de surface ; assainissement

INTRODUCTION environmental problem is usually a side effect of

Acid mine drainage (AMD) is one of the most mining for sulphides and coal. Its origin is related
serious types of water contamination due to its nat- to the presence of sulphides, which increase in reac-
ure, magnitude, difficult solution and remediation tivity due to mining and the processing of ore such as
costs (Azcue 1999, Younger et al. 2002). This milling.

2014 IAHS Press

 1214
Sulphide minerals are stable and insoluble under
reductive conditions. Therefore, pyrite and other
sulphides stay preserved in anoxic environments,
preventing the mobilization of metals and acids.
However, when the reactive mineral comes into
contact with oxygen and atmospheric moisture, the
sulphide oxidation process occurs (Sinz 1999). A com-
plex mechanism begins on the mineral surface, which
leads to the production of acids and sulphates, as well as
to the mobilization of metals and metalloids (Nordstrom
and Alpers 1999, Younger et al. 2002, Banks 2004).
At low pH values, the overall sulphide oxidation
process may be catalysed by acidophilic chemo-auto-
trophic micro-organisms that increase the oxidation
rate by a factor of 102 (Singer and Stumm 1970,
Cnovas et al. 2007). The biological action assures
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014
the oxidation of iron, which acts as a strong oxidant,
leading to the intensification of acidity and the main-
tenance of weathering chain reactions (Nordstrom
and Alpers 1999, Younger et al. 2002).
AMD contamination in the Iberian Pyrite Belt
(IPB) is widely known for its antiquity and scale
(Grande et al. 2010a). The IPB is one of the largest
metallogenic regions of the world, with numerous
giant and supergiant massive sulphide ore deposits
(Sez et al. 1999), comprising 1700 Mt of sulphide
reserves (Pinedo-Vara 1963). Consequently, the
regional drainage network is strongly affected by
AMD and acid rock drainage (ARD), as described
by several authors: Elbaz-Poulichet et al. (1999,
2000, 2001), Davis et al. (2000), Grande et al.
(2003a, 2003b, 2005a, 2005b, 2010a, 2010b, 2010c,
2010d, 2010e, 2011a, 2011b), Leblanc et al. (2000),
Borrego et al. (2002), Sinz et al. (2002, 2003a,
2003b, 2004, 2005), Olas et al. (2004, 2005a,
2005b, 2006), Aroba et al. (2007), Jimnez et al.
(2009), de la Torre et al. (2009, 2010, 2011), Carro
et al. (2011) and Grande (2011).
Mining activity was shut down for several years
in the IPB and is now being slowly reactivated.
Nevertheless, the regional water courses, such as
the Odiel River basin, have continued to carry metals
and sulphates from the continent to the ocean
throughout this time (Sainz and Ruiz 2006).
Taking into consideration rainfall intensity
and the duration of the dry period, the Odiel
River basin presents a dry Mediterranean climate,
with annual precipitation around 500700 mm.
Precipitation is rather seasonal, being more fre-
quent between October and May. In summer, it is
almost absent. In the period 19802010, the aver-
age temperature was 17.4C, while the minimum
J.C. Cern et al.
and maximum temperatures were 11.1 and 23.6C,
respectively.
In this type of semi-arid climate, dam construc-
tion is one of the most common solutions to meet
population and industrial water needs. However, the
vulnerability of the water surfaces to contamination is
much greater than that of underground water (Grande
et al. 2010d).
Until now, the Odiel River has seldom been
controlled by dams due to its high AMD contamina-
tion levels (Olas et al. 2004, Grande et al. 2010a).
However, Spanish hydrological plans foresee the
construction of two dams in the Odiel River basin
for public water supply: the Alcolea Dam (300 hm3;
372719N, 65819W) and the Coronada Dam
(800 hm3; 37434N, 64547W). It is expected
that untreated waters received by the Alcolea
Reservoir will have high levels of acidity, aluminium
and other toxic elements. Therefore, it will be useful
to understand the hydrogeochemical processes that
occur in other AMD-affected reservoirs, such as the
Sancho Reservoir (Fig. 1).
The Sancho Dam was built in 1962 and is fed
by the Meca River (Fig. 1). Its waters are used for
industrial purposes, supplying a pulp mill located
15 km downstream, in San Juan del Puerto (south-
west Spain). It has a maximum storage capacity of
58 hm3, with a crest length of 224 m and a height of
56 m a.s.l., and the impounded water covers an area
of 4.27 km2. The total watershed area is 314 km2.
The Meca River (Fig. 1) receives contaminated
waters from different subsidiary tributaries affected
by AMD, mostly from the abandoned Tharsis and
Carpio mines (southwest Spain). These mines define
an important AMD-generating zone, referred to as the
Rivera Meca-Sancho by Grande et al. (2010a), and its
typical AMD properties are presented in Table 1.
In accordance with the above scenario, the
present study has the following objectives:
1. to discover the relationship between the variables
and the hydrochemical variations related to AMD
in the Sancho Reservoir;
2. to describe horizontal stratification related to ver-
tical salinity and variations in metals; and
3. to understand the mechanisms that control the
physico-chemical processes responsible for toxi-
city and a reduction in the mobility of metals.
The information obtained may be used to establish
risk evaluation criteria and to design future reme-
diation strategies, which could be useful for new
dams.
 Hydrochemical characterization of an acid mine drainage-affected reservoir 1215
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014

Fig. 1 Location of the study area.

Table 1 Statistical data of the variables of the 28 samples obtained at the Rivera Meca-Sancho AMD zone (Grande et al.
2010a). EC: electrical conductivity in S cm-1; Eh: in mV; As and Cd in g L-1; Cu, Fe, Zn, Mn and sulphate in mg L-1.
pH EC Eh As Cd Cu Zn Fe Mn SO42-

Minimum 2.15 2560 425 0.0105 20.11 340.7 190.1 25.7 55.9 5317
Maximum 2.72 15 810 623 2.1101 45.26 607.3 556.5 261.0 183.6 11 700
Average 2.43 6035 520.7 0.8938 32.36 443.3 440.9 91.4 147.5 7937
Variance 0.0460411 2.05646E7 4325.07 0.845027 104.524 10 949.8 12 256.8 5257.17 1518.21 4.12289E6

Geological framework sedimentary complex (VSC), and the Devonian pre-

volcanic sediments (PQ group).
The Odiel River is located in the IPB, in the south-
The Culm group comprises the sedimentary
west of Spain (Fig. 2). The IPB covers an area of
and post-volcanic rocks of the IPB (Moreno and
about 6900 km2. It runs from Seville in southern
Gonzlez 2004). Petrographic studies reveal that
Spain to the west coast of Portugal, and contains
fragments of sedimentary and volcanic origin are
numerous Palaeozoic massif sulphide deposits
the major lithic components of the Culm litharenites.
(mainly, Cu, Pb and Zn), the largest in the world
The VSC is the most metallogenically impor-
according to Sez et al. (1999).
tant unit. It consists of a heterogeneous sedimentary
The IPB reveals a highly complex lithology with
series with interbedded magmatic rocks of varying
many different types of rock that vary greatly in their
nature and composition. Among sedimentary rocks,
spatial and temporal distribution. Essentially, there
those of detrital and volcanoclastic origin predomi-
are three major units: the Culm group, the volcano-
nate. The presence of common chemical
 1216 J.C. Cern et al.
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014
Fig. 2 Geological scheme of the studied zone.
sedimentary rocks may also be observed, including
massive sulphides, manganese jaspers and some dis-
continuous levels of fossiliferous limestones (Sez
et al. 2010).
The PQ group has a minimum thickness of
2000 m and its lithostratigraphic features are the
same throughout the whole IPB, except near the top
where some differentiation is observed in various
places. Most of the stratigraphic column units consist
of dark shales (grey to black) with fine sandstone
layers (Moreno and Sez 1990, Sez and Moreno
1997).
MATERIALS AND METHODS
The hydrochemical characterization was based on a
sampling campaign performed in October 2011.
Sample collection was carried out from the surface
to the bottom of the reservoir; 28 samples were
obtained at 1-m-deep intervals. Unlike previous
studies (Sarmiento et al. 2009, de la Torre et al.
2010), which used three sampling points, the pre-
sent study was based on comprehensive stratified
sampling.
A Hydro-Bios water sampler allowed samples to
be extracted at various depths. The temperature, pH,
EC and total dissolved solids (TDS) were measured
in situ, using a portable multiparametric multimeter
(Crison MM 40; Crison Instruments, Barcelona,
Spain). Dissolved oxygen (DO) was measured using
a Hydrolab Quanta probe.
Duplicate samples were taken at each depth.
Three per cent nitric acid was added to one sample
to prevent the metals precipitating out before labora-
tory analysis, so that they could be analysed without
their concentration being altered. The second sample,
to which no type of acid was added, was used for
sulphate analysis. Following collection, the samples
were immediately refrigerated, transported in poly-
ethylene bottles (100 mL), kept in the dark and stored
at 4C until analysis.
Metal concentrations (Al, Zn, As, Sb, Ni, Cd, Cu
and Mn) were determined using an air-acetylene
flame atomic absorption spectrometer (PerkinElmer
AAnalyst 800; PerkinElmer, Norwalk, CT, USA),
equipped with a graphite furnace and hydride gen-
erator. Sulphates were determined by ion chromato-
graphy with suppressed conductivity detection
(Standard Methods 4110). All samples were analysed
twice to check accuracy. The results were also com-
pared with those from ENCE (the dam operator
company), which performs monthly sampling, and
identical results were obtained.
The results of the analyses were submitted to
statistical treatment using Statgraphic Centurion XV
package. This allowed a statistical summary to be
obtained and, additionally, multivariate factor analy-
sis to be performed. Factor analysis was applied to
 Hydrochemical characterization of an acid mine drainage-affected reservoir 1217

the variables, using all the samples in the database, in
order to find hydrogeochemical affinities. It was also
applied to observations, in order to find affinities
between the samples.
RESULTS
Table 2 shows the volume of data obtained from
sampling, which was carried out at a point in the
Sancho Reservoir, at 28 different point depths, with
a distance of 1 m depth between each. In addition,
Table 2 shows the basic statistical parameters (mini-
mum, maximum, average and variance) obtained for
each parameter. Since As was below the detection
limit (<0.001 mg L-1) in all samples, the data are not
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014
Taking into account the average concentrations
of the Mecca River (Table 1), sulphates and metals
are well below the expected values in a mining dam
or an AMD stream (Grande et al. 2005a, 2010d,
Valente and Leal Gomes 2009). Arsenic is always
below the detection limit, and Ni and Sb are the
metals with the lowest concentrations (about 100
times less).
Table 3 shows the correlation coefficient
between pairs of variables, which varies between 1
and 1. Depth has a high positive correlation (>0.8)
with Pb (0.82), Al (0.88) and pH (0.85). However, it
has a negative correlation with temperature (0.88),
DO (0.92) and, although slightly lower, with Zn
(0.74). Zinc shows equally high negative correla-
tions with Fe (0.82) and pH (0.9), and positive

shown. Higher acidity was found in the surface

water; therefore, all samples present pH of less than
4, except at depths below 19 m, where it increases,
reaching a maximum value of pH 4.67 (Table 2). The
EC has values of between 401 and 472 S cm-1, with
a drop towards the intermediate zone; then there is a
relative increase towards deeper areas.
correlations with temperature, T (0.92) and
DO (0.89).
EC has high positive correlation with Mn (0.86)
and TDS (0.98), and rather lower values with DO
(0.75). Lower correlations were found: for Fe with
T (0.76) and pH (0.73); for Al with DO (0.75), T

Table 2 Hydrochemical data of the Sancho Reservoir (October 2011). Statistical data of the variables (S: sample; D: depth
in m; T: temperature in C; EC: electrical conductivity in S cm-1; ions in mg L-1; TDS: total dissolved solids in mg L-1;
DO: dissolved oxygen in mg L-1).
S D Fe Cu Zn Mn Cd Ni Sb Pb Al SO4 T pH CE TDS DO

1 1 0.816 0.786 2.375 1.516 0.131 0.01043 0.0017 0.778 0.0395 190 25.7 3.55 472 302 6.16
2 2 0.706 0.692 2.467 1.677 0.127 0.01049 0.0019 0.657 0.0278 199 25.7 3.54 465 298 5.94
3 3 0.783 0.807 2.396 1.593 0.144 0.00989 0.0016 0.275 0.0544 197 25.8 3.54 458 293 6.01
4 4 0.723 0.741 2.484 1.559 0.122 0.01004 0.0023 0.804 0.0435 188 25.8 3.57 459 293 5.78
5 5 0.607 0.689 2.463 1.571 0.138 0.01005 0.0031 0.871 0.0637 171 25.8 3.59 445 285 5.58
6 6 0.564 0.627 2.445 1.517 0.142 0.01047 0.0032 0.78 0.0502 172 25.8 3.59 443 284 5.39
7 7 0.61 0.62 2.435 1.523 0.142 0.01045 0.0026 0.636 0.0502 176 25.8 3.51 456 292 5.13
8 8 0.679 0.618 2.429 1.531 0.143 0.01041 0.0019 0.566 0.0502 180 25.7 3.57 449 287 4.72
9 9 0.79 0.663 2.54 1.582 0.146 0.01049 0.0023 0.574 0.0495 181 25.7 3.57 450 288 4.89
10 10 0.651 0.71 2.595 1.519 0.138 0.01044 0.003 0.758 0.0596 178 25.6 3.54 454 291 4.99
11 11 0.54 0.518 2.545 1.496 0.147 0.01036 0.0032 1.214 0.0653 185 25.7 3.5 444 284 4.81
12 12 0.643 0.61 2.629 1.522 0.14 0.01047 0.002 1.063 0.0641 187 25.6 3.56 447 286 5.45
13 13 0.748 0.611 2.678 1.577 0.131 0.01049 0.0031 0.968 0.1042 198 25.7 3.57 443 284 4.86
14 14 0.614 0.614 2.723 1.519 0.135 0.01005 0.0031 0.926 0.1170 198 25.6 3.56 451 289 5.19
15 15 0.67 0.585 2.722 1.59 0.118 0.01033 0.0018 1.065 0.1676 196 25.7 3.55 458 293 5.28
16 16 0.591 0.575 2.639 1.489 0.126 0.01049 0.0031 0.946 0.1615 180 25.3 3.65 445 285 4.5
17 17 0.639 0.526 2.426 1.44 0.119 0.01021 0.0015 0.976 0.0987 172 24.9 3.72 430 275 3.95
18 18 0.643 0.447 2.139 1.272 0.122 0.01043 0.0018 1.106 0.1183 171 23.3 3.83 402 257 0.8
19 19 0.848 0.608 2.104 1.079 0.129 0.01046 0.0026 1.36 0.1226 170 21.2 4.3 401 257 0.93
20 20 0.64 0.418 2.064 1.358 0.131 0.01042 0.0015 1.262 0.1356 181 19.0 4.54 419 268 0.98
21 21 1.16 0.624 1.493 1.339 0.131 0.01036 0.0017 1.443 0.1301 171 17.7 4.5 425 272 0.85
22 22 0.916 0.669 2.014 1.465 0.123 0.01027 0.0021 1.647 0.1030 184 17.1 4.66 425 272 0.68
23 23 0.968 0.673 1.923 1.367 0.108 0.01047 0.0034 1.181 0.1460 171 16.4 4.66 435 278 0.56
24 24 0.947 0.648 1.845 1.454 0.139 0.00947 0.0017 1.193 0.1947 173 15.9 4.6 434 278 0.55
25 25 0.816 0.689 1.829 1.429 0.125 0.01039 0.0012 1.467 0.2018 182 15.3 4.62 436 290 0.42
26 26 0.816 0.689 1.83 1.549 0.126 0.01016 0.0032 1.053 0.1456 187 14.8 4.67 442 283 0.37
27 27 1.042 0.662 1.646 1.452 0.137 0.01018 0.0012 1.27 0.1764 179 15.2 4.61 435 279 0.22
28 28 0.977 0.694 1.730 1.571 0.133 0.00973 0.0013 1.912 0.1404 172 14.6 4.29 441 282 0.16
Minimum 0.54 0.418 1.493 1.079 0.108 0.00947 0.0012 0.275 0.0278 170 14.6 3.5 401 257 0.16
Maximum 1.16 0.807 2.723 1.677 0.147 0.01049 0.0034 1.912 0.2018 199 25.8 4.67 472 302 6.16
Average 0.755 0.6362 2.2717 1.484 0.132 0.01028 0.0023 1.0268 0.1029 182 22.4 3.93 442 283 3.4
Variance 0.02508 0.00763 0.12881 0.01409 9.2E-05 6.61E-08 5.2E-07 0.12669 0.00267 91.2 20.1 0.23 279 116 5.51
 1218 J.C. Cern et al.

Table 3 Correlation matrix (D: depth; T: temperature; EC: electrical conductivity; TDS: total dissolved solids; DO:
dissolved oxygen).
D Fe Cu Zn Mn Cd Ni Sb Pb Al SO4 T pH EC TDS DO

D 1.00
Fe 0.57 1.00
Cu 0.28 0.37 1.00
Zn 0.74 0.82 0.07 1.00
Mn 0.47 0.26 0.44 0.45 1.00
Cd 0.38 0.22 0.10 0.22 0.28 1.00
Ni 0.25 0.31 0.30 0.31 0.18 0.13 1.00
Sb 0.23 0.39 0.01 0.42 0.07 0.05 0.27 1.00
Pb 0.82 0.51 0.26 0.65 0.46 0.36 0.19 0.25 1.00
Al 0.88 0.45 0.25 0.57 0.40 0.42 0.28 0.23 0.66 1.00
SO4 0.38 0.23 0.26 0.49 0.59 0.04 0.05 0.01 0.37 0.22 1.00
T 0.88 0.76 0.05 0.92 0.36 0.31 0.35 0.32 0.75 0.73 0.36 1.00
pH 0.85 0.73 0.04 0.90 0.50 0.37 0.24 0.27 0.72 0.72 0.38 0.97 1.00
EC 0.64 0.25 0.59 0.52 0.86 0.27 0.04 0.12 0.59 0.49 0.60 0.48 0.59 1.00
TDS 0.59 0.24 0.61 0.47 0.84 0.25 0.02 0.07 0.54 0.41 0.60 0.42 0.53 0.98 1.00
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014

DO 0.92 0.66 0.22 0.89 0.61 0.36 0.22 0.29 0.78 0.75 0.51 0.93 0.94 0.75 0.69 1.00

(0.73) and pH (0.72); and for Pb with DO (0.78), T
(0.75) and pH (0.72). Temperature has a high posi-
tive correlation with DO (0.93) and negative correla-
tion with pH (0.97). Finally, sulphate is not
significantly correlated with the other variables.
Before using the multivariate statistical method,
all parameters data were standardized with the corre-
sponding z-score to ensure homogeneity, as follows:
z x  =
where x is the variable value; and and are the
average and the standard deviation of all data,
respectively.
Figures 3 and 4 present the results of factor ana-
lysis. Factors I and II explain 78% of the total data
variance in relation to the studied variables (I: 59%, II:
19%; Fig. 3). Those variables with more weight on the
positive side of Factor I are temperature and Zn, while
pH, Al, depth, Pb and Fe are on the negative side
(Fig. 3). Factor II is defined by EC, TDS, sulphates,
Mn and Cu. DO is in a close to intermediate position in
relation to factors I and II, but affects the former more
(1) than the latter. Finally, the variables Ni, Cd and Sb are
located away from the extremes, so they have no clear
influence on either factor.
In terms of observations (Fig. 4), the following
groups can be distinguished: a first group (G1) con-
sisting of samples 116 (more superficial), a second
group (G2) defined by samples 1720 and a third

Fig. 3 Factor analysisvariables (D: depth from water

surface; C: electrical conductivity; TDS: total dissolved
solids; DO: dissolved oxygen). Fig. 4 Factor analysissamples.
 Hydrochemical characterization of an acid mine drainage-affected reservoir
Fig. 5 Thermal stratification and respective areas in the
Sancho Reservoir.
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014
(G3) consisting of samples 2128. The thermal stra-
tification and its respective areas in the Sancho
Reservoir are shown in Fig. 5.
The evolution in depth of various factors is
shown in Fig. 6. Temperature is almost stable, vary-
ing from around 26C down to 16 m, and decreasing
rapidly at 20 m. From here it continues to fall more
slowly, reaching values of around 15C. The evolu-
tion of pH, as mentioned above, is similar to that of
temperature, being stable down to 15 m. Below this
Fig. 6 Depth vs temperature, pH, electrical conductivity (EC), total dissolved solids (TDS), dissolved oxygen (DO), Al and
sulphate.
Fig. 7 Depth vs Zn, Mn, Fe, Cu, Pb, Ni, Cd and Sb ions.
1219
depth, down to 20 m, there is a sharp increase; pH
tends to stabilize at close to 4.6. EC shows a slow
decline down to 16 m (from 472 to 458 mS cm-1).
From here it decreases until 19 m (401 mS cm-1), and
below that there is a new evolution in depth leading
to increasing values (up to 441 mS cm-1). The TDS
behave similarly. The highest EC and TDS values
were observed at the surface (Fig. 6). DO shows a
slow decrease (between 6 and 5 mg L-1) down to
16 m, then a very rapid decrease down to 17 m
(0.8 mg L-1). Finally, it continues to decline more
slowly towards the deepest point, with values of up
to 0.16 mg L-1. For Al, there is a general increase in
concentration with depth: values increase from the
surface down to 15 m, at which point they begin to
fall irregularly, until there is a new increase towards
the end of the column. In turn, sulphate, which is
most responsible for salinity, shows irregular change
throughout the whole profile. However, similar to
EC, a maximum can be observed at around 15 m
(196 mg L-1), with values falling with depth.
The evolution with depth of other ions is
shown in Fig. 7: Zn concentration increases initi-
ally down to 15 m, falls rapidly at about 20 m, and
then continues to decrease more slowly; Mn
remains at about the same value down to 15 m,
then drops quickly at about 20 m and finally fol-
lows a smooth, continuous rise; Fe fluctuates down
 1220 J.C. Cern et al.
to nearly 20 m, followed quickly by an increase;
Cu shows a decreasing trend until 20 m, then
increases suddenly in the opposite direction; Pb,
like Al, increases with depth; Ni and Cd do not
show large fluctuations in concentration as the
depth increases; and, finally, Sb has very irregular
behaviour without showing a clear tendency
towards an increase or decrease.
DISCUSSION
As the statistical summary reveals, the waters
of the Sancho Reservoir present typical AMD char-
acteristics, i.e. low pH and high concentrations of
metals. However, this pollution is less pronounced
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014
than that in the River Meca, whose waters it col-
lects, due to dilution processes that occur in the
Sancho Reservoir.
According to Wetzel and Wilkin (1991) and
Wetzel (2001), a relative depth index (equation (2))
can be defined for an aquatic environment. This
allows the comparison of different types of lakes
and gives a preview of certain limnology aspects:
p.p lence, than on biological activity. The surface of the
Relative depth 50zm A0 (2)
where zm is the maximum depth and A0 is the surface
area.
Relatively shallow lakes, which present results
of between 3% and 10%, are known as holomictic
lakes. These generally undergo mixing at least once a
year, which affects the entire water column, introdu-
cing oxygen from the surface to the deepest layers. If
the temperature is above 4C, the lake is called warm
monomictic. Lakes with a high relative depth, of
between 10% and 40%, are called meromictic. They
are characterized by a permanent chemical stratifica-
tion, caused by the lack of mixing processes in the
deepest layer.
In the present case, the Sancho Reservoir, with
an area of 4.27 km2 and a maximum depth of 28 m,
would have a low relative depth of 1.2%. As a result,
it could be included in the group of holomictic lakes.
It would show thermal stratification for most of the
year and a complete homogenization of the whole
column in the cold months. Additionally, and taking
into account that its temperature is higher than 4C,
it would also be considered a monomictic lake.
The evolution of temperature over depth (Fig. 5)
describes this type of lake, in which three areas are
distinguished: the epilimnion (the warmest and most
shallow, with temperatures around 25C, and about
15 m thick), the metalimnion or thermocline (where a
sharp drop in temperature is produced, about 10C
and measuring only 5 m), and the hypolimnion (the
deepest, thickest layer, with a nearly constant tem-
perature of around 14.5C).
The fact that the highest values for EC and
TDS were found at the surface could be explained
by evaporation processes and salt concentrations
produced in the most superficial epilimnion layer.
Therefore, the parameters pH, EC, TDS, DO and
temperature reveal a vertical transition zone, which
would be located at a depth of approx. 1520 m.
This defines an area called the metalimnion or ther-
mocline, which separates the epilimnion from the
hypolimnion (Fig. 5). In Fig. 7, it can be seen that
at around 1520 m, corresponding to the metalim-
nion, most of the ions evolve in one direction or the
other.
If we consider temperature and DO (Fig. 6), it
can be seen that the thermocline and oxycline are in
the same position. This suggests that oxygen concen-
tration depends more on mixing, due to wind turbu-
reservoir is quite large (4.27 km2), which would
favour wind action on its waters, leading to an
increase in the depth of the epilimnion (about
15 m). This thicker epilimnion may promote greater
connection with the oxygenated surface layer.
Therefore, deeper areas are not too disconnected
from the oxygenated surface, inhibiting the occur-
rence of reducing conditions.
Additionally, there is an input of nutrients from
the epilimnion. Such nutrients may favour the growth
of algae, increasing the DO. According to Peine and
Peiffer (1998) and Wendt-Potthoff and Neu (1998),
phytoplankton activity leads to an increase in alkali-
nity in lakes and reservoirs. In the Sancho Reservoir,
this may, in part, neutralize the acidity received
from AMD.
In the metalimnion, at a depth of approx.
1520 m, almost all the oxygen is consumed
rapidly in the course of stratification of the profile
(Fig. 6). These anoxic or low DO conditions are
found in the hypolimnion. These reducing condi-
tions are followed by pH increase in the hypolim-
nion, with values of between 4.5 and 5. At this pH
range, reduction and dissolution of Fe(III) phases
may occur (Younger et al. 2002), such as the
oxyhydroxysulphate Schwertmannite:
 Hydrochemical characterization of an acid mine drainage-affected reservoir
Fe8 O8 OHx SO4 y 24  2yH ! 8Fe3
ySO4 2 24  2y x=2H2 O
This mineral has a typical pH formation range of 24
(Bigham et al. 1996, Sidenko and Sherriff 2005),
which would cause an increase in Fe and H + con-
sumption in the hypolimnion (equation (3)). This is
in agreement with Snchez-Espaa et al. (2009), who
consider Schwertmannite a major controller of Fe(III)
concentrations in the mine waters of the IPB.
Furthermore, a pH increase noticed in the hypo-
limnion may be related to sulphate reduction under
anaerobic conditions. This process occurs in the bottom
of the reservoir, and is related to the organic matter that
has accumulated in the sediment (Drever 1997):
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014
2CH2 Oaq SO4 2
aq 2H aq ! H2 Saq
CO2 H2 O
It may cause alkalinity (Drever 1997, Heijs and van
Gemerden 2000) and is in agreement with the
observed decrease in sulphates and increase in EC.
In AMD systems, sulphate reduction to sulphide
occurs at a pH of between 2 and 3 (Koschorreck
et al. 2003). Nevertheless, Church et al. (2007) show
sulphate reduction at a pH of between 4.0 and 7.5
when catalysed by anaerobic bacteria.
Additionally, the anoxic conditions in the hypo-
limnion are associated with an increase in Fe and Mn
concentrations in this zone (Fig. 7). Wetzel (2001)
has described a reduction in metal compounds
according to the following equations:
CH2 O 4FeOH3 8H ! Fe2
CO2 11 H2 O
2CH2 O 2MnO2
4H 2Mn2 CO2 H2 O
This oxidation of organic matter may contribute to
the increase in EC and dissolved solids observed in
the deeper layer. In turn, and according to Peiffer
et al. (1999) and Tipping et al. (2002), Fe and Mn
increases should be enhanced by the formation of
stable humic complexes. Besides these two metals,
metallic load increase in the hypolimnion is also
evident for Cu, Pb and Al. In the case of Cd, Ni
and Sb, with smaller concentrations than those
reported above (g L-1), the changes are smaller.
1221
These increases may be related to an iron particulate
(3) dissolution process that promotes the release of other
adsorbed metals.
The only metal that does not follow the above
tendency is Zn. Its decreasing concentration seems to
be directly controlled by pH, as indicated by the
high correlation coefficient between both variables
(0.90). One possible explanation could be that it
was adsorbed by clay, organic matter or aluminium
hydroxides when pH increased.
Additionally, and as can be seen above, factor
analysis shows the geochemical affinities between
the two sets of variables (Fig. 3), defined according
to factors I (59%) and II (19%). These groups may be
related to the following processes: sulphate reduction
(F1) and salinity (F2). Since the Sancho Reservoir
receives major contributions from AMD (Nordstrom
and Alpers 1999, Younger et al. 2002, Lpez-Pamo
(4) et al. 2009), its hydrochemistry is mainly determined
by sulphide oxidation processes. The sulphate reduc-
tion process (F1) may take place in the deepest parts of
the reservoir that are depleted of oxygen. Therefore,
the major controlled variables are DO and temperature
(the positive side), and depth, pH, Al, Pb and Fe (the
negative side). The proximity between pH and Al
suggests that pH is related to precipitation of this ion.
The process has already been described in the IPB by
Lpez-Pamo et al. (2009) and Santofimia-Pastor et al.
(2011), who indicate that this ion may cause a buffer
effect, precipitating and increasing H+ concentration.
In terms of salinity (F2), ion sulphate dissolution
(coming from pyrite oxidation) may be the main
variable responsible for an increase in EC and TDS.
This process may occur in the shallower areas of the
reservoir, which are richer in oxygen.
The groups observed in Fig. 4 also satisfy these
(5)
two processes: group G1 brings together the shal-
lower conditions (down to 16 m), which are more
oxygenated, with more salinity (this high sulphate
(6) concentration and lower pH define the epilimnion);
G2 corresponds to conditions in the intermediate
zone (between 17 and 20 m) and defines the meta-
limnion; and G3 brings together the deepest condi-
tions, the hypolimnion, with higher pH and lower
oxygen, salinity and sulphate concentration.
CONCLUSIONS
The hydrogeochemical study of the Sancho Reservoir
has shown that the dilution effect is not sufficient to
neutralize AMD contributions from the mining activ-
ity in the River Meca basin. This is revealed by the
 1222 J.C. Cern et al.
high average sulphate levels, high EC and low pH. In
terms of metallic charge, the high concentrations of
Fe, Mn, Zn, Pb and Cu, among others, stand out.
Sampling carried out from the surface water to
the deepest layers reveals the stratification of the
reservoir, allowing it to be included in the group of
monomictic and holomitic lakes. Therefore, and tak-
ing temperature into account, the epilimnion can be
identified from the surface down to 15 m; the meta-
limnion at 1621 m below the surface; and the hypo-
limnion at 2128 m below the surface. This
stratification also responds to EC, TDS, DO and pH.
The reservoir shows a more oxygenated upper
part (mainly because of wind turbulence), defining
the eplimnion. This extends to the upper part of the
metalimnion (possibly due to the contribution of
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014
nutrients from the epilimnion). Conversely, in the
deeper areas of the hypolimnion, anoxic conditions
or low concentrations of DO are found. The pH
increases with depth, being higher in the hypolim-
nion, where oxygen shortage favours highly reducing
conditions. In turn, there is sulphate reduction from
the organic matter, which may increase alkalinity, as
shown by a decrease in sulphates and an increase
in EC.
Most of the metal ions increase in the hypolim-
nion. This is most evident for Fe, Mn, Cu, Pb and Al.
Such an increase may be due to Fe particulate dis-
solution, together with the release of other metals
adsorbed on the precipitates. But, there is a decrease
in Zn concentration, which could be adsorbed by
clays, organic matter or aluminium hydroxides.
The statistical treatment, by factor analysis, also
revealed the stratification of the reservoir. In addition,
it demonstrated the hydrogeochemical affinities
related to sulphate reduction processes (F1) and sali-
nity (F2). Factor 1 reflects hypolimnion conditions,
more depleted in oxygen; while F2 may be related to
the epilimnion, with ion sulphate being the main
variable responsible.
These conclusions match those of a preliminary
study (Sarmiento et al., 2009); the information may
be used to establish risk evaluation criteria and to
design future remediation strategies, which could be
useful in the design of new dams.
Funding This study is a contribution to the projects
(CICYT-REN2002-1,897/HID, CICYT-TIN2004-
6,689-C03-03 and DGCICYT-CGL2010-21,268-C02-
01) financed by the Spanish Ministry of Education and
Science; and the Andalusian Autonomous Government
Excellence Projects (project P06-RNM-2,167).
REFERENCES
Aroba, J., et al., 2007. Application of fuzzy logic and data mining
techniques as tools for qualitative interpretation of acid mine
drainage processes. Environmental Geology, 53 (1), 135145.
doi:10.1007/s00254-006-0627-0.
Azcue, J.M., 1999. Environmental impacts of mining activities.
Berlin: Springer.
Banks, D., 2004. Geochemical processes controlling minewater pollu-
tion. In: G. Prokop, P. Younger, and K.E. Roehl, eds.
Groundwater management in mining areas. Proceedings of the
2nd IMAGE-TRAIN Advanced Study Course. Vienna, 1744.
Bigham, J.M., et al., 1996. Schwertmannite and the chemical modeling
of iron in acid sulfate waters. Geochimica Et Cosmochimica Acta,
60, 21112121. doi:10.1016/0016-7037(96)00091-9.
Borrego, J., et al., 2002. Geochemical characteristics of heavy metal
pollution in surface sediments of the Tinto and Odiel river
estuary (southwestern Spain). Environmental Geology, 41,
785796. doi:10.1007/s00254-001-0445-3.
Cnovas, C.R., et al., 2007. Hydrogeochemical characteristics of
the Tinto and Odiel rivers (SW Spain). Factors Controlling
Metal Contents. Science of the Total Environment, 373,
363382.
Carro, B., et al., 2011. Impact of acid mine drainage on the hydro-
chemical characteristics of the Tinto-Odiel estuary (SW Spain).
Journal of Iberian Geology, 37 (1), 8796.
Church, C.D., et al., 2007. Microbial sulfate reduction and metal
attenuation in pH 4 acid mine water. Geochemical
Transactions, 8, 10. doi:10.1186/1467-4866-8-10.
Davis Jr, R.A., et al., 2000. Rio Tinto estuary (Spain): 5000 years
of pollution. Environmental Geology, 39, 11071116.
doi:10.1007/s002549900096.
de la Torre, M.L., et al., 2009. Time evolution of an AMD-affected
river chemical makeup. Water Resources Management, 23 (7),
12751289. doi:10.1007/s11269-008-9326-9.
de la Torre, M.L., et al., 2010. Relationships between pH, colour and
heavy metal concentrations in the Tinto and Odiel rivers
(southwest Spain). Hydrology Research, 41 (5), 406413.
doi:10.2166/nh.2010.082.
de la Torre, M.L., et al., 2011. Characterization of AMD pollution in
the river Tinto (SW Spain). Geochemical comparison between
generating source and receiving environment. Water Air and
Soil Pollution, 216, 319. doi:10.1007/s11270-010-0510-1.
Drever, J.I., 1997. The geochemistry of natural waters. Surface and
groundwater environments. Upper Saddle River, NJ: Prentice
Hall, 436pp.
Elbaz-Poulichet, F., et al., 1999. Trace metal and nutrient distribution
in an extremely low pH (2.5) river-estuarine system, the Ria of
Huelva (south-west Spain). Science of the Total Environment,
227, 7383. doi:10.1016/S0048-9697(99)00006-6.
Elbaz-Poulichet, F., et al., 2000. Influence of sorption processes by
iron oxides and algae fixation on arsenic and phosphate cycle
in an acidic estuary (Tinto River, Spain). Water Research, 34,
32223230. doi:10.1016/S0043-1354(00)00073-7.
Elbaz-Poulichet, F., et al., 2001. Metal biogeochemistry in the Tinto-
Odiel rivers (Southern Spain) and in the Gulf of Cadiz: a synthesis
of the results of TOROS project. Continental Shelf Research, 21,
19611973. doi:10.1016/S0278-4343(01)00037-1.
Grande, J.A., 2011. Impact of AMD processes on the public water
supply: hydrochemical variations and application of a classifica-
tion model to a river in the Iberian Pyritic Belt S.W. Spain.
 Hydrochemical characterization of an acid mine drainage-affected reservoir
Hydrology Research, 42 (6), 472478. doi:10.2166/
nh.2011.159.
Grande, J.A., et al., 2003a. A description of how metal pollution
occurs in the TintoOdiel rias (Huelva-Spain) through the
application of cluster analysis. Marine Pollution Bulletin, 46,
475480. doi:10.1016/S0025-326X(02)00452-6.
Grande, J.A., et al., 2003b. Application of cluster analysis to
the geochemistry zonation of the estuary waters in the Tinto
and Odiel rivers (Huelva, Spain). Environmental Geochemistry
and Health, 25, 233246. doi:10.1023/A:1023217318890.
Grande, J.A., et al., 2005a. Acid mine drainage and acid rock
drainage processes in the environment of Herreras Mine
(Iberian Pyrite Belt, Huelva-Spain) and impact on the
Andevalo dam. Environmental Geology, 47, 185196.
doi:10.1007/s00254-004-1142-9.
Grande, J.A., et al., 2005b. Precipitation, pH and metal load in AMD
river basins: an application of fuzzy clustering algorithms to
the process characterization. Journal of Environmental
Monitoring, 7, 325334. doi:10.1039/b410795k.
Grande, J.A., et al., 2010a. Overall hydrochemical characterization
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014
of the Iberian Pyrite Belt. Main acid mine drainage-generating
sources (Huelva, SW Spain). Journal of Hydrology, 390,
123130. doi:10.1016/j.jhydrol.2010.06.001.
Grande, J.A., et al., 2010b. Fuzzy modeling of the spatial evolution
of the chemistry in the Tinto River (SW Spain). Water
Resources Management, 24, 32193235. doi:10.1007/s11269-
010-9603-2.
Grande, J.A., et al., 2010c. Presence of As in the fluvial network
due to AMD processes in the Riotinto mining area (SW Spain):
a fuzzy logic qualitative model. Journal of Hazardous
Materials, 176 (13), 395401. doi:10.1016/j.jhazmat.2009.
11.043.
Grande, J.A., et al., 2010d. Quantification of heavy metals from A.
M.D. Discharged into a public water supply dam in the Iberian
Pyrite Belt (SW Spain) using centered moving average. Water
Air and Soil Pollution, 212, 299307. doi:10.1007/s11270-
010-0343-y.
Grande, J.A., et al., 2010e. Relationships between conductivity and
pH in channels exposed to acid mine drainage processes: study
of a large mass of data using classical statistics. Water
Resources Management, 24, 45794587. doi:10.1007/s11269-
010-9680-2.
Grande, J.A., et al., 2011a. Tinto versus Odiel: Two AMD pol-
luted rivers and an unresolved issue. An artificial intelli-
gence approach. Water Resources Management, 25,
35753594.
Grande, J.A., et al., 2011b. Arsenic speciation in the Riotinto mining
area (SW Spain) during a hydrological year. Water Practice
and Technology, 6 (1) doi:10.2166/WPT.2011.011.
Heijs, S.K. and van Gemerden, H., 2000. Microbiological and environ-
mental variables involved in the sulfide buffering capacity
along eutrophication gradient in a coastal lagoon (Basin
dArcachon, France). Hydrobiologia, 437, 121131. doi:10.
1023/A:1026590520603.
Jimnez, A., et al., 2009. Model of behaviour of conductivity
versus pH in acid mine drainage water, based on fuzzy
logic and data mining techniques. Journal of
Hydroinformatics, 11 (2), 147153. doi:10.2166/hydro.
2009.015.
Koschorreck, M., Wendt-Potthoff, K., and Geller, W., 2003.
Microbial sulfate reduction at low pH in sediments of an acidic
lake in Argentina. Environmental Science and Technology, 37,
11591162. doi:10.1021/es0259584.
Leblanc, M., et al., 2000. 4.500 year-old mining pollution in
Southwestern Spain: long-term implications for modern mining
pollution. Economic Geology, 95, 655662.
1223
Lpez-Pamo, E., et al., 2009. Cortas mineras inundadas de la Faja
Pirtica Ibrica: inventario e hidroqumica. Instituto geolgico
y Minero de Espaa. Serie: medio Ambiente. Nmero, 13 (in
Spanish).
Moreno, C. and Gonzlez, F., 2004. Estratigrafa de la Zona
Surportuguesa. In: J.A. Vera, ed. Geologa de Espaa.
Madrid: SGE-IGME, 201205 (in Spanish).
Moreno, C. and Sez, R., 1990. Sedimentacin marina somera en el
Anticlinorio de Puebla de Guzmn. Geogaceta, 8, 6264
(in Spanish).
Nordstrom, D.K. and Alpers, C.N., 1999. Geochemistry of acid mine
waters. In: G.S. Plumlee and M.J. Logson, eds. The environ-
mental geochemistry of mineral deposits. Reviews in Economic
Geology, vol. 6A. Littleton: Society of Economic Geologists,
133160.
Olas, M., et al., 2004. Seasonal water quality variations in a river
affected by Acid Mine Drainage: The Odiel River (South West
Spain). Science of the Total Environment, 333, 267281.
doi:10.1016/j.scitotenv.2004.05.012.
Olias, M., et al., 2005a. Distribution of rare earth elements in an
alluvial aquifer affected by acid mine drainage: the Guadiamar
aquifer (SW Spain). Environmental Pollution, 135, 5364.
doi:10.1016/j.envpol.2004.10.014.
Olas, M., et al., 2005b. State of contamination of the waters in the
Guadiamar valley five years after the Aznalcllar spill. Water
Air and Soil Pollution, 166, 103119. doi:10.1007/s11270-
005-8201-z.
Olas, M., et al., 2006. Water quality of the Guadiamar River after
the Aznalcllar spill (SW Spain). Chemosphere, 62, 213225.
doi:10.1016/j.chemosphere.2005.05.015.
Peiffer, S., Walton-Day, K., and Macalady, D.L., 1999. The
interaction of natural organic matter with iron in a wetland
(Tennessee Park, Colorado) receiving acid mine
drainage. Aquatic Geochemistry, 5, 207223. doi:10.1023/
A:1009617925959.
Peine, A. and Peiffer, S., 1998. In-lake neutralization of acid
mine lakes. In: W. Geller, H. Klapper, and W. Salomons,
eds. Acidic mining lakes: acid mine drainage, limnology and
reclamation. Berlin: Springer Verlag, 4763.
Pinedo-Vara, I., 1963. Piritas de Huelva. Su historia, minera y
aprovechamiento. Madrid: Summa.
Sarmiento, M., et al., 2009. Natural attenuation processes in two
water reservoirs receiving acid mine drainage. Science of the
Total Environment, 407 (2009), 20512062.
Sez, R. and Moreno, C., 1997. Geology of the Puebla de Guzmn
anticlinorium. In: F. Barroga and Carvalho, eds. Geology
and VMS deposits of the Iberian Pyrite belt. Littleton, CO:
Society of Economic Geologists, Guidebook Series, 27,
131136.
Sez, R., et al., 1999. The Iberian type of volcanosedimentary
massive sulphide deposits. Mineralium Deposita, 34, 549570.
Sez, R., et al., 2010. Black shales and massive sulfides: causal or
casual relationships? Insights from Rammelsberg, Tharsis, and
Draa Sfar. Mineralium Deposita, 130. doi:10.1007/S00126-
010-0311-X.
Sinz, A., 1999. Estudio de la contaminacin qumica de origen minero
en el ro Odiel. Thesis (PhD). University of Huelva.
Sinz, A., Grande, J.A., and de la Torre, M.L., 2003a. Analysis of the
impact of local corrective measures on the input of contami-
nants from the Odiel river to the Ria of Huelva (Spain). Water
Air and Soil Pollution, 144, 375389. doi:10.1023/
A:1022905502320.
Sinz, A., Grande, J.A., and de la Torre, M.L., 2003b. Odiel river,
acid mine drainage and current characterisation by means of
univariate analysis. Environment International, 29, 5159.
doi:10.1016/S0160-4120(03)00006-0.
 1224 J.C. Cern et al.
Sinz, A., Grande, J.A., and de la Torre, M.L., 2004. Characterisation
of heavy metal discharge into the Ria of Huelva.
Environment International, 30, 557566. doi:10.1016/j.envint.
2003.10.013.
Sinz, A., Grande, J.A., and de la Torre, M.L., 2005. Application
of a systemic approach to the study of pollution of the
Tinto and Odiel rivers (Spain). Environmental Monitoring
and Assessment, 102, 435445. doi:10.1007/s10661-005-
6396-5.
Sainz, A. and Ruiz, F., 2006. Influence of the very polluted
inputs of the TintoOdiel system on the adjacent littoral
sediments of southwestern Spain: a statistical approach.
Chemosphere, 62, 16121622. doi:10.1016/j.chemosphere.
2005.06.045.
Sinz, A., et al., 2002. Characterisation of sequential leachate dis-
charges of mining waste rock dumps in the Tinto and Odiel
rivers. Journal of Environmental Management, 64 (4),
345353. doi:10.1006/jema.2001.0497.
Snchez-Espaa, J., et al., 2009. Physico-chemical gradients
and meromictic stratification in Cueva de la Mora and
Downloaded by [Universitaria De Huelva] at 05:55 11 June 2014
other acidic pit lakes of the Iberian Pyrite Belt. Mine Water
and the Environment, 28, 1529. doi:10.1007/s10230-008-
0059-z.
Santofimia-Pastor, E., Lpez-Pamo, E., and Montero-Gonzlez, E.,
2011. La corta inundada de Aznalcllar y su uso como verte-
dero de residuos mineros (Sevilla, Espaa). Boletn Geolgico
Y Minero, 122 (2), 235246.
The author has requested enhancement of the downloaded file. All in-text references underlined in blue are linked to publications on ResearchGate.
Sidenko, N.V. and Sherriff, B.L., 2005. The attenuation of Ni, Zn,
and Cu, by secondary Fe phases of different crystallinity from
surface and ground water of two sulfide mine tailings in
Manitoba, Canada. Applied Geochemistry, 20, 11801194.
doi:10.1016/j.apgeochem.2005.01.012.
Singer, P.C. and Stumm, W., 1970. Acidic mine drainage: the rate-
determining step. Science, 167, 11211123. doi:10.1126/
science.167.3921.1121.
Tipping, E., et al., 2002. Al(iii) and Fe(iii) binding by humic sub-
stances in freshwaters, and implications for trace metal specia-
tion. Geochimica Et Cosmochimica Acta, 66, 32113224.
doi:10.1016/S0016-7037(02)00930-4.
Valente, T. and Leal Gomes, C., 2009. Occurrence, properties and
pollution potential of environmental minerals in acid mine
drainage. Science of the Total Environment, 407, 11351152.
doi:10.1016/j.scitotenv.2008.09.050.
Wendt-Potthoff, K. and Neu, T.R., 1998. In-lake neutralization of
acid mine lakes. In: W. Geller, H. Klapper, and W. Salomons,
eds. Acidic mining lakes: acid mine drainage, limnology and
reclamation. Berlin: Springer, 269284.
Wetzel, D.B., 2001. Limnology: lake and river ecosystems. 3rd ed.
San Diego, CA: Academic Press, 1006.
Wetzel, R.G. and Wilkin, R.T., 1991. Limnological analysis. New York:
Springer-Verlag, 391pp. ISBN 0-387-97331-1.
Younger, P.L., Banwart, S.A., and Hedin, R.S., 2002. Mine water:
hydrology, pollution, remediation. Dordrecht: Kluwer
Academic, 464pp.