Environ Earth Sci (2010) 60:121–138
DOI 10.1007/s12665-009-0174-6
ORIGINAL ARTICLE
Arsenic and metal mobility from Au mine tailings
in Rodalquilar (Almerı́a, SE Spain)
Andrés Navarro Flores Æ
Luis Miguel Doménech Rubio
Received: 27 May 2008 / Accepted: 21 April 2009 / Published online: 9 May 2009

Springer-Verlag 2009
Abstract In the old mining area of Rodalquilar, mine
wastes, soil and sediments were characterized and the
results revealed high concentration of Au, Ag, As, Bi,
Cu, Fe, Mn, Pb, Se, Sb and Zn in tailings and sediments.
The contaminant of greatest environmental concern is
As. The mean concentration in the tailings was 679.9,
and 345 mg/kg in the sediments of Playazo creek. The
groundwater samples from the alluvial aquifer showed
high concentration of Al, As, Cd, Fe, Hg, Mn, Ni, Pb,
Se, Sb and Zn and very high concentration of chloride
and sulfate, which were above the concentration defined
in the European standards for drinking water. The pres-
ence of As in groundwater may be caused by the oxi-
dation of arsenian pyrite, the possible As desorption
from goethite and ferrihydrite and the jarosite dissolu-
tion. Groundwater concentrations of Cd, Fe, Mn, and
possibly Cu, were associated with low values of Eh,
indicating the possible dissolution of oxy-hydroxides of
Fe and Mn. The mobility of metals in the column
experiments show the release of Al, Fe, Mn, Cr, Cu, Ni,
V and Zn in significant concentrations but below the
detected values in groundwater. However, As, Cd, Sb, Se
Pb and Au, are generally mobilized in concentrations
above the detected values in groundwater. The possible
mass transfer processes that could explain the presence
of the contaminants in the aquifer and the leachates was
simulated with the PHREEQC numerical code and
revealed the possible dissolution of the following mineral
A. Navarro Flores (&)
L. M. Doménech Rubio
Departamento M. Fluidos, ETSEIAT,
Universidad Politécnica de Cataluña (UPC),
Colón 7, 08222 Terrassa, Spain
e-mail: navarro@mf.upc.edu
phases: jarosite, natrojarosite, arsenian pyrite, alunite,
chlorite, kaolinite and calcite.
Keywords Mine tailings
Arsenic
Groundwater

Metals
PHREEQC
Introduction
In SE Spain, the mining of base metals and Au–Ag, mainly
during the nineteenth century, generated huge quantities of
mine wastes such as tailings, mine-waste calcines, heap
leach impoundments and smelting slags. These wastes
were abandoned at hundreds of mine sites and, because of
the oxidation process of pyrite and other sulfide minerals,
they represent a potential threat to the environment (Wray
1998; Viladevall et al. 1999; Navarro et al. 2000, 2004,
2006, 2008; Robles-Arenas et al. 2006; Navarro and
Cardellach 2008).
The problems associated with unremediated mine sites
containing sulfide minerals included the liberation of
metals (Al, Cd, Cu, Fe, Hg, Mn, Ni, Pb and Zn) and
metalloids (As, Sb, Se and V) and occasionally the
generation of acid mine drainage (AMD). However, if
the climatic conditions do not favor the generation of
AMD, as in semi-arid environments, the flow rate of
acidic waters may be negligible, or it might happen only
during ephemeral wet periods. These episodes may be
associated with the generation of efflorescent salts
(Blowes and Ptacek 1994; Jambor et al. 2000; Dold and
Fontboté 2001, 2002; Lottermoser 2003; Ashley et al.
2004; Blowes et al. 2003, 2004; Romero et al. 2006,
2007; Smuda et al. 2007).
Thus, soluble metal sulfate salts may play a key role in
the generation of acid mine drainage in epithermal deposits
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such as Summitville (Plumlee et al. 1999), in which jaro-
site, halotrichite and other sulfates were identified. The
mine waters draining these high-sulfidation (HS) deposits
and/or mine waste dumps can contain very high concen-
trations of Al, As, REE, Co, Ni, Cr, U, Th and Be, due to
low pH. However, adit waters collected in dry periods or
water draining propylitically altered rocks may contain
lower metal concentrations and near neutral pH values
(Plumlee et al. 1999).
In exploited epithermal high-sulfidation deposits such as
Rodalquilar, mineralization is characterized by the geo-
chemical association Au–Ag–Cu–As–Bi–Te–Sn (Seal and
Hammarstrom 2003). These are elements that can be
mobilized in the soil, sediments, groundwater, and surface
waters. The effluents and leachates from these mine sites
can have pH levels between 2.0 and 8.9, Fe concentrations
between 0.01 and 50,000 mg/L, an Al concentration
between 0.001 and 5000 mg/L, and sulfate concentrations
from 0.8 to 100,000 mg/L. Furthermore, significant con-
centration of Cu, Zn, Co, Ni, Cd and As are not uncommon
(Seal and Hammarstrom 2003).
In similar situations, the migration of contaminants such
as As, Cu, Zn, Pb and Cd is controlled by the presence of
secondary phases. In the case of As these secondary phases
may be amorphous Fe-sulfoarsenates, jarosite–beudantite
(Gieré et al. 2003), schwertmannite (Fukushi et al. 2003) or
Fe oxyhydroxides (Sracek et al. 2004; Courtin-Nomade et al.
2005). Moreover, during dry periods the weathering of As-
bearing sulfides may produce secondary Fe oxyhydroxides
(goethite, ferrihydrite) and sulfates (jarosite), which are
efficient scavengers of As oxyanions (Savage et al. 2000).
The objectives of this study are the following:
• To determine the geochemical features of the environ-
mental impact of the abandoned tailings in the
Rodalquilar mining area.
• To determine the extension of the main contaminants
around the waste deposits, in sediments and in
groundwater.
• To define the geochemical processes controlling the
mobilization of contaminants, especially As, from the
main waste impoundment to the groundwater.
• To analyze the solid-phase controls on the mobility of
main metals, by a mineralogical study of the tailings
and mine waste samples.
• To evaluate the potential mass transfer between the
mine wastes and the groundwater, analyzing the
experimental data (column experiments) and interpret-
ing these results using the numerical code PHREEQC.
These objectives are based on the situation of the
abandoned mine tailings located at the head of Playazo
creek network. The Playazo creek network meets the
Mediterranean Sea 4 km downstream.
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Environ Earth Sci (2010) 60:121–138
Site description
The old mining district of Rodalquilar is located in the
Sierra del Cabo de Gata (Fig. 1) at an altitude of 0–300 m
above sea level in a semi-arid region 40 km east of the city
of Almerı́a. The main Rodalquilar deposit is the first doc-
umented example of caldera-related epithermal Au min-
eralization in Europe (Hernández et al. 1989; Sänger-von
Oepen and Friedrich 1991; Arribas et al. 1995). Mining in
this region started in the nineteenth century with the
exploitation of the Pb–Zn–Ag (Au) epithermal veins of San
José, 10 km south of the study area. The exploitation of
low-sulfidation epithermal veins at Rodalquilar (Las Niñas)
began towards the end of the nineteenth century.
The main period of exploitation took place between
1943 and 1966 by the Spanish government’s company
ADARO, which operated in the Cerro Cinto area by open
pit and in some of the low-sulfidation epithermal veins
(Consulta, Ma Josefa, Triunfo, Las Niñas, Ronda and
Resto, etc.) by underground mining. During this period, the
main tailing dump was created as a result of the ore cy-
anidation treatment at the Denver plant. This led to an
uncontrolled impoundment of waste over an area of
approximately 50 ha. The most recent mining operation
was carried out by St. Joe-Transacción between 1989 and
1991, using a heap leaching facility near the Cerro Cinto
open pit. At present (2008) there is no mining activity; the
area is now part of the Cabo de Gata national park.
Regional geology and ore deposits
The high- and low-sulfidation deposits of Rodalquilar are
associated with Miocene calc-alkalic volcanic rocks of the
Almerı́a–Cartagena volcanic belt. The volcanic rocks in the
Rodalquilar district comprise pyroxene and hornblende
andesites, ash-flow tuffs, postmineralization pyroxene
andesite flows, and flow breccias (Fig. 1). In the eastern
margin of the Rodalquilar caldera there is an alluvial–
colluvial quaternary system that ends at the Mediterranean
Sea.
The ore deposits consist of low-sulfidation Pb–Zn–Ag
(Au) quartz veins along the north–south-trending faults and
high-sulfidation Au–(Cu–Te–Sn) ores that are enclosed in
areas of acid sulfate alteration (Sänger-von Oepen et al.
1990; Arribas et al. 1995). These high-sulfidation ores are
found in the shallowest parts of the central core of
hydrothermal activity (about 10.4 Ma) and are associated
with silicified rocks, found at depths of 100–300 m. They
occur in advanced argillic zones (quartz–alunite–jarosite)
surrounding the cores of vuggy silica and enclosing most of
the Au deposits (Arribas et al. 1995). The majority of
primary Au mineralization (high sulfidation) is composed
of chalcedonic quartz veins (elemental Au and pyrite-rich
Environ Earth Sci (2010) 60:121–138
Fig. 1 a Synthetic geological map of Rodalquilar area. E faults, MV
tertiary volcanics, MA miocene limestones, marls and conglomerates,
Q recent fluvial terraces. Modified from Arribas (1993). b Location of
Au) and hydrothermal breccias with high Te and Sn con-
centration, as well as secondary Au associated with Fe
oxides, scorodite and jarosite.
Mine wastes
Ore cyanidation treatment during the periods 1930–1936
and 1943–1966 led to a period of uncontrolled tailing
dumping close to the town of Rodalquilar. This became the
main mine waste impoundment, and during these periods
the amount of waste was evaluated at 1,500,000 t
(Hernández 2002). The tailings were deposited above the
unconfined aquifer of Playazo creek and consisted of sev-
eral terraces with a thickness of up to 10 m. They are
typically red and composed of fine particles derived from
grinding to a size of \ 63 lm (Wray 1998). The mechan-
ical dispersion of fine particles by rainwater runoff and
wind has transported the contaminant particles to Playazo
creek and the houses in the town of Rodalquilar.
A geochemical study by Wray (1998) revealed that the
dominant mineralogy of tailings is quartz, kaolinite, alunite
and jarosite. The study also demonstrated that Mo, Sb, Te,
Bi and As are found at elevated concentrations in stream
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sediment, soil and tailing samples. c Groundwater and superficial
water samples (Tables 6, 7). W16 and W17 surface water of lagoons,
W15 sea water
sediments. High concentration of Cu, Pb and Zn have also
been reported. An analysis by Moreno et al. (2007) of fine
particles (\ 10 lm) by X-ray diffraction and SEM showed
that the fine fraction is dominated by silica, Al–Si clay,
alunite, jarosite and oxidized iron minerals associated with
high concentration of As. Preliminary results of the envi-
ronmental impact of the Rodalquilar tailings were reported
by Navarro et al. (2007).
Climate and hydrology
The climate in the Cabo de Gata region is characterized by
average rainfall of 175–250 mm/year, the lowest in the
Iberian Peninsula, most of which occurs between October
and March. The average annual temperature is between 15
and 22C. The main body of water in this area is Playazo
creek, which because of the semi-arid climate is a non-
permanent fluvial stream. Rainfall events are often sporadic
and may mobilize the contaminants of the tailings in two
ways: by surface runoff at the waste dump slopes and by
infiltration and subsequent leaching of the waste dumps.
The alluvial aquifer of Playazo creek shows a thickness
of 8–20 m, and the grain size of the deposits vary between
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fine sand, gravel and boulders. Also, there is a semi-con-
fined aquifer, which may be associated with the presence of
a geothermal system of low enthalpy. The alluvial mate-
rials include quartz, calcite, aragonite, albite, dolomite,
spinel and shcherbakovite [NaK(Ba,K)Ti2(Si2Ox]2 as the
dominant mineral phases. The upper alluvial aquifer is
enclosed at depth both laterally and partially by volcanic
impermeable materials (Fig. 1). The alluvial aquifer is
composed of materials derived from the surrounding bed-
rock and contains fragments of andesites and ignimbrites,
occupying a width of 0.5–2 km and a length of 4 km,
approximately.
The transmissivity of the aquifer, calculated from
pumping tests and using the equation of Logan (Logan
1964), was estimated to be between 6 and 10 m2/day. The
water table is located 9–14 m below the ground and an
average Darcy velocity of 0.021 m/day was calculated
using an average hydraulic conductivity of 1.75 m/day and
a hydraulic gradient of 0.012. Assuming the porosity of the
alluvial materials to be 0.10, the mean pore water velocity
can be estimated as 0.21 m/day. In the groundwater sys-
tem, the main recharge input is precipitation and surface
water that may recharge the aquifer from Playazo creek
during wet periods. The aquifer flows into the Mediterra-
nean Sea at Playazo beach (Fig. 1).
Methods
Sampling and analyses of sediments, tailings and soils
The mineralization, mine wastes and soils were manually
extracted to obtain samples of approximately 1.5 kg. These
samples comprised 12 samples of outcropping minerali-
zation and mining wastes, and 32 samples of sediments,
tailings and soils (Fig. 1). The mining wastes (host-rock
and low grade stockpiles) had been deposited around the
main mining works and the mine tailings were located near
the town of Rodalquilar (Fig. 1). Mining wastes, mineral-
ization, tailings, sediments and soil samples were passed
through a jaw crusher to a particle size of 10 mesh, quar-
tered, pulverized in an agate mortar, rehomogenized and
repacked in plastic bags. Au, Ag, As, Ba, Br, Ca, Ce, Co,
Cr, Cs, Eu, Fe, Hf, Hg, Ir, La, Lu, Na, Ni, Nd, Rb, Sb, Sc,
Se, Sm, Sn, Sr, Ta, Th, Tb, U, W, Y and Yb were quan-
titatively analyzed by instrumental neutron activation
analysis (INAA), which involves bombarding the unaltered
samples with neutrons. Mo, Cu, Pb, Zn, Ag, Ni, Mn, Sr,
Cd, Bi, V, Ca, P, Mg, Tl, Al, K, Y and Be were analyzed by
ICP-OES. These analyses used a ‘‘near total’’ digestion
employing HF, HClO4, HNO3, and HCl to get as much of
the sample into solution and the resulting metals are
determined by ICP-OES at Actlabs (Ontario, Canada).
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Environ Earth Sci (2010) 60:121–138
Mineralogical determinations
Mine waste, mineralization, sediments and soil samples
were studied using binocular microscopy, transmitted and
reflected light microscopy and X-ray diffraction (XRD)
using a Bragg–Brentano PANalytical X’Pert PRO Alpha 1
geometry diffractometer (radius = 240 mm). Also, the
microtextures of any thin sections were examined using a
scanning electron microscope. These techniques enabled us
to identify the mineral phases and later analyze the major
and trace element concentration of the most abundant
minerals.
Sampling and analyses of groundwater
Eighteen surface water and groundwater samples (Fig. 1)
were collected from lagoons, mine shafts and agricultural
wells (August 2004), the depths of which ranged between 6
and 38 m, from a saturated zone of variable thickness.
The pH, redox potential [Eh (mV)], temperature and
electrical conductivity [EC (lS/cm)] were corrected using
standard solutions and measured in situ with portable
devices (HACH model sensION TM378). The groundwater
and leachate samples were filtered with a cellulose nitrate
membrane with a pore size of 0.45 lm. The samples for
cation analysis were later acidified to pH \ 2.0 by adding
ultrapure HNO3. The samples were collected in 110-ml
high-density polypropylene bottles, sealed with a double
cap and stored in a refrigerator until analysis. The
groundwater samples were obtained after purging each
well, using a bailer sampler and the submersible pumps of
agricultural wells.
The metal concentrations were measured with ICP using
ICP-MS at the ACTLABS laboratories. The concentrations
of chloride, nitrate and sulfate (in a second, untreated
sample) were analyzed by ion chromatography. The alka-
linity of the waters was analyzed by titration. Standard
reference material NIST 1640 (ICP-MS) was used to
confirm accuracy.
Leaching experiments
In order to study the metal mobilization processes from
tailing material, two column experiments were conducted
with tailings, using low mineralized water and acidic
mineralized water with a mean pH value of 1.0. In this
way, under controlled laboratory conditions, it was possible
to eliminate unknown influences that may have affected the
geochemical evolution of the pore water and thus obtain
geochemical samples of pore water (Jurjovec et al. 2002).
The column experiment with low-mineralized water was
conducted to represent an approximation of the rain water
effect over the tailing impoundments, and also to analyze
Environ Earth Sci (2010) 60:121–138 125

the geochemical nature of leachates in environmental of albite, illite and possibly iron oxides as primary phases,
conditions. The column experiment in acidic conditions and kaolinite, jarosite, okenite, schulenbergite and whit-
was chosen to represent an approximation of acidic pore lockite as secondary phases (Table 1). The quantification
water generated in an unsaturated tailing, which had been of arsenian pyrite metal concentration indicates a concen-
exposed to atmospheric conditions with high concentra- tration of 0.8 wt% As, 52–53 wt% S, 44–46 wt% Fe, 0.1–
tions of pyrite for prolonged periods of time. 1.9 wt% Cu and 0.1 wt% Zn.
The column experiments setup consisted of a water The mining wastes obtained from the main areas that
reservoir, a peristaltic pump, a methacrylate column and a were mined (Cerro Cinto, Consulta and Las Niñas) and
series of instruments, in order to determine some parame- those close to the tailing deposit showed the presence of
ters of the effluents in situ. These included pH, Eh, EC, quartz, jarosite, galena, arsenian pyrite, chalcopyrite,
temperature and dissolved O2. Details of the column sphalerite, orthoclase, gold, nantokite and alunite as main
experiment can be found in Navarro and Cardellach (2008) primary phases, and goethite, jarosite, hematite, pumpel-
and Navarro and Martı́nez (2008). Low mineralized water lyite, anglesite, ferrihydrite, covellite and scorodite as
entered the column through an injection system connected
to a metering pump. A constant head reservoir was used to
deliver influent water at a flow rate of 1.8 L/h. The samples Table 1 Identified mineral phases in the Rodalquilar tailings and
were collected at the bottom of the column as a function of mining wastes impoundments
time. The first sample, corresponding to time 0, was taken Mineral phases Formula
when the water started to flow from the lower part of the
column. Flow, pH and EC were measured immediately Primary phase (tailings)
after sample collection. Quartz SiO2
In addition, the number of pore volumes reached in the Alunite KAl3(SO4)2(OH)6
column experiments was estimated, which may be defined Arsenian pyrite Fe(S1-xAsx)2
by: Albite Na0.986(Al1.005Si2.995O8)
Illite KAl2Si3AlO10(OH)2
3H2O
Ta ¼ Vt
L1 ;
Jarosite KFe3(SO4)2(OH)6
where Ta is the number of pore volumes, V is the pore Secondary phase (tailings)
velocity, L is the column length and t is the time of Goethite FeOOH
leaching. The final Ta is 20.3 pore volumes, indicating a Whitlockite Ca3(PO4)
time period that may be considered to be representative. Schulenbergite (CuZn)7(SO4)2(OH)10
The hydrogeochemical analyses of leachates were per- Jarosite KFe3(SO4)2(OH)6
formed using the PHREEQC numerical code (Parkhurst Kaolinite Al4(Si4O10)(OH)8
and Appelo 1999) to evaluate the speciation of dissolved Primary phase (mineralization and mining wastes)
constituents and calculate the saturation state of the efflu- Quartz SiO2
ents. The Minteq thermodynamic database was used for the Jarosite KFe3(SO4)2(OH)6
chemical equilibrium calculations. The total concentrations Galena PbS
of As, Fe, Mn and other elements were used in the geo- Chalcopyrite CuFeS2
chemical modeling. Arsenian pyrite Fe(S1-xAsx)2
Sphalerite ZnS
Orthoclase K(Al, Fe)Si2O8
Results Gold Au
Alunite KAl3(SO4)2(OH)6
Mineralogical results Secondary phase (mineralization and mining wastes)
Goethite FeOOH
An X-ray diffraction (XRD) analysis, binocular micro- Jarosite KFe3(SO4)2(OH)6
scope analysis, EDAX electron microscope analysis and Hematite Fe2O3
ore microscope image revealed the mineralogical nature of
Nantokite CuCl
the tailings; the dominant mineralogical fractions were
Pumpellyite Ca2FeAl2(SiO4)(Si2O7)(OH)2
H2O
silica, alunite and arsenian pyrite (Table 1). These minerals
Anglesite PbSO4
were derived from the auriferous quartz extracted during
Ferrihydrite Fe(OH)3
the periods 1930–1936 and, more significantly, 1943–1966
Covellite CuS
from the Cerro Cinto open pit and low-sulfidation veins.
Scorodite FeAsO4
2H2O
Besides, the mineralogical analysis indicates the presence

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secondary phases (Table 1). Other mineral phases detected
in the Rodalquilar area were barite, smectite, calaverite,
tellurite, rodalquilarite, enargite, cassiterite, tetraedrite,
bismutite and bornite (Arribas et al. 1995).
Moreover, sulfate–Fe–Al salts with high concentration
of As (110 mg/kg), Cd (6.8 mg/kg), Zn (1070 mg/kg), Cu
(1,664 mg/kg), Mn (908 mg/kg), and low-to-medium
concentration of Sb (4.1 mg/kg), Ni (41 mg/kg), Pb
(82 mg/kg) and Bi (4 mg/kg) were detected at ephemeral
AMD pools.
Geochemical results
The analysis of sampled tailings and sediments revealed
high concentrations of Au, Ag, As, Bi, Cu, Fe, Mn, Pb, Se,
Sb, V and Zn (Table 2), which were above the metal
concentration of non-contaminated soils. Such soils have
low concentration of these metals in comparison with
contaminated materials. The contaminant of greatest
environmental concern is As, which showed a mean con-
centration of 679.9 mg/kg in the tailings. The highest
concentration of As in the tailings was 1,410 mg/kg, and in
the sediments of Playazo creek this concentration was
345.5 mg/kg.
The high As concentration may be explained by the
presence of arsenian pyrite, associated with auriferous ore
(Table 3). This is the case with other gold deposits (Savage
et al. 2000) and it seems to be associated with the weath-
ering crusts of ferric oxides and Fe-oxyhydroxides (Mo-
reno et al. 2007). Therefore, during weathering, the
substitution of As into pyrite may be responsible for the
rapid oxidation and dissolution of arsenian pyrite (Savage
et al. 2000), which liberates As and other pollutants into the
pore water and seepages, that may be released from tailings
during wet periods. The presence of As in the tailing
material, also, may be associated with Fe-bearing particles,
probably ferric oxide and ferric oxyhydroxide, which
contain around 1% As (Moreno et al. 2007).
In tailings, the concentration of copper, zinc and cad-
mium is high (mean concentration of 202, 472.9 and
0.8 mg/kg, respectively), and, also, in sediments (172.5,
241.2 and 1.1 mg/kg, respectively). The high concentra-
tions of these metals may be explained by the presence of
nantokite, sphalerite, chalcopyrite and covellite in the
processed ore. Thus, the concentration of these metals in
the mining wastes and the ore samples is high, particularly
in the low-sulfidation quartz veins samples (Table 3).
In both tailings and sediments, the concentrations of
antimony are high (mean concentration of 141.6 and
53.5 mg/kg, respectively). Antimony is also found in high
concentrations in Fe-fine particles of the tailing material
(Moreno et al. 2007). Lead has elevated concentrations in
both tailings and sediments (mean concentration of 924.1
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Environ Earth Sci (2010) 60:121–138
and 379.2 mg/kg, respectively). The presence of anglesite,
an alteration product of galena, may help to explain the
elevated concentration of Pb in tailings and sediments.
In tailings, high concentrations of Au and Bi were
detected (mean values of 472.3 lg/kg and 22.7 mg/kg,
respectively), indicating that the efficiency of the metal
extraction process was poor. The concentration of Au in
the ore was moderate (4,420–11,900 mg/kg; Table 3).
Hernández (2002) reported that the ore processed during
the period 1956–1966 had a mean Au concentration of only
1.56–4.38 mg/kg.
The mean concentration of zinc was moderate both in
tailings (472.9 mg/kg) and in sediments (241.2 mg/kg),
derived from the presence of sphalerite. The elevated
concentration of Cd seem to be associated with the pres-
ence of sphalerite, which explains the Cd concentrations of
up to 661 mg/kg found in the low-sulfidation ore samples
enriched with sphalerite (Table 3).
Leaching tests
The measurements of effluent leachate pH during the
experiment with low-mineralized water showed that pH
values varied only slightly between 7.0 and 8.2 at the end of
the experiment. These high pH values may be attributed to
the alkaline nature of the cyanide solution (pH = 10.3), used
in gold extraction, to which quicklime is added (Lottermoser
2003). Results show the mobilization of Al, Cr, Fe, Mn, Ni,
Cu, Zn, As, Se, Cd, Sb, Ba, Pb, Sn, Te, V and Au, as well as
Na, Mg, K and Ca (Tables 4, 5).
The mobility of metals in the column experiment for Al,
Fe, Mn, Cr, Cu, Ni, V and Zn were significant, but below that
of groundwater samples (Tables 4, 5). However, As, Cd, Sb,
Se Pb and Au are mobilized in concentrations above those
detected in groundwater. The evolution of Al and Fe (Fig. 2)
showed decreases in concentrations from 1,200 and
1,680 lg/L to 54 and 33 lg/L, respectively at the end of the
experiment. Concentrations increased between 100 and
1,500 min, possibly due to the increase in pH. These values
are below those reported for Al and Fe leached during the
experiment under low pH conditions (Fig. 2).
Concentrations of Cu, Se and Sb are below those
detected in the acidic leaching experiment (Fig. 3). Mn and
Ni were below those detected in the acidic leaching
experiment, in which Mn concentrations were above 1 mg/
L (Fig. 4). The total elemental concentrations of the
leached sample (sample CEX in Table 2) indicate that most
of the metal mass remained in the mine waste sample and
was not leached during the experiment. However, the con-
centrations detected in the experiment with low-mineralized
water could indicate a considerable risk of contamination.
This implies that metals in tailings may be present in at least
three forms: (1) dissolved metals in the pore water and
Environ Earth Sci (2010) 60:121–138 127

Table 2 Concentrations of metals and metalloids in tailings and sediments in Rodalquilar (Almerı́a)
Au Ag As Ba Bi Cd Cu Hg Fe Mn Pb Se Sb V Zn

Tailings
R1 511 0.9 1,410 100 23 0.4 85 \1 2.95 198 1,044 22 225 76 205
R2 492 0.9 1,110 135 23 0.3 97 \1 3.16 51 257 36 206 89 152
R3 372 0.9 833 71 41 \0.3 100 \1 3.04 59 189 31 253 83 110
R4 533 0.6 483 215 13 1.1 84 \1 2.94 708 155 8 91.7 105 248
R5 365 0.7 504 480 11 0.6 197 \1 3.57 1,003 191 15 65.5 118 1,130
R6 340 6.5 71.5 405 8 2.8 826 \1 4.47 331 183 \3 4.2 216 1,804
R7 984 4.0 122 230 46 4.6 957 \1 2.73 939 8,744 5 18.9 83 1,870
R8 233 1.2 606 185 14 0.0 130 \1 2.79 731 1,092 16 122 106 356
R9 246 0.3 634 375 21 0.6 70 \1 3.40 519 168 22 221 136 206
R10 438 0.4 977 120 31 0.3 85 3 3.32 57 283 29 244 94 247
R11 444 0.7 555 105 13 \0.3 71 \1 2.39 100 180 16 89.3 67 91
R12 644 1.0 678 100 18 0.5 105 \1 2.76 206 553 17 115 72 185
R13 968 0.9 528 95 15 0.5 101 3 2.30 217 402 18 88.6 68 173
R14 340 1.6 859 165 53 0.6 133 \1 3.38 123 431 26 221 97 264
R15 175 0.9 829 250 20 0.7 87 \1 3.19 73 510 27 159 90 381
Mean 472.3 1.4 679.9 202.0 22.7 0.8 202.0 – 3.0 346.6 924.1 19.0 141.6 97.8 472.9
Min 175.0 0.3 71.5 71.0 8.0 \0.3 70.0 \1 2.3 51 155.0 \3 4.,2 66.0 91.0
Max 984.0 6.5 1410 480.0 53.0 4.6 957.0 3.0 4.4 1,003 8,744.0 36.0 253.0 216.0 1,870
Sediments
RS16 142 0.5 204 380 6 0.7 59 \1 3.00 747 311 \3 31.4 124 182
RS17 171 0.5 220 400 5 0.6 66 2 2.89 655 293 10 33.2 118 197
RS18 74 0.5 132 345 3 1.0 54 2 2.73 763 263 \3 19.3 120 207
RS19 364 0.8 470 250 14 0.7 85 \1 2.83 376 328 18 74.9 92 176
RS20 20 \0.3 61.3 305 \2 0.8 64 \1 2.45 441 131 \3 8.6 110 76
RS21 309 0.8 320 365 6 0.6 73 \1 2.82 702 332 8 51.6 98 198
RS22 268 0.7 241 390 5 0.8 65 \1 2.45 405 217 6 36.0 98 195
RS23 346 0.9 464 330 13 0.7 95 \1 3.11 511 612 11 64.3 110 209
RS24 575 1.0 352 365 9 0.8 87 \1 2.82 635 439 12 55.2 119 174
RS25 509 1.0 794 165 19 0.4 108 \1 3.34 448 588 24 130 77 153
RS26 435 0.8 507 430 18 0.6 94 \1 3.44 550 579 16 89.1 114 232
RS27 765 1.3 540 405 21 0.9 96 \1 3.15 630 725 18 88.7 114 197
RS28 242 1.3 400 320 18 0.6 80 \1 3.14 645 380 12 65.4 103 237
RS29 38 0.7 132 620 5 1.3 77 \1 2.86 616 336 \3 14.5 126 259
RS30 435 1.1 581 145 18 0.4 70 \1 2.65 127 204 17 89.8 69 117
Mean 296.0 0.7 345.5 336.8 10.5 1.1 172.5 – 2.8 583.9 379.2 8.5 53.5 104.1 241.2
Min 20.0 \0.3 61.3 145.0 \2 0.4 54.0 \1 1.9 127 82.0 \3 4.1 69.0 76.0
Max 765.0 1.3 794.0 620.0 21.0 6.8 1,664 2.0 3.4 908 725.0 24.0 130.0 126.0 1,114
CEX 867 2.6 1330 \50 33 1.8 206 \1 3.4 381 3,190 \3 283 70 432
NCD 11.0 \0.3 24.1 825 \2 0.8 12 \1 1.08 208 19 \3 2.1 43 4
NIL (*) – 15a 55 625 – 12 190 10 – – 530 100a 15 250a 720
Values in mg/kg except Fe (%) and Au (lg/kg)
NIL(*) The Netherlands soil intervention values, NCD non-contaminated soils, sampled in old alluvial sediments far away the mining area, CEX
tailings used in the column experiments
a
Indicative level of serious contamination

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128 Environ Earth Sci (2010) 60:121–138

Table 3 Concentration of metals in mineralization and mining wastes of Rodalquilar

Au Ag As Ba Bi Cd Cu Hg Fe Mn Pb Se Sb V Zn

Mineralization
Q-Cerro Cintoa 5,910 15 551 286 2 \0.3 52 \1 4.29 312 370 43 33.7 16 26
Q-Consultab 5,270 34 33.7 198 \2 661.6 6,374 \1 2.41 233 48,770 \3 30.8 11 99,553
Q-Ma Josefab 1,190 40 658 429 \2 17.5 4,574 \1 4.53 371 2,629 19 570 10 2,847
Q-Las Niñasb 4,420 61 1,040 \50 157 62.6 2,190 \1 0.98 43 [5,000 \3 980 15 265
Mining wastesc
Mean 1,466.6 2.9 325.7 236.2 13.6 0.53 208.8 0.8 4.47 336.6 1,339.1 21.3 31.2 83.2 120.2
Min 15.0 0.3 53 50 2 0.3 13 0.5 0.76 5.0 38 3 4.8 10 1
Max 3,840 5.6 1,700 1,000 37 1.5 485 3.0 14.3 2,226 [5,000 150 110 183 599
Values in mg/kg except Fe (%) and Au (lg/kg)
a
Main high-sulfidation mineralization
b
Low-sulfidation veins with galena, sphalerite, pyrite and calcopyrite
c
Host-rocks and low-grade stockpiles

Table 4 In situ determinations and main cations of low-mineralized water leaching experiment
Sample Conductivity pH Na Mg Si K Ca Al Fe

RL-1 8,590 8.03 [30,000 4,950 13,800 4,980 [20,000 1,200 1,680
RL-2 5,720 7.76 [30,000 7,270 11,800 18,000 12,000 562 1,310
RL-3 2,230 7.6 [30,000 5,080 11,800 9,640 [20,000 77 94
RL-4 1,890 7.54 [30,000 4,060 10,900 5,950 [20,000 60 71
RL-5 1,568 7.5 [30,000 3,970 10,700 5,770 [20,000 97 100
RL-6 527 7.35 [30,000 3,300 10,400 3,200 [20,000 153 103
RL-7 379 7.25 [30,000 3,360 10,100 2,560 [20,000 200 113
RL-8 305 7.03 [30,000 3,470 9,980 2,160 [20,000 149 100
RL-9 239 6.8 [30,000 3,390 9,770 1,960 [20,000 77 55
RL-10 249 8.26 [30,000 3,320 9,390 1,710 [20,000 64 63
RL-11 174 8.24 27,900 3,390 10,100 1,720 [20,000 161 144
RL-12 167 8.2 25,900 3,360 9,320 1,620 [20,000 54 33
LMW 133 6.98 16,500 3,660 9,100 1,090 [20,000 55 51
Values in lg/L, except conductivity (lS/cm), and pH
RL1: 0 min, RL2: 20 min, RL3: 40 min, RL4: 60 min, RL5: 80 min, RL6: 100 min, RL7: 120 min, RL8: 150 min, RL9: 180 min, RL10:
210 min, RL11: 240 min, RL12: 300 min. LMW: low mineralized water

metals associated with high soluble efflorescent salts
mobilized at the beginning of the experiment, (2) pos-
sible reducible fractions associated with Fe and Mn
oxyhydroxides and (3) low-mobility fractions associated
with sulfide minerals in the tailings. An important point
here is that Ribet et al. (1995) and Jurjovec et al. (2002)
showed that Fe(III) oxyhydroxides were the source of
Zn, Ni, Co, Pb and Cd, in mine tailings, and Fe, Ni, Cu,
Cr and Co, otherwise.
Groundwater
The analysis of groundwater samples taken from the allu-
vial aquifer revealed high concentrations of Al, As, Cd, Fe,
Hg, Mn, Ni, Pb, Se, Sb and Zn (Table 6) and very high
concentrations of chloride and sulfate (Table 7), above the
European standards for drinking water (Real Decreto 149/
2003, Boletı́n Oficial del Estado, BOE, 21/02/03).We also
detected high values of Au, Cu, V and Zn in groundwater
samples.
The results from field studies (Table 7) indicated that
pH is neutral-alkaline and ranges between 6.7 and 8.3. The
exception to this is the surface water sample, S-13, which
had a low pH representing the conditions of acidic drainage
at the old mine, Blanca y Negra. The field-measured redox
potential indicates moderate oxidant conditions, except in
S-6 and S-9 samples, obtained from deep wells and S-10
and S-14 samples, associated with possible organic dumps.

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Environ Earth Sci (2010) 60:121–138 129

Table 5 Main metal concentration of low-mineralized water leaching experiment

Sample Cu Se Sb Mn Ni Cd Zn As V Au Hg Pb Bi

RL-1 50.5 51.9 20.2 41.4 4.1 5.46 [250 [200 4.6 0.423 \0.2 [200 0.8
RL-2 42 238 21.8 34 19 6.4 26.0 1,970 21.0 2.97 \2 200 \3
RL-3 14.7 97.6 16.0 1.7 11.4 2.94 45.6 [200 0.9 1.21 \0.2 4.96 \0.3
RL-4 10.9 57.6 11.7 1.3 5.1 2.25 42.4 [200 2.1 0.726 \0.2 3.42 \0.3
RL-5 10.6 60.1 11.2 2.0 3.1 2.38 54.8 [200 2.3 0.676 \0.2 8.63 \0.3
RL-6 8.0 29.3 9.3 1.4 1.1 1.73 74.1 [200 2.5 0.297 \0.2 5.30 \0.3
RL-7 9.3 19.7 8.0 2.5 0.7 1.93 134 [200 2.4 0.201 \0.2 18.7 \0.3
RL-8 5.3 13.9 8.0 2.3 \0.3 1.92 76.1 [200 1.8 0.148 0.2 11.9 \0.3
RL-9 5.8 11.8 6.0 1.3 0.3 1.50 55.0 [200 1.6 0.129 0.2 4.02 \0.3
RL-10 4.4 10.8 5.5 1.8 0.7 1.37 71.2 [200 1.5 0.105 \0.2 8.20 \0.3
RL-11 11.9 6.8 8.1 3.1 1.4 1.45 95.5 [200 1.6 0.091 \0.2 27.5 \0.3
RL-12 8.4 9.2 4.2 1.1 1.0 1.14 79.6 [200 1.7 0.086 \0.2 4.41 \0.3
LMW 14.5 0.7 2.9 1.6 1.3 0.29 87.9 1.90 2.0 0.002 \0.2 9.45 \0.3
Values in lg/L
RL1: 0 min, RL2: 20 min, RL3: 40 min, RL4: 60 min, RL5: 80 min, RL6: 100 min,RL7: 120 min, RL8: 150 min, RL9: 180 min, RL10: 210 min,
RL11: 240 min, RL12:300 min, LMW: low mineralized water

Al, Fe evolution Mn, Ni evolution

100,000 10000
Mn Mn-acid
Ni Ni-acid
10,000 1000

1,000 100

100 10

10
1
Al Al-acid
0 20 40 60 80 100 120 150 180 210 240 300
Fe Fe-acid
1
0 20 40 60 80 100 120 150 180 210 240 300 0.1
time (min)
time (min)
Fig. 4 Evolution of Mn and Ni in the leaching experiments. Values
Fig. 2 Evolution of Al and Fe in the leaching experiments. Values in in lg/L. Metal–acid: change of Mn and Ni concentration in time,
lg/L. Metal–acid: change of Al and Fe concentration in time, measured in effluent solution of acid input
measured in effluent solution of acid input

Cu, Sb, Se evolution

10000
Cu Sb Se-acid Electrical conductivity varies considerably between sam-
Se Cu-acid Sb-acid
ples W-15 (sea water) and S-13; the samples with the
1000 highest values were those taken close to tailing impound-
ments (S-18) or those affected by marine intrusion (S-7 to
S-12). The temperature varied considerably, between 14
100
and 23C in sample S-6, possibly due to the influence of
the current geothermal system.
10 The major ion chemistry showed that groundwater
samples had high concentrations of chloride, sulfate, Ca,
1
Mg and K (Table 7). The samples with marine intrusion
0 20 40 60 80 100 120 150 180 210 240 300 (S-7, S-11 and S-12) contained chloride concentrations
time (min) above 1,562 mg/L and Mg concentrations above 200 mg/
L. The salinization of groundwater near the shoreline may
Fig. 3 Evolution of Cu, Se and Sb in the leaching experiments.
Values in lg/L. Metal–acid: change of Cu, Se and Sb concentration in have been caused by the elevated groundwater pumping in
time, measured in effluent solution of acid input the area with a scarce recharge potential.

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123
Table 6 Metal concentrations of groundwater. Values in lg/L. EC: electrical conductivity in mS/cm. EDWS: European drinking water standards
Sample Au Al Ag Cd Cu Ni As Se Sb Pb Fe Mn Hg V Zn Cr
(lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L)

S-1 \0.02 \20 \2 1.6 13 5 12 7 3.1 14.7 1,900 730 \2 29 426 19

S-2 1 60 \2 \0.1 83 645 6.3 25 2.7 2.9 1,300 1750 \2 9 108 34
S-3 \0.02 \20 \2 \0.1 24 9 0.3 10 2.7 0.4 400 \1 \2 5 190 15
S-4 0.08 \20 \2 \0.1 10 4 1.6 8 6.4 0.3 500 10 \2 4 99 13
S-5 0.08 30 \2 \0.1 10 \3 2.8 4 6.3 0.8 1,000 3 \2 4 33 13
S-6 0.21 2,890 \2 5 65 119 16.5 \2 2.4 22.3 76,300 416 \2 7 125 6
S-7 0.13 90 \2 0.2 18 39 13 \2 2.4 1.6 10,200 115 \2 2 191 10
S-8 \0.02 \ 20 \2 \ 0.1 4 \3 1.4 \2 2.7 1.2 100 14 \2 4 62 12
S-9 \0.02 40 \2 2.4 22 42 2.1 \2 2.7 21.7 46,100 624 \2 4 297 \5
S-10 \0.02 \20 \2 \0.1 14 4 \ 0.3 \2 3.1 8.4 5,500 70 \2 \1 83 \5
S-11 0.22 350 \2 \0.1 21 4 224 \2 3.9 8.2 800 45 \2 8 79 11
S-12 0.11 130 \2 \0.1 17 \3 \ 0.3 \2 2.6 1.7 300 107 \2 4 67 16
S-13 \0.02 [20,000 \2 62.1 1,300 95 66.1 18 0.9 3.9 4,800 912 \2 11 [2500 17
S-14 \0.02 400 \2 1.2 9 24 7.1 \2 0.2 2.9 73,500 519 \2 \1 146 \5
W-15a \0.2 5,800 \20 \1 90 130 \3 \20 \1 35 4,000 540 \20 \10 70 \50
W-16b 0.07 260 \2 0.3 11 6 71.7 \2 2.9 8.5 200 10 \2 4 17 \5
W-17b \0.02 490 \2 0.2 11 18 14.3 4 3.7 9.6 \100 142 4.0 4 58 26
S-18 \0.02 \20 \2 0.1 4 54 \0.3 \2 0.3 2.5 62,200 1720 \2 \1 12 \5
EDWS – 200 – 5.0 2,000 20 10 10 5 10 200 50 1.0 – – 50.0
Values in lg/L
RL1: 0 min, RL2: 20 min, RL3: 40 min, RL4: 60 min, RL5: 80 min, RL6: 100 min, RL7: 120 min, RL8: 150 min, RL9: 180 min, RL10: 210 min, RL11: 240 min, RL12: 300 min, LMW: low
mineralized water
a
Sea water
b
Superficial water of lagoons near the Playazo beach
Environ Earth Sci (2010) 60:121–138
Environ Earth Sci (2010) 60:121–138 131

Table 7 In situ determinations and main anions of groundwater

Sample Conductivity pH Eh T (8C) Na Mg K Ca Cl NO3 SO4 HCO3

S-1 \0.02 7.7 136 15.6 [300 78.6 23.3 90 711 \0.1 465 201
S-2 1 7.6 134 16.5 [300 [200 92.6 [200 3,983 \0.1 1,851 623
S-3 \0.02 7.6 136 – [300 144 19.5 [200 848 \0.1 874 295
S-4 0.08 7.8 121 – [300 185 21.3 [200 1,086 \0.1 717 189
S-5 0.08 7.8 110 – [300 183 20.7 [200 217 \0.1 100 191
S-6 0.21 7.1 -40 23.0 [300 [200 19.4 [200 1734 \0.1 1,082 122
S-7 0.13 7.7 40 20.8 [300 [200 27.9 [200 1562 \0.1 640 202
S-8 \0.02 8.3 112 18.2 174 46.7 11.0 91 335 \0.1 164 190
S-9 \0.02 8 -20 22.7 [300 86.5 21.5 114 720 \0.1 507 334
S-10 \0.02 7.4 0 20.9 [300 [200 22.3 [200 1,612 \0.1 1,212 259
S-11 0.22 8.1 135 14.0 [300 [200 77.8 [200 1,645 \0.1 1,299 395
S-12 0.11 8.2 147 14.3 [300 136 26.5 131 1,981 \0.1 127 531
S-13 \0.02 3.1 280 – 20.8 20.6 1.8 51 24.6 11.9 1,350 \2
S-14 \0.02 6.7 -45 – 350 142 11.0 [200 1,770 1.3 1,030 \2
W-15a \0.2 8.1 74 19.8 10,500 1,510 461.0 860 20,400 8.8 2,830 122
W-16b 0.07 – – – 350 36.8 25.5 80 974 0.8 161 56
W-17b \0.02 – – – 216 24.2 21.2 155 1,870 28.3 704 226
S-18 \0.02 6.97 210 – [350 187 19.5 110 1,190 \1.3 1,120 65
EDWL – – – – 200 – – – 250 50 250 –
Values in mg/L, Eh in mV
EC electrical conductivity in mS/cm, EDWS European drinking water standards
a
Sea water
b
Superficial water of lagoons near the Playazo beach

The distribution of the higher Cd, Fe, Mn, and possibly Relation Eh-As-Fe
100000
Cu concentrations in the groundwater from samples S-6, Fe
As
S-9, S-13, S-14 and S-18 (Table 6) is associated with the 10000

low Eh levels (except in samples S-13 and S-18). This

possibly indicates that the dissolution of Fe and Mn oxy- 1000
As, Fe (ppb)

hydroxides may be the main cause of the elevated con-

100
centration of these metals in the groundwater. Furthermore,
the very low concentrations of nitrate and high concen- 10

trations of dissolved Fe and Mn may be an indication of the

1
reducing condition in part of the aquifer. Also, in the -100 -50 0 50 100 150 200 250 300

groundwater samples with low Eh levels (S-6, S-9 and S- 0.1

14), the concentrations of Fe and Mn were higher than
those detected in the leaching tests using neutral low-
mineralized water (Figs. 2, 4). This may suggest a variation
in the mobilization mechanism of these metals in the
groundwater and tailing impoundments.
There is no clear relationship between the distribution of
total As and the possible reductive dissolution of Fe and
Mn; the highest concentrations of As ([ 10 lg/L) are
found in those groundwater samples with elevated con-
centrations of Fe and Mn (samples S-1, S-6, S-7 and S-13)
and samples with low-to-medium concentration of Fe and
Mn (samples S-11, W-16 and W-17) (Fig. 5). Thus, the
arsenic concentration of Bangladesh groundwater is well
correlated with Fe, Mn, and Al oxides in fine-particle
Eh (mV)
Fig. 5 Bivariate plot showing the relationship between Eh and As
and Fe concentrations in groundwater
sediments and total organic carbon (TOC) in large-particle
sediments (Anawar et al. 2003), contributing different
phases to the total arsenic concentrations in groundwater.
Also, by analyzing the relationship between concentrations
of Eh, As and Fe (Fig. 5), a possible inverse relationship
between Eh and Fe was discovered. This may be indicative
of the reductive dissolution of oxyhydroxides as the source
of dissolved Fe. However, the relationship between Eh and
As concentrations is unclear.

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132 Environ Earth Sci (2010) 60:121–138

Table 8 Distribution of species for groundwater, seawater (W-15) and leachate RL-2
SPECIES RL-2 S-18 S-9 S-3 S-7 S-11 S-12 W-15

As
HAsO42- 2.49 9 10-5 2.99 9 10-8 2.52 9 10-8 3.70 9 10-9 1.63 9 10-7 2.92 9 10-6 3.93 9 10-9 3.97 9 10-8
H2AsO4- -6
1.39 9 10 1.01 9 10 -8
8.70 9 10-10
3.07 9 10 -10
1.01 9 10-8
7.21 9 10 -8
8.11 9 10-11
6.73 9 10-10
AsO43- 8.39 9 10-9 1.42 9 10-12 1.52 9 10-11 8.05 9 10-13 5.38 9 10-11 2.13 9 10-9 3.32 9 10-12 5.41 9 10-11
Fe
Fe2? 3.48 9 10-6 8.67 9 10-4 6.97 9 10-4 5.72 9 10-6 8.02 9 10-8 7.37 9 10-6 1.49 9 10-6 6.17 9 10-5
-7 -4 -4 -6 -8 -6 -8
FeSO4 6.06 9 10 2.26 9 10 1.17 9 10 1.23 9 10 1.15 9 10 1.85 9 10 4.38 9 10 4.42 9 10-6
2? -5 -5 -7 -7 -4 -6 -7
Fe(OH) 1.00 9 10 2.04 9 10 3.45 9 10 1.27 9 10 1.03 9 10 1.26 9 10 7.02 9 10 1.26 9 10-6
Fe(OH)3 5.50 9 10-6 1.81 9 10-6 3.38 9 10-7 4.88 9 10-8 4.90 9 10-5 1.48 9 10-6 1.06 9 10-6 1.23 9 10-6
Pb
PbCO3 8.56 9 10-7 4.01 9 10-9 8.99 9 10-8 1.73 9 10-9 6.88 9 10-9 3.40 9 10-8 6.65 9 10-9 9.34 9 10-8
Pb2? 2.67 9 10-8 2.05 9 10-9 5.61 9 10-10 3.80 9 10-11 1.81 9 10-10 2.20 9 10-10 2.31 9 10-11 6.71 9 10-9
PbSO4 1.37 9 10-8 1.81 9 10-6 2.95 9 10-10 2.86 9 10-11 8.41 9 10-11 2.04 9 10-10 2.47 9 10-12 2.35 9 10-9
Zn
Zn2? 2.05 9 10-6 1.22 9 10-7 8.62 9 10-7 1.26 9 10-6 1.43 9 10-6 2.06 9 10-7 8.78 9 10-8 5.28 9 10-7
-7 -8 -7 -7 -7 -8 -9
ZnSO4 5.09 9 10 4.55 9 10 1.95 9 10 3.92 9 10 2.85 9 10 7.72 9 10 3.81 9 10 5.27 9 10-8
-7 -9 -6 -7 -7 -7 -7
ZnCO3 8.02 9 10 2.93 9 10 1.66 9 10 6.99 9 10 6.64 9 10 3.87 9 10 3.07 9 10 6.00 9 10-8
Al
Al(OH)3 9.45 9 10-6 5.71 9 10-7 1.91 9 10-7 4.71 9 10-7 1.04 9 10-6 6.73 9 10-6 2.15 9 10-6 2.69 9 10-5
Al(OH)-
4 1.12 9 10-5 1.11 9 10-7 1.29 9 10-6 2.60 9 10-7 2.27 9 10-6 6.23 9 10-6 2.66 9 10-6 1.90 9 10-4
Data calculated using PHREEQC and database MINTEQ. Values in mol/kg

High concentrations of Al ([ 0.4 mg/L) are associated
with Ni-rich groundwater and surface water samples (S-6,
S-13, S-14 and W-17). High concentrations of Fe were also
found, which suggests a possible control of Ni by Fe and Al
oxyhydroxides in groundwater. Moreover, sea water sam-
ples (W-15) contained high concentrations of Ni and Cu;
this has also been reported in other Mediterranean areas.
High Pb and Zn concentrations are also associated with
high Fe groundwater samples (S-1, S-6 and S-9), which
indicates a possible sorption mechanism of Pb, and Zn
control by Fe oxyhydroxides.
Calculations using PHREEQC for groundwater specia-
tion (Table 8) revealed that the most abundant species of
Fe along a possible flow path in the alluvial aquifer are
Fe2? and FeSO4. In samples S-7 and RL-2 (leachate),
however, the dominant species are Fe(OH)2? and Fe(OH)3.
Similarly, the saturation index (Table 9) indicates that
ferrihydrite, goethite, and jarosite are clearly saturated.
However, siderite appears undersaturated in several sam-
ples, and close to equilibrium in the remainder of samples.
This may indicate a possible control of dissolved Fe by
FeCO3. Furthermore, jarosite-Na is undersaturated in
samples S-3 and S-12, which could indicate the mobiliza-
tion of Fe from this mineral under certain conditions. The
presence of high concentrations of dissolved Fe and Mn
with very low concentration of nitrate but with high
dissolved concentrations of As may be caused by the
reductive dissolution of Fe and Mn oxyhydroxides, while
the presence of low concentrations of dissolved Fe and Mn
and high As (sample S-11) could have originated from
siderite precipitation. The possible control of dissolved Fe
by siderite in the Eh–pH conditions of the aquifer is shown
in Fig. 6, where FeCO3 is the most stable species for pH
values of 7.5–8 and moderate reducing conditions.
The calculated As-dominant species are As (V) species,
such as HAsO42- and H2AsO4- (Table 8). This is based on
the pH–Eh conditions of the groundwater (Fig. 7) and results
from other contaminated mining areas (Eapaea et al. 2007).
There is a possible relationship between dissolved As, and Fe
and Mn, since groundwater with high Fe and Mn (and low
Eh) generally have a significant dissolved As concentration.
Taggart et al. (2004) also showed the association between As
and Fe, and As–Mn in the contaminated soils of Aznalcóllar.
Furthermore, the reductive dissolution of Fe oxyhydroxides
was proposed by Nickson et al. (2000) and Hasan et al.
(2007) to explain the high concentrations of dissolved As
found in groundwater samples from Bangladesh. Other
potential adsorbents of As may include Al oxyhydroxides,
Mn oxides and clay minerals (Stollenwerk 1994).
Similarly, groundwater is undersaturated in relation to
scorodite (Table 9), suggesting the possible mobilization of
As from reductive dissolution of the oxyhydroxides of Fe

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Environ Earth Sci (2010) 60:121–138 133

Table 9 Calculated saturation index for groundwater, seawater (W-15) and lixiviate RL-2
Phase mineral RL-2 S-18 S-9 S-3 S-7 S-11 S-12 W-15

Iron oxy-hydroxides and siderite

FeCO3 -0.70 0.40 2.35 -0.36 -2.23 0.25 -0.17 0.10
Fe(OH)3 3.46 2.97 2.24 1.40 4.41 2.89 2.74 2.87
Goethite 7.59 7.11 6.55 5.48 8.65 6.87 6.74 7.08
Fe(OH)2.7Cl0.3 8.60 8.34 7.24 6.54 9.59 7.96 7.81 8.22
Sulfate minerals
Jarosite 7.33 8.65 3.25 1.76 10.59 5.35 2.25 5.76
Jarosite-Na 5.57 6.46 1.00 -0.52 8.21 2.44 -0.19 3.76
Gypsum -0.69 -0.59 -0.79 -0.39 -0.57 -0.32 -1.35 -0.04
Melanterite -5.89 -3.32 -3.68 -5.56 -7.65 -5.34 -6.97 -5.04
Alunite 2.40 1.51 -3.55 -0.79 -0.30 2.06 -2.12 -1.40
Lead minerals
Anglesite -2.72 -3.66 -4.47 -5.45 -5.01 -4.58 -6.50 -3.49
Cerrusite -0.09 -2.41 -1.12 -2.76 -2.21 -1.43 -2.15 -1.01
Zinc minerals
Goslarite -6.62 -7.67 -7.09 -6.71 -6.90 -7.39 -8.70 -7.62
As minerals
Scorodite -3.54 -5.38 -8.17 -9.10 -4.66 -5.76 -8.95 -7.87
Al minerals
Gibbsite 1.81 0.59 0.38 0.42 1.02 1.43 0.95 2.43
Saturation indices calculated using PHREEQC and database MINTEQ

[Fe 2+ ] TOT = 10.00 µM [ CO 3 2 −] TOT = 10.00 mM [AsO4 3 −] TOT = 10.00 mM [Fe 2+ ] TOT = 0.80 mM

1.0 FeO42− 1.0

Fe 3+

H 3 AsO4 FeAsO 4 :2H 2 O(c)

0.5 Fe 2 O 3(cr) 0.5

HAsO 4 2 −
E SHE / V

H 2 AsO4 −

AsO 4 3 −
E SHE / V

0.0 As(OH) 3
0.0
Fe 2+ FeCO3(c)

-0.5 Fe3O4(c) As(c) AsO(OH) 2 −

Fe(OH)2(c) -0.5
Fe(c)

-1.0 AsH 3
2 4 6 8 10 12
-1.0
pH t= 25°C 2 4 6 8 10 12
pH t= 25°C
Fig. 6 Eh–pH diagram for the system Built by Fe–CO32-–H2O.
MEDUSA code (Puigdomenech 2004). (c): solid phase, ESHE/V: Eh
Fig. 7 Eh–pH diagram for the system As–Fe–H2O. Built by
(volts)
MEDUSA code (Puigdomenech 2004). (c): solid phase, ESHE/V: Eh
(volts)

and Mn, and scorodite dissolution. This mineral was also

detected in the mineralogical study. The significant con- phases. However, in the groundwater samples, the high As
centrations of As (110 mg/kg) found in poor crystalline concentrations are associated with pH values above 8 and
efflorescent salts and the undersaturation of soluble sulfates close to neutrality.
such as melanterite (Table 9) may explain the mobilization The Al-dominant species are Al(OH)- 4 and Al(OH)3
of As from the waste deposits. Moreover, an increase in pH (Table 8), whereas gibbsite is saturated in all the samples
causes the anionic forms of As to be desorbed from solid of the flow path. Alunite is undersaturated in samples S-9,

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134 Environ Earth Sci (2010) 60:121–138

S-3, S-7, S-12 and in seawater samples (Table 9). This The most abundant species of Pb are PbCO3, Pb2? and
indicates the possibility of Al mobilization. These high PbSO4 (Table 8). Besides, groundwater is undersaturated
aluminium concentrations may derive from the weathering with respect to anglesite and cerrusite (Table 8), suggesting
of aluminosilicate minerals such as albite, illite, alunite and the mobilization of Pb by anglesite dissolution, which was
orthoclase (Table 1), or from the dissolution of the sec- detected in the mineralogical study. Moreover, Pb has a
ondary minerals that were detected: kaolinite and pump- strong affinity to adsorb onto oxyhydroxides and hydro-
ellyite (Table 2). In fact, under the pH conditions of the sulfates of Fe3? (Gunsinger et al. 2006). The high values
leaching tests (7.03–8.26), aluminium can be solubilized. detected in this study are associated with high concentra-
However, the colloidal mobilization could be an important tions of Fe, Mn and Zn (Table 6). Thus, when reducing
transport mechanism (Lottermoser 2003). Other leaching conditions exist in groundwater, the reductive dissolution
tests have indicated that aluminium concentrations from of the oxyhydroxides may release Pb and other metals into
mine tailings are limited by gibbsite solubility, and only the groundwater system.
minor concentration of aluminium are expected to be
derived from muscovite dissolution (Jurjovec et al. 2002). Metal mobilization from mine tailings
The elevated concentrations of dissolved SO42- were
detected near the tailing impoundments and close to The PHREEQC code was used to study the mobilization of
Playazo beach, indicating a possible double origin of pollutants from the tailings using the hydrogeochemical
SO42-: sulfate dissolution from tailing material and from analysis of leachate RL-2 and the chemical composition of
marine intrusion. In fact, seawater samples had an ele- low mineralized water used in the leaching tests
vated concentration of SO42-, 2,830 mg/L, and ground- (Table 10). The code allows inverse modeling in a way that
water samples located near the shoreline had elevated quantifies the chemical changes that occur in the water
concentrations of chloride, sulfate and Mg, which indi- during its trajectory (Parkhurst and Appelo 1999). It uses
cates the influence of seawater in their composition. an optional set of defined minerals and gases, which when
Also, gypsum was undersaturated in groundwater sam- related to an entry solution and an output solution explain
ples with saturation index values close to equilibrium the hydrogeochemical differences in the flow path. This
(Table 9). This may indicate that gypsum and jarosite numerical code in the form of inverse modeling has pre-
limit the concentration of dissolved SO42-. The Ca2? viously been applied to environmental mining problems
required for the formation of gypsum may be derived (Armienta et al. 2001; Eary et al. 2003; Sracek et al. 2004;
from the mining process (addition of lime) in the tailing Navarro et al. 2006, 2008) and used to interpret the geo-
impoundments, and also from the dissolution of calcite chemical properties of aquifers (Mahlknecht et al. 2004).
and dolomite, which were detected in the aquifer sedi- Moreover, based on the mineralogical analysis of the mine
ments. Furthermore, marine intrusion is a potential
source of dissolved Ca2? in groundwater by cationic
exchange of saline water with the clay minerals present
in the aquifer. Table 10 Input data and output concentrations used in the inverse
modeling
Together with Al, Fe and Mn, Zn was observed as being
the most mobile metal in groundwater and leachates Parameter Input (1) Output (2)
(Tables 5, 6). The release of Zn into the tailing pore water pH 7.0 7.76
and groundwater may be attributed to the oxidation of pe 4.44 4.06
sphalerite, which is associated with the high Cd concen- Ca (mg/L) 38.2 122
tration in mining wastes. This relationship is also found in Mg (mg/L) 3.36 7.2
groundwater. The most abundant species of Zn are Zn2?,
Na (mg/L) 13.5 869.4
ZnCO3 and ZnSO4 (Table 8), while goslarite is undersat-
K (mg/L) 1.06 18.0
urated in groundwater and in leachate sample RL-2
SO4 (mg/L) 10.3 630
(Table 9). The apparent correlation between high concen-
HCO3 (mg/L) 129.2 146.4
trations of Zn and high concentrations of dissolved Fe and
Cl (mg/L) 7.35 1,340.0
Mn in groundwater (Table 6) may be an indication that Zn
O2 (mg/L) 8.5 5.6
is associated with Fe and Mn oxyhydroxides. In fact, Zn in
Al 0.055 0.562
near-neutral environments is adsorbed by oxides, hydrox-
Si 9.1 11.8
ides and aluminosilicates. Furthermore, high Zn concen-
Fe (lg/L) 1 1,310
trations in groundwater and soils are usually related to
As (lg/L) 3 1,970
ferrihydrite desorption or dissolution processes (Jurjovec
et al. 2002). (1) demineralized water, (2) lixiviate RL-2

123
Environ Earth Sci (2010) 60:121–138 135

Table 11 Minerals used in the inverse modeling

Mineral phase Reaction Log k (Minteq)

Gypsum CaSO4:2H2O = Ca2? ? SO2-

4 ? H2O -4.848
Jarosite KFe3(SO4)2(OH)6 ? 6H? = K?? 3Fe3??2SO42-?6H2O -14.8
Jarosite-Na NaFe3(SO4)2(OH)6 ? 6H? = Na?? 3Fe3??2SO42-?6H2O -11.2
? -
Halite NaCl = Na ? Cl 1.582
Arsenian pyrite Fe(S0.88 As0.12)2 ? 3.32O2 ? 1.12H2O = Fe2? ? 1.76SO42- ? 0.24H3AsO3 ? 1.52H? -18.47
Kaolinite Al2Si2O5(OH)4 ? 6H? = 2Al?3 ? 2H4SiO4 ? H2O 5.726
Alunite KAl3(SO4)2(OH)6 ? 6H? = K?? 3Al3??2SO42-?6H2O -1.346
Goethite FeOOH ? 3H? = Fe3? ? 2H2O 0.5
Ferrihydrite Fe(OH)3 ? 3H? = Fe3? ? 3H2O 4.891
2?
Calcite CaCO3 = Ca ? CO-2
3 -8.47
Chlorite Mg5Al2Si3O10(OH)8 ? 16H? = 5 Mg2? ? 2Al?3 ? 3H4SiO4 ? 6H2O 68.38
Scorodite FeAsSO4:2H2O = Fe3? ? AsO-3
4 ? 2H2O -20.249

Table 12 Models and molar transfers calculated by PHREEQC F e( S 0 . 8 8 As 0 . 1 2 ) 2 → AsO 4 * α- FeO OH + KFe3 ((As,S)O4)2 (OH)6
TAILINGS
Phases M1 M2 M3
(1)
Gypsum -1.21 9 10-2 -1.24 9 10-2 -1.21 9 10-2
Jarosite 4.33 9 10-4 4.48 9 10-4 4.34 9 10-4 A sO 4 * α-FeOOH + KFe3 ((As,S)O4)2 (OH)6
-3 -3 PLAYAZO Sediments
Jarosite-Na 8.00 9 10 8.12 9 10 8.00 9 10-3
Halite 3.69 9 10-2 3.68 9 10-2 3.69 9 10-2
-5 (2) (3)
Kaolinite -3.42 9 10 – -3.23 9 10-5
-6 -5
Alunite 1.30 9 10 -1.35 9 10 – HA sO 4 2 - * α- FeOOH + SO42-
PLAYAZO Sediments Pore Water
Chlorite 3.23 9 10-5 2.03 9 10-5 3.23 9 10-5
-3 -3 -3
Arsenian pyrite 1.00 9 10 1.02 9 10 1.00 9 10 (4)
-4 -4 -4
Scorodite -2.15 9 10 -2.19 9 10 -2.15 9 10
HA sO 4 - + Fe(OH) 3
Siderite -1.44 9 10-2 -1.47 9 10-2 -1.44 9 10-2 GROUNDWATER
-2 -2 -2
Calcite 1.45 9 10 1.47 9 10 1.45 9 10 (5)
Ferrihydrite -1.16 9 10-2 -1.17 9 10-2 -1.16 9 10-2
H 3 AsO 3 + Fe 2 +
Negative values indicate precipitation and positive values indicate GROUNDWATER
dissolution
Fig. 8 Possible mobilization path of As from tailings to groundwater.
(1): wind transport, erosion and tailings leaching, (2): desorption, (3):
dissolution, (4): sorption, (5): reductive dissolution
wastes and surrounding contaminated soils, the following
phases were used in the inverse modeling: gypsum, calcite,
siderite, jarosite, jarosite-Na, halite, kaolinite, alunite, fer- inverse modeling were not conditioned and the results were
rihydrite, chlorite, arsenian pyrite and scorodite. The consistent (Table 12) with the saturation indices previously
thermodynamic database Minteq was used for the chemical calculated in the study of leachate RL-2, except for jarosite
equilibrium calculations. Results are shown in Table 11. and jarosite-Na (Table 8). Consequently, the three models
The inverse modeling calculations included primary resulting from inverse modeling showed that the dissolu-
sulfides (arsenian pyrite) and secondary phases, adding tion of jarosites and arsenian pyrite and/or the mobilization
gypsum and scorodite as representative minerals of sec- of Fe-rich pore water from oxidative dissolution of arse-
ondary soluble sulfates, which may exist as minority nian pyrite, may be the main source of the dissolved Fe.
minerals (\ 1%) in the tailing material. Calcite and siderite Besides, the oxidized iron fine particles detected by
minerals detected in the sediments located downstream Moreno et al. (2007) that may constitute around 3% of
from the tailing impoundments were also included. material tailings, containing approximately 1% As, may be
The arsenian pyrite dissolution was assumed like pyrite with arsenian pyrite the main primary source of As.
dissolution, using the pyrite equilibrium constant from Moreover, scorodite was not dissolved in any of the
Minteq (log K = -18.47). The main reactions obtained by models, indicating that Fe oxides and oxyhydroxides

123
136
together with arsenian pyrite may be the possible origin of
dissolved Fe and As in pore water. This As and Fe then
migrates from tailing impoundments and surrounding
sediments to soil and groundwater. Therefore, residual ar-
senian pyrite exposed to weathering in the tailing
impoundments may have produced fine-grained secondary
Fe3? oxyhydroxides (goethite, hematite, ferrihydrite) and
sulfates (jarosite), which have significant concentration of
As adsorbed and/or coprecipitated.
The greater reactivity of arsenian pyrite (Savage et al.
2000; Blanchard et al. 2006), which mobilizes As to the
pore water, represents the main source of As. In addition,
the possible dissolution of jarosite, estimated by inverse
modeling, may increase the As concentration of the pore
water. The mobilization of As from the mine tailings to
Playazo creek sediments and nearby soils, initiated by the
oxidation of arsenian pyrite, may be accompanied by the
wind transport of fine particles of Fe oxyhydroxides and
jarosite. The possible As desorption from goethite and
ferrihydrite and the jarosite dissolution could be responsi-
ble for the release of As into Playazo sediments pore water
and for the mobilization of the contaminants to the
groundwater. A possible mobilization path, based on
Savage et al. (2000), is shown in Fig. 8. Also, there may be
a possible reductive dissolution of Fe oxyhydroxides in the
deeper zone of mine tailings, which may mobilize As and
other metals adsorbed (McCreede et al. 2000).
Conclusions
Samples of tailings and sediments contained high concen-
trations of Au, Ag, As, Bi, Cu, Fe, Mn, Pb, Se, Sb, V and
Zn, which were higher than the metal concentrations of
non-contaminated soils. The contaminant of greatest
environmental concern is As. The mean concentration of
As in tailings was 679.9 mg/kg but was found at concen-
trations as high as 1,410 mg/kg; in the sediments of
Playazo creek this concentration was 345.5 mg/kg.
Copper, zinc and cadmium were found in elevated
concentrations in tailings (mean concentration of 202,
472.9 and 0.8 mg/kg, respectively) and also in sediments
(172.5, 241.2 and 1.1 mg/kg, respectively). Antimony was
also found in high concentrations in tailings (mean con-
centration of 141.6 mg/kg), sediments (mean concentration
of 53.5 mg/kg) and mining wastes, where concentrations
were as high as 1,020 mg/kg. Concentrations of lead were
high in tailings and sediments (mean concentration of
924.1 and 379.2 mg/kg, respectively). In tailing material,
high concentrations of Au (mean values of 472.3 lg/kg)
were detected, indicating a poor efficiency in the metal
extraction process.
123
Environ Earth Sci (2010) 60:121–138
The mobility of metals in the column experiments
showed the release of Al, Fe, Mn, Cr, Cu, Ni, V and Zn in
significant concentrations, but below those detected in
groundwater samples. However, in the column experi-
ments, As, Cd, Sb, Se Pb and Au are usually mobilized in
higher concentrations than those detected in groundwater
samples.
The analysis of groundwater samples revealed high
concentrations of Al, As, Cd, Fe, Hg, Mn, Ni, Pb, Se, Sb
and Zn and high concentration of chloride and sulfate.
These concentrations were above the maximum concen-
trations defined by the European standards for drinking
water, in some groundwater samples. The high concentra-
tions of Cd, Cu, Fe, and Mn found in groundwater samples
may be associated with the low values of Eh, suggesting
that the dissolution of Fe and Mn oxyhydroxides is the
main cause for the elevated concentration of these metals
in groundwater. The distribution of total As in groundwater
is not totally related to the reductive dissolution of Fe and
Mn, since the higher concentrations of As ([ 10 lg/L) are
found in groundwater samples, which have elevated con-
centrations of Fe and Mn and samples with low-to-medium
concentrations of Fe and Mn.
The inverse modeling applied to the leaching tests
indicated the possible dissolution of jarosites and arsenian
pyrite and/or the mobilization of Fe-rich pore water from
the oxidative dissolution of arsenian pyrite into the tailing
impoundments. The mobilization of As from the tailing
material, caused by the oxidation of arsenian pyrite, may
also be influenced by the wind transport of fine particles of
Fe oxyhydroxides and jarosite to Playazo creek sediments
and nearby soils. The potential desorption of As from
goethite and ferrihydrite and the dissolution of jarosite
could result in the release of As into Playazo sediments and
groundwater.
Acknowledgements This research was supported by the Spanish
Ministry of Science and Technology (projects REN2003-09247-C04-
03 and ENE2006-13267-C05-03), in collaboration with the Energy,
Environmental and Technological Research Centre (CIEMAT). We
would like to thank the staff at the Department of Fluid Mechanics at
UPC for carrying out the leaching experiments.
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