Applied

Geochemistry
Applied Geochemistry 20 (2005) 13201356
www.elsevier.com/locate/apgeochem

Acid mine drainage in the Iberian Pyrite Belt (Odiel

river watershed, Huelva, SW Spain):
Geochemistry, mineralogy and environmental implications
Javier Sanchez Espana *, Enrique Lopez Pamo, Esther Santomia,
Osvaldo Aduvire, Jesus Reyes, Daniel Barettino
Direccion de Recursos Minerales y Geoambiente, Instituto Geologico y Minero de Espana (IGME), Rios Rosas, 23, 28003 Madrid, Spain

Received 15 July 2004; accepted 2 January 2005

Editorial handling by R. Fuge
Available online 24 May 2005

Abstract

This work reports the physical properties and water chemistry of 64 AMD discharges from 25 dierent mines in the
IPB draining to the Odiel river watershed, which have been investigated during the hydrologic year 20032004. These
AMD solutions vary largely in ow rate and chemical composition both spatially (between the dierent mine sites, sug-
gesting a strong geologic control on AMD chemistry) and seasonally (due to marked hydrologic variations), and
include cases with very low pH (mostly in the range 1.44), and extreme sulphate (up to 44 g/L SO2
4 ) and metal content
(e.g., up to 7.7 g/L Fe, 2.6 g/L Al, or 1.4 g/L Zn). Dierent hydrogeochemical facies of AMD (namely, Fe(II)/anoxic,
Fe(III)/suboxic, and aluminous/oxic) are recognized in the eld, as a response to the continuous oxidation and hydro-
lysis of dissolved Fe. Relevant geochemical aspects of these AMD environments are discussed, including: (i) the redox
chemistry of the Fe(II)/Fe(III) couple, (ii) the reaction rates for bacterially catalyzed oxidation of Fe(II) and hydrolysis
of Fe(III), (iii) the role played by dissolved Fe and Al in the acidity and chemical buering of the AMD systems, and
(iv) the solubility and trace metal retention capacity of the Fe oxyhydroxysulphate and hydrated sulphate minerals com-
monly associated with AMD. In addition, the mineralogy and chemistry of the Fe precipitates (schwertmannite, jaro-
site, goethite, ferrihydrite), Al phases (e.g., basaluminite) and MgFeAl eorescent SO4 salts (e.g., epsomite,
hexahydrite, copiapite, halotrichite, rozenite, coquimbite) present in the AMD-generating mine sites, have also been
studied. The mineralogy of the Fe precipitates is well correlated with the water pH (with jarosite at pH  2, schwert-
mannite at pH 24, basaluminite at pH 45, and ferrihydrite at pH > 6). Schwertmannite appears to be the most impor-
tant mineral phase, both in controlling the Fe solubility at pH 24, and as sorbent of trace elements (As, Cu, Zn), which
favours natural attenuation. Finally, a basin-scale environmental perspective is given in order to evaluate the impact of
AMD on the water quality, including calculation of metal loadings transported by AMD from the most important mine
districts in the province.
2005 Elsevier Ltd. All rights reserved.

1. Introduction and scopes

*
Corresponding author. Fax: +34 91 349 5834. A long history of metalliferous mining (currently ex-
E-mail address: j.sanchez@igme.es (J. Sanchez Espana). hausted) has left the Iberian Pyrite Belt (IPB) massive

0883-2927/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2005.01.011
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
sulphide province (Huelva, SW Spain) with a legacy of
abandoned mines and attendant spoil tips, including
enormous sulphide-bearing waste rock piles, tailings
and ooded pits. These mine wastes are continuing
sources of environmental contamination, mostly in the
form of acid mine drainage (AMD). These acid mine
waters have caused severe pollution of the Odiel and
Tinto uvial systems, with transference of large amounts
of acidity and dissolved metals (Fe, Al, Mn, Cu, Zn, Cd,
Pb), As and SO4 (see for example Van Geen et al., 1991,
1997; Nelson and Lamothe, 1993; Elbaz-Poulichet et al.,
1999, 2001; Davis et al., 2000; Cossa et al., 2001; Achter-
berg et al., 2003; Braungardt et al., 2003; for a review on
trace metal anomalies in the Tinto-Odiel estuarine sys-
tem and the Gulf of Cadiz). Acidity and metal concen-
trations of the AMD-aected streams have caused the
loss of most forms of aquatic life, with the exception
of some types of microorganisms adapted to these ex-
treme environments (Lopez-Archilla and Amils, 1999;
Lopez-Archilla et al., 2001; Gonzalez-Toril et al., 2003;
Amaral Zettler et al., 2003).
During the last decade, the Junta de Andaluca (Re-
gional Government) has made a considerable economic
contribution to various remediation and restoration at-
tempts aimed at reducing the environmental impact of
acid mine waters (e.g., Serrano et al., 1995). These ini-
tiatives have included the geotechnical stabilization and
revegetation of waste piles, construction of rain water
drainage systems and sealing of mine adits, as well as
passive treatments such as anoxic limestone drainage
(ALDs) and anaerobic compost wetlands (Vinas and
Lopez Fernandez, 1994; AYESA, 1996). Unfortu-
nately, these attempts have been highly ineective
due to chemical and climatic constraints (high acidity
and metal contents, seasonal variability of water
discharge).
A range of papers have been published on the eects
of this mine-related pollution in the Tinto-Odiel estua-
rine system (see above), although unfortunately, very lit-
tle work has been carried out to unravel the
geochemistry of these acid mine waters in origin, their
seasonal chemical variations, their interaction with the
stream waters, or the mineralogical and chemical com-
position of the AMD-related ochreous precipitates.
These questions are important not only from a theoret-
ical viewpoint, but also from a practical aspect, as they
are critical for the design of remediation/attenuation
strategies.
The Geological Survey of Spain (IGME) is investigat-
ing the geochemistry of the AMD systems and their
interaction with fresh water courses in the Odiel river ba-
sin, which receives the great majority of AMD discharge
from the IPB mines. This study includes the following
objectives: (1) physico-chemical characterization of
AMD and its relation to geological, mineralogical and
hydrological factors; (2) seasonal variations of AMD
1321
chemistry and metal loads; (3) mineralogical and chem-
ical transformations taking place in the AMD-generat-
ing mine sites; (4) processes favouring natural
attenuation; and (5) GIS-based, basin-scale, hydrogeo-
chemical mapping according to water quality criteria.
This paper summarises the results obtained from
February-2003 to May-2004, describing the main geo-
chemical features of the AMD systems, the mineralogi-
cal and chemical characteristics of mine drainage
precipitates and eorescent sulphate salts, and the envi-
ronmental implications.
2. Methodology and analytical techniques
2.1. Sampling
Field work was performed during several seasons
through 2003 (FebruaryMarch, April, June, July, Sep-
temberOctober, November) and 2004 (January, March,
May) and included a comprehensive and detailed explo-
ration of the study area, with identication and sam-
pling of the dierent acid mine euents and stream
waters, as well as sediments and precipitates naturally
occuring in the AMD systems, and subsequent chemical
and mineralogical-diractometric analyses of the col-
lected samples.
Water samples for chemical analyses of major ions
were taken with 60 ml-syringes and Millipore standard
sampling equipment. All samples were ltered in the
eld with 0.45 lm cellulose acetate membrane lters,
stored in 125 ml-polyethylene bottles, acidied down
to pH < 2 with concentrated HNO3, and refrigerated
during transport. The polyethylene bottles were washed
with HNO3 for 12 h prior to sampling, and a trace metal
clean procedure was always employed during sample
collection.
The solid samples (ferric crusts, sulphate eores-
cences) were directly stored in 125 ml-polyethylene bot-
tles, while the ochreous, colloidal precipitates were
taken with 60 ml-syringes and/or by ltering acid water
using a manual suction kit.
2.2. Field measurements
Field parameters such as pH, Eh, temperature (T),
dissolved O2 (DO), and electric conductivity (EC), were
measured in situ with Hanna portable instruments
(probe types HI 9025C, HI9033 and HI9025, respec-
tively) properly calibrated on site against supplied cali-
bration standards (Hanna standard solutions HI 7004
(pH 4.01) and HI 7007 (pH 7.01) for pH; Hanna stan-
dard solutions HI 7021 (240 mV) and 7022 (470 mV)
for Eh). For Eh measurements, the mV reading obtained
with the PtAg/AgCl electrode system was corrected for
temperature and adjusted to a potential relative to that
1322 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
of the standard hydrogen electrode (see Method in
Nordstrom, 1977).
Flow rates have been calculated in all cases by con-
ventional methods using digital ow meters (GLOBAL
WATER) in previously dened stream sections.
Quantitative measurement of acidity, alkalinity and
Fe(III)/Fe(II) concentrations, were performed in situ
with Hach titration-based test kits using the digital titra-
tion methods 8201 (bromophenol blue) and 8202 (phe-
nolphthalein (total) acidity; AC-DT model), 8203
(phenolphthalein (total) alkalinity using H2SO4; AL-
DT model), and 8214 (citrate, sodium periodate and
sulfosalicylic acid with TitraVer standard solution
titration cartridge for Fe(III) and total Fe) reported by
the Hach Instruments company. Titration tests for the
measurement of AMD acidity were performed at inter-
mediate pH values of 3.7 and 5, and total acidity (pH
8.3), with NaOH 1.6 N and continuous measurement
of pH and the amount of base used in every step.
For routine, semiquantitative estimations of Fe(II)
concentration, Merckoquant-type (MercK) Fe(II)
strips were also used. Similar methods were occasionally
applied for semiquantitative estimations of other ele-
ments such as SO2
4 ; Zn and Mn.
2.3. Laboratory analyses
All samples were analyzed in the IGME laboratories.
Natural water samples were analyzed using diverse spec-
trometric techniques, such as spectrophotometry (ALLI-
ANCE Integral Plus) for SO4, NO3, Cl and PO4, AAS
(ame operation, VARIAN FS-220) for Na, K, Mg,
Ca and Fe, and ICP-MS (LECO Renaissance) for trace
metals. AMD samples were analyzed by AAS for Na, K,
Mg, Ca, Fe, Cu, Mn, Zn and Al, ICP-AES for Be, Ni
and Se, and ICP-MS for Ag, As, Ba, Cd, Co, Cr, Hg,
Mo, Pb, Sb, Th, Tl, U and V. Sulphate was gravimetri-
cally measured as BaSO4, whereas Cl was analyzed titri-
metrically with AgNO3. The accuracy and precision of
the analytical methods were veried against certied ref-
erence waters such as SRM 1643 (trace elements in
water, NIST), APG 4073 (trace metals in waste water,
APG) and others (e.g., internal samples of industrial
mine euents, control samples of the Water Research
Centre
s AQUACHECK international program) and
close agreement with certied values was achieved for
all metals. 115In was used as internal standard for cali-
bration of the ICP-MS analyses. The detection limits
for trace elements in natural waters were 2.5 lg/L for
Se, 2 lg/L for Al, Be, Cr, Hg and Zn, 1 lg/L for Ni,
and 0.5 lg/L for Ag, As, Ba, Cd, Co, Cu, Mn, Mo,
Sb, Tl, Th, U and V. The detection limits for trace ele-
ments in acid mine waters were 100 lg/L for Se and
Ni, 10 lg/L for Be and Zn, 2 lg/L for Ag, Ba, Co, Cr,
Hg and Pb, 1 lg/L for U, 0.5 lg/L for V, 0.4 lg/L for
As, Cd, Cu and Sb, and 0.2 lg/L for Mo, Tl and Th.
The detection limits for major cations (Na, K, Ca,
Mg, Mn, Fe, Al) was <1 mg/L in all cases.
Solid samples were analyzed using XRF (PHILIPS
1404) for the elements Si, Al, Fe, Ca, Ti, Mn, K, Mg
and P, elemental analyzer (Eltra CS-200) for total S,
ICP-MS (after digestion with HNO3 and H2O2 follow-
ing the method described in USEPA 3050B) for Cd,
Co, Cr, Hg, Mo, Sb, Th, Tl, U, V, Zn, and AAS for
Na, Cu, As and Pb. A number of certied international
reference materials (BCS 175/2, BCS 302/1 and BCS 378,
from the British Chemical Standards; FER-1 and FER-2
from the Canada Centre for Mineral and Energy Tech-
nology) were used to check the accuracy of the analytical
data. The detection limits for trace elements in solids
were 10 ppm for Ni and Se, 2 ppm for Be, Co, Cu,
Hg, Th, V and Zn, 1 ppm for Cr, 0.5 ppm for Mo and
0.2 ppm for Cd, Sb and U.
The solid samples have been mineralogically charac-
terized by powder XRD using a PHILIPS PW 1710 dif-
fractometer with Cu Ka radiation (40 kV, 30 mA), and a
diracted-beam monochromator. For routine XRD
inspections (for samples of sediment and sulphate salts),
060 2h scans were used with 0.5 s counting time per
step. For more detailed XRD proles (for the Fe colloi-
dal precipitates), slower counting times of 50 s per step
interval in 1080 2h scans, were selected.
2.4. Geochemical modelling
The PHREEQC code (version 2.0; Parkhurst and
Appelo, 1999) was used for geochemical modelling,
including calculation of theoretical Eh (pe) values based
on the Fe(II)/Fe(III) redox couple, activity and chemical
speciation of dissolved species, and saturation index of
analyzed minerals in the parent acid solutions. The ther-
modynamic database of PHREEQC was enlarged with
data from other geochemical codes (MINTEQA2,
WATEQ4F (Ball and Nordstrom, 1991)) for the solubil-
ity of schwertmannite and ferrihydrite.
3. Geological and hydrological framework
3.1. Geology
The Odiel uvial system (1360 km in length) drains a
vast area of 2300 km2, crossing the Province of Huelva,
from Sierra de Aracena in the North to the Huelva estu-
ary in the South, and receives most of the acid mine
euents emerging from IPB mines (Fig. 1).
The upper, northernmost part of the basin is under-
lain by plutonic and metamorphic rocks (sericitic schists,
quartzites, granites, gneises, marbles and tus) of Upper
Precambrian to Devonian age. The middle and lower
basin is characterized by the Upper Devonian to Middle
Carboniferous volcanic and sedimentary rocks of the
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1323

Fig. 1. Location map of the Odiel river watershed and the IPB massive sulphide mines studied in the present work.

IPB (comprising the PQ group, with phyllites and
quartzites, the volcanic-sedimentary complex (VSC),
formed by shales, greywakes, acid to basic volcanic
and volcaniclastic rocks, and the Culm group, made of
a ysch-like sequence of shales and greywakes). Finally,
the southernmost area of the Odiel basin drains Miocene
detrital materials (sands, silts, clays).
The IPB represents the largest concentration of mas-
sive sulphide on Earth, and despite its long history of
extensive mining (dating from the Chalcolitic age, 3 ka
1324 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
B.C.) still hosts 1700 Mt of unmined massive sulphides,
including 35 Mt Zn, 14.6 Mt Cu, 13 Mt Pb, 46,100 t Ag
and 880 t Au (e.g., Leistel et al., 1998). From the North
of Seville to the South of Lisbon, the IPB comprises
more than 80 mines, including historical deposits with
more than 100 Mt such as Ro Tinto, Tharsis, La Zarza,
Sotiel and Aznalcollar in the Spanish part, or Aljustrel,
Loussal and Neves-Corvo in the Portuguese zone.
This mining legacy has resulted in a total of 57 aban-
doned waste piles (with a total volume of 107 Hm3) and
10 tailings dumps (42 Hm3) in the province of Huelva
alone (IGME, 1998), which represents one of the
World
s largest accumulations of pyritic mine wastes.
The mineralization is dominated by pyrite (>90% in
volume), with variable amounts of sphalerite, chalcopy-
rite and galena. Other minor minerals are tetrahedrite-
tennantite, arsenopyrite, pyrrhotite, cassiterite,
magnetite and hematite. Pyrite is texturally variable from
ne-grained (colloform, framboidal) to coarse-grained
crystals (Velasco et al., 1998; Sanchez Espana, 2000).
Gangue minerals include abundant silicates (quartz,
chlorite, sericite and feldspars), and minor amounts of
carbonate and barite (Sanchez Espana, 2000).
The chemical composition of the sulphide ores is
highly variable among the dierent deposits and ore fa-
cies (massive, banded, stockwork). Whole-rock compo-
sitions of sulphide ores normally show ranges of
1842% S, 1157% Fe2O3, 020% SiO2, 05% Al2O3,
05% MgO, 01.5% MnO, 07% CaO, with element
contents of 400305,000 ppm Zn, 30084,000 ppm Cu,
75230,000 ppm Pb, 5617,600 ppm As, 234500 ppm
Sb, 7800 ppm Cd and 8612 ppm Co, among others
(e.g., Sanchez Espana, 2000).
In short, the mineralogical and textural characteris-
tics of the IPB ores (namely, (1) dominantly pyritic,
ne-grained, usually brecciated and fractured, highly
reactive sulphide grains and (2) a lack of carbonates to
neutralize acidity), favour pyrite oxidation/dissolution
and the subsequent formation of AMD.
3.2. Hydrology
The hydrological characteristics of the province of
Huelva are typical of a semi-arid, Mediterranean-type
climate. The average water ow at Gibraleon (near
the Odiel river mouth) has been estimated to be around
320 Hm3/a (10 m3/s) for the period 19691997 (Confed-
eracion Hidrograca del Guadiana, unpublished data).
However, this is just an oversimplied calculation that
masks a complex reality dened by marked variations
in water discharge and subsequent water ow rates
from summer (JuneSeptember) to winter, as well as
between dierent hydrologic years (Fig. 2). Rainfall
discharge (up to 1070 mm/day in winter, approaching
0 mm/day in summer; Fig. 2), evapotranspiration
(<1 mm/day in winter, and up to 10 mm/day during
the summer), and consequently, acidity and metal loads
transported by AMD (see Section 5.3.1, Table 10), are
also very randomly distributed through the year, mak-
ing the predictions and calculations neccessary for the
design of any remediation/attenuation technique very
dicult.
4. Results
4.1. Chemical characterization of stream waters
With the aim of obtaining a chemical reference back-
ground for stream water quality in the area, 12 samples
of natural stream waters collected from several locations
were chemically analyzed (Table 1). These samples in-
cluded water courses close to or upstream of the mine
sites, but always unaected by AMD discharge based
on EC, Eh and pH eld data. Six of these samples come
from streams draining unmineralized rocks of the miner-
alization-hosting lithostratigraphic unit (VSC), and the
rest come from streams draining undierentiated sedi-
mentary rocks of the IPB (comprising shales, phyllites,
quartzites and greywakes from the PQ and Culm
groups) and Sierra de Aracena (including sericitic
schists, quartzites, granites, gneises, marbles and tus).
Additionally, water alkalinity has been measured by
titration-based tests performed in situ in 31 dierent
stream water samples to cover the whole basin (Table 2).
The chemical composition of these waters shows
lower SO4 and Cl concentrations (632 mg/L SO2
4 ,
1226 mg/L Cl
) with respect to bicarbonate content
(69 mg/L HCO
3 on average). There is no clear chemical
distinction between waters draining VSC materials and
those draining undierentiated rocks (e.g., SO2
4 vs.
pH; Fig. 3).
In all cases, natural stream waters are characterized
by low redox potential (Eh = 250470 mV), circumneu-
tral pH, low conductivity values (EC = 98578 lS/cm),
and very low metal concentrations. The correlations be-
tween trace metals are poor and do not show any signif-
icant trend. The most signicant contents are those of Fe
(26445 lg/L), Al (23253 lg/L), Mn (653 lg/L) and
Ba (561 lg/L). The Cu and Zn contents are in the
ranges of 17 and 112 lg/L, respectively. The concen-
trations of other trace elements such as Ag, Be, Cd,
Co, Cr, Hg, Ni, Mo, Sb, Se, Th, Tl and U were always
close to or below the detection limit of the analytical
technique (some of these elements have been conse-
quently omitted in Table 1). Such element concentra-
tions are always below drinking-water standards
(50 lg/L for As, Cu, Pb, Mn and Cr; 5 lg/L for Cd,
3 mg/L for Zn, 0.3 mg/L for Fe; EU Council Directive
75/440/EEC of 16 June 1975 concerning the quality re-
quired of surface water intended for the abstraction of
drinking water in the Member States).
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1325

90

Rainfall discharge (mm/day)

80 C
70
Diary rainfall discharge
0.6 60
50 Odiel waterheads 2003
B
40
30
0.4
Frequency

20
10
A 0
0.2 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
2000

Months
1800

1600 0
0 4 8 12 16 20 24 28 32 36 40 44 48 52 56 60
1400 Daily Water Flow (m 3/s)
Flow rate (Hm /year)

1200
3

Yearly Flow Rate

1000 Odiel outlet 1969-1997

800

600

400

200

0
1969 1971 1973 1975 1977 1979 1981 1983 1985 1987 1989 1991 1993 1995 1997

Years

Fig. 2. Hydrological characteristics of the Odiel river watershed, including: (A) annual ow rate, (B) daily water ow, and (C) rainfall
discharge. Annual and daily ow rate data (A and B) correspond to the period 19691997 for the Odiel river mouth in Gibraleon
(unpublished data from Confederacion Hidrograca del Guadiana), whereas (C) shows the distribution of rainfall discharge in the
uppermost basin during 2003.

Consequently, it can be stated that, from a geochem- sedimentary rocks of the IPB (PQ, VSC and Culm
ical viewpoint, the IPB stream waters of unmined areas units).
do not show any signicant chemical signature, with In general, these data indicate a limited acid-neutraliz-
water quality standards akin to water courses draining ing capacity for most stream waters in the area, which has
siliciclastic rocks. drastic environmental consequences (the potential acidity
Another important chemical feature of the stream of the acid mine euents is about 23 orders of magnitude
waters is their relatively low alkalinity values (Table higher than alkalinity of stream waters see below , and
2). Alkalinity of these waters is basically determined therefore, they cause a rapid pH decrease of the natural
by the concentration of HCO
3 ions, being therefore very water courses, even when AMD volumes are low in rela-
variable between dierent lithological areas. Thus, water tion to stream water volumes).
alkalinity is in the range 120240 mg/L CaCO3 eq. in the
upper basin (which drains Precambrian to Devonian 4.2. Location and description of acid mine euents
metamorphic and plutonic rocks of the Sierra de Arac-
ena), and between 10 and 115 mg/L CaCO3 eq. in the By May-2004, 64 AMD discharges from 25 dierent
middle and lower basin, characterized by volcanic and mines of the IPB have been studied. AMD-generating
1326 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

mine sites include, in decreasing order of importance,

The corresponding sample number, site description, drained area (km2), are provided in all cases. All samples were collected in April 2003 except (*), which was collected in March 2004. Abbreviations: Q,
waste rock piles (50%), mine adits (30%), tailings
impoundments (10%), mine holes (7%), and mine pit
lakes (3%). These mine sites include some of the largest
and most important deposits in the IPB (Ro Tinto,
Tharsis, La Zarza, San Telmo, Sotiel-Almagrera) and
many others of medium size (Lomero-Poyatos, San
Miguel, Cueva de la Mora, Aguas Tenidas, Concepcion,
San Platon, Poderosa, Tinto-Sta. Rosa), which repre-
sent, as a whole, the total of acid emissions received
by the Odiel uvial system.
A site description with eld parameters of the studied
AMD discharges is given in Table 3. The chemical com-
position of these acid euents is reported in Table 4,
Fe(II)/Fe(III) and acidity data are given in Table 5,
and some signicant AMD euents from various mine
sites of the area are shown in Fig. 4. All analyses have
been performed in the laboratory except for acidity
and Fe(II)/Fe(III) (calculated in situ by titration-based
tests). Most AMD discharges have been sampled and
analyzed several times through the period 20032004,
in order to study their seasonal variations in chemistry
and ow rate.
Both water volume and chemical composition of
AMD are very variable seasonally and among dierent
deposits (Table 3). The most important AMD dis-
charges come from the largest deposits (e.g., Ro Tinto,
Tharsis, La Zarza and San Telmo), whereas acid mine
waters coming from the smaller deposits (e.g., El Carpio,
Field parameters and chemical composition of natural stream waters of the Odiel river watershed

La Torerera, San Platon, Esperanza, El Soldado,

Angostura) always show very low water volumes. Many
acid leachates from waste rock piles (e.g., Monte Ro-
mero, Confesionarios) are ephemeral, being active only
after rainfall episodes.
water ow rate; DO, dissolved O2; EC, electric conductivity; n.a., not analysed.

4.3. Chemical composition of AMD

The data reported in Tables 4 and 5 show also that

the acid emissions are far from being chemically uni-
form. In fact, they can be dierentiated in terms of sea-
sonal continuity (permanent, seasonal or ephemeral
drainage), water volume (ow rates are in the range
0.1220 L/s), acidity (20030,000 mg/L CaCO3 eq.), re-
dox conditions (Eh = 400800 mV; pe = 6.713.5), elec-
tric conductivity (EC = 100024,000 lS/cm), dissolved
O2 content (from totally anoxic to O2-saturated), dis-
solved Fe(II) to Fe(III) ratio (Fe(II)/Fet = 0.11), and
colour (green, yellow to reddish, white, blue). Based
on this eld evidence, 3 main hydrogeochemical facies
for AMD can be recognized in the area, namely: (1) fer-
rous/anoxic (pH 1.44.0, Eh = 400640 mV, DO  0
20% sat., Fe(II)/Fet  0.51, green-coloured), (2) ferric/
suboxic (pH 2.03.5, Eh = 640800 mV, DO = 50
100% sat., Fe(II)/Fet  0.10.5, yellow to reddish-
Table 1

coloured), and (3) aluminous/oxic (pH 4.05.7,

Eh 6 500 mV, DO  100% sat., Fe(III)  0 mg/L,
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1327

Table 2
Alkalinity values (mg/L CaCO3 eq.) for stream waters in the Odiel river basin
Sample River/creek Lithostratigraphic Sampling pH EC Alkalinitya
No. unit date
959-3 Aserrador Miocene, PQ, VSC May-04 7.4 557 146
981-5 Ayo. San Bartolome Miocene, PQ, VSC May-04 7.3 578 157
937-11 Ayo. Sepultura Culm May-04 7.4 168 58
959-3 Aserrador Culm Nov-03 7.0 460 66
937-18 Bco. Ovejeros Culm May-04 7.4 266 69
937-14 Tallisca Culm May-04 7.2 388 100
959-8 Chapinero Culm May-04 7.3 270 104
937-5 Escalada Culm, Pulo de Lobo, VSC May-04 7.1 131 21
937-12 Fresnera Culm, Pulo de Lobo, VSC May-04 6.5 123 11
960-11 Palanco VSC May-04 6.9 322 94
960-6 Carrasco VSC May-04 7.8 331 114
938-52 Bco. Hocino VSC, Culm May-04 7.8 220 88
937-9 Tamujoso VSC, Culm May-04 7.4 370 68
959-9 Cascabelero VSC, Culm May-04 7.8 302 83
938-26 Rivera Seca VSC, Granites, PQ May-04 7.4 135 39
960-12 Rivera del Villar VSC, PQ May-04 7.8 353 107
959-19 Vega del Almendro VSC, PQ May-04 8.4 433 113
938-45 Olivargas PQ Nov-03 7.7 162 34
938-5 Olivargas (before reservoir) PQ, Culm Jan-04 9.0 165 65
937-12 Fresnera Pulo de Lobo, PQ May-04 6.5 123 11
937-5 Rivera Pelada Pulo de Lobo, PQ, VSC Nov-03 6.8 166 18
938-55 Valdehornos Pulo de Lobo, Culm May-04 7.4 98 20
938-54 Bco. del Perro Pulo de Lobo, Culm May-04 8.8 161 65
917-1 Acebuche Pulo de Lobo, Sierra de Aracena Maassif May-04 8.4 211 80
938-28 Escalada (before San Miguel) Sierra de Aracena Maassif May-04 8.3 275 121
917-3 Casares Sierra de Aracena Maassif May-04 8 235 135
917-2 Almonaster Sierra de Aracena Maassif May-04 8.1 324 137
938-8 Santa Eulalia Sierra de Aracena Maassif May-04 8.4 300 143
938-1 Odiel Sierra de Aracena Maassif May-04 8.7 335 148
917-4 Linares Sierra de Aracena Maassif May-04 8.5 383 197
918-1 Jabuguillo Sierra de Aracena Maassif May-04 8.1 472 236
The corresponding sample number, site description, lithostratigraphic units drained, date of sampling, and some other relevant eld
data (pH and EC), are provided in all cases. Data have been organized from top (Miocene, southernmost basin) to bottom (Upper
Precambrian to Devonian, Northernmost basin) in increasing age of the rocks drained by the corresponding rivers and creeks. See text
for explanation.
a
In mg/L CaCO3 eq.
35
VSC rocks
white-coloured). This distinction is only valid at the 30
Undifferentiated rocks
source points (mine adits, waste pile leachates), as the
25
SO4 (mg/L)

oxidation and hydrolysis of Fe at pH  2.53 in these

waters is very fast after their contact with atmospheric 20
O2 (see Section 5.1.2), and provokes the transition from 15
Fe(II)/anoxic to Fe(III)/suboxic and, when mixed with
10
stream waters, aluminous/O2-saturated facies, in a very
short distance. Type 2 (ferric/suboxic) AMD is, by far, 5
the most common and volumetrically important among 0
the acid emissions in the IPB, with ferrous and alumi- 5 6 7 8
nous euents being scarce and always having very low pH
water volumes (Table 3).
Fig. 3. SO2

4 vs. pH diagram for natural stream waters in the
The chemical composition of these waters include ex- Odiel river basin. Waters draining dierent types of rocks
treme concentrations of dissolved SO4 (up to 44 g/L) (siliceous volcanic and sedimentary rocks of the volcanic-
and metals (up to 7.7 g/L Fe, 2.6 g/L Al, 2.9 g/L Mg, sedimentary complex (VSC), and undierentiated rocks from
1.4 g/L Zn, 435 mg/L Cu and 440 mg/L Mn; Tables 4 other lithostratigraphic units of the IPB such as the Culm, PQ
and 5). Trace elements are also signicantly enriched or Pulo do Lobo Units) are distinguished.
 1328
Table 3
Relation of the AMD discharges recognized and studied in the IPB (Odiel river basin), with description of the mine sites, AMD type, geographic location (in UTM coordinates), and eld measurements (including water ow (Q), pH, dissolved
O2 (DO), Eh, electric conductivity (EC), and temperature (T))

Mine AMD type AMD No. Sampling date Site position Field measurements

Year Month Day X-utm Y-utm Altitudea Q pH DO DO Eh EC T

(L/s) (mg/L) (%) (mV) (ls/cm) (C)

Aguas Tenidas Mine hole 938-109 2003 6 19 160425 4188518 305 0 2.5 1.6 17 704 25.5
2003 2 28 160425 4188518 305 2 3.1 0.0 2 604 1950 20.0
Angostura Mine adit 938-110 2003 6 19 172771 4186494 276 0.1 2.7 8.7 95 655 2240 18.9
2003 3 1 172771 4186494 276 0.2 2.7 7.4 77 678 1945 17.0
Angostura Mine hole 938-11 OB 2003 6 19 172771 4186494 276 0 2.2 2.2 20 636 3750 20.5

J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

2003 3 1 172771 4186494 276 0 2.2 2.2 17 653 3150 15.0
Angostura ALD outow 938-111 2003 6 19 172976 4186597 324 0.1 3.2 1.3 17 521 2140 24.3
2003 3 1 172976 4186597 324 0.2 3.0 0.0 0 563 2000 15.6
Campanario Waste-rock pile leachate 960-105 2003 7 30 162318 4162098 166 0 3.4 1.7 20 495 3720 21.2
Campanario Mine hole 960-109 2004 3 12 162182 4162073 167 1 2.6 0.8 9 589 3970 19.2
Castillo Buitron ALD inow 960-108 2003 9 25 167621 4171913 139 0.7 2.5 0.2 2 616 1010 19.5
Concepcion Waste-rock pile leachate 938-105 2004 3 12 176582 4187684 224 2.8 2.3 6.1 66 703 4560 16.4
2003 9 26 176582 4187684 224 2.4 2.5 4.1 45 733 3050 22.0
Confesionarios Waste-rock pile leachate 937-101 2003 2 27 157912 4190185 344 2 2.0 0.0 0 733 5700 20.0
Confesionarios Waste-rock pile leachate 937-113 2004 3 18 157875 4189355 311 15 2.6 8.9 100 633 12,500 21.0
Confesionarios Waste-rock pile leachate 937-114 2004 3 18 157592 4189631 314 7 2.0 6.2 68 648 18,230 20.0
Cueva de la Mora Mine adit 938-107 2004 3 10 165893 4187971 254 3.5 3.3 1.3 14 565 4190 20.7
2003 9 27 165893 4187971 254 1.6 3.2 4.6 52 548 3790 20.7
Descamisada Mine adit/ALD outow 960-106 2004 3 12 161488 4162711 145 0.2 3.9 0.3 4 438 2740 19.2
2003 7 30 161488 4162711 145 3 4.2 1.1 14 360 2050 22.0
Descamisada Mine hole 960-107 2003 7 30 161557 4162741 151 1 2.4 1.7 21 687 3080 24.0
El Carpio Mine adit 937-110 2004 3 10 149233 4192241 289 1.56 2.8 6.3 75 663 2980 24.8
2003 9 27 149233 4192241 289 0 2.1 1.5 19 643 4700 27.0
2003 7 29 149233 4192241 289 0 2.6 3.4 47 641 4660 32.0
El Soldado Mine adit 938-119 2003 4 1 178259 4185728 339 2 2.5 6.5 73 661 1800 20.9
Esperanza Mine adit 938-122 2004 3 12 175738 4185620 248 2.2 2.7 0.4 4 599 4470 20.3
2003 6 19 175738 4185620 248 2.3 2.8 0.0 0 551 3580 21.6
Gloria Mine adit 960-103 2003 6 23 165708 4172769 130 0.1 2.8 4.5 53 673 1970 24.0
La Poderosa Waste-rock pile leachate 938-103 2003 9 23 177782 4183954 258 0.2 1.9 2.9 32 659 5040 21.1
La Poderosa Mine adit 938-113 2003 3 6 177896 4184244 298 0 3.2 3.5 38 633 5500 20.0
La Poderosa Mine adit 938-114 2004 3 18 177028 4184430 241 4.5 1.7 0.0 0 618 13,000 21.0
2003 9 23 177028 4184430 241 0.3 1.6 0.1 1 632 9540 21.3
2003 6 18 177028 4184430 241 1.6 1.4 0.6 7 595 10,080 20.4
2003 4 1 177028 4184430 241 3.5 1.6 1.7 19 614 16,000 24.0
2004 3 6 177028 4184430 241 3.7 1.7 0.3 3 599 15,200 22.0
La Poderosa Waste-rock pile leachate 938-118 2003 4 1 177861 4184226 289 0.05 5.4 8.2 87 501 2200 20.9
La Torerera Waste-rock pile leachate 959-100 2003 3 3 156170 4168339 85 1 3.1 9.5 96 683 1200 16.0
La Zarza-Perrunal Mine adit 937-108 2004 3 10 159407 4180411 229 2.0 2.9 2.1 27 486 7450 29.0
2003 9 28 159407 4180411 229 0.5 3.2 1.4 18 513 7230 27.9
2003 6 21 159407 4180411 229 0.6 2.9 0.7 10 491 7750 31.1
La Zarza-Perrunal Mine adit 937-109 2004 3 10 159961 4180148 198 0.9 3.6 4.4 47 610 2470 18.5
2003 9 28 159961 4180148 198 0.3 3.4 2.2 25 618 1990 20.8
2003 6 21 159961 4180148 198 0.5 3.5 2.7 32 615 2820 21.2
Lomero-Poyatos Mine adit 937-102 2004 3 13 154380 4191826 348 0.5 2.8 8.3 89 648 4510 17.8
2003 9 27 154380 4191826 348 0.4 3.2 4.3 53 591 4770 24.3
2003 6 21 154380 4191826 348 5.0 2.7 3.2 38 612 4880 22.7
2003 2 28 154380 4191826 348 8 3.0 3.6 45 571 6000 25.5
Monte Romero Waste-rock pile leachate 938-101 2003 2 28 166209 4188237 264 2.8 8.2 82 693 1150 15.6
Rio Tinto Ore dump leachate 938-116 2003 4 1 181556 4183015 306 0.1 2.7 7.4 75 621 7300 15.7
Rio Tinto Ore dump leachate 938-117 2003 4 1 181215 4182846 339 0.05 2.6 8.7 92 689 6100 16.7
Rio Tinto (embalse del Cobre) Water reservoir outow 938-48 2004 3 18 183632 4182736 370 48 4.0 9.8 99 633 2200 15.0
2003 4 5 183632 4182736 370 220 4.6 9.5 102 478 1240 19.1
Rio Tinto (Corta Atalaya) Mine adit 938-102 2004 3 16 180507 4180177 221 1 2.3 5.0 57 667 10,050 21.0
2003 9 23 180507 4180177 221 <0.5 2.2 7.7 91 799 12,370 13.4
2003 7 29 180507 4180177 221 <0.5 2.4 5.0 60 762 9760 22.2
Rio Tinto (Corta Atalaya) Waste-rock pile leachate T-1 2004 3 16 181427 4179918 270 28 2.6 0.5 6 570 17,200 24.7
2003 7 29 181427 4179918 270 10 3.0 0.9 11 537 17,120 25.9
2003 6 17 181427 4179918 270 15 2.8 0.8 10 544 15,330 24.8
2003 3 5 181427 4179918 270 90 2.7 0.0 0 614 16,000 24.0
Rio Tinto (Corta Atalaya) Waste-rock pile leachate 938-112 2003 6 17 181429 4179951 328 1 2.6 0.4 4 622 19,400 30.8
2003 4 1 181429 4179951 328 2 2.5 1.1 12 655 10,500 16.5
Rio Tinto (Corta Atalaya) Waste-rock pile leachate 938-124 2004 3 16 180135 4180482 21 2.8 9.3 97 823 7700 17.0

J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

2004 1 15 180135 4180482 25 2.5 848 6850 16.8
2003 11 13 180135 4180482 20 60 18,000 16.2
Rio Tinto (Corta Atalaya) Waste-rock pile leachate 938-125 2004 3 16 182091 4180510 331 6 2.5 0.0 0 622 13,500 21.0
2004 1 15 182091 4180510 331 20 2.5 7 636 14,300 21.0
2003 11 13 182091 4180510 331 15 2.7 4.2 48 620 14,200 21.0
Rio Tinto (Corta Atalaya) Waste-rock pile leachate 938-126 2004 3 16 180607 4179004 290 10 2.4 0.0 0 643 10,200 17.5
2004 1 15 180607 4179004 290 17 2.3 0.0 0 636 11,850 17.0
2003 11 13 180607 4179004 290 5 1.7 4.4 46 656 8300 17.6
Rio Tinto (Corta Atalaya) Waste-rock pile leachate 938-127 2004 3 17 181473 4181168 277 <0.5 2.6 9.1 95 748 9400 16.0
Rio Tinto (Corta Atalaya) Ore dump leachate 938-128 2004 3 17 181527 4181164 298 1 4.2 0.0 0 396 7000 20.0
Rio Tinto (Corta Atalaya) Waste-rock pile leachate 938-129 2004 3 17 181360 4181323 13 3.8 8.5 93 477 5850 19.0
San Miguel Waste-rock pile leachate 938-108 2003 9 24 169325 4185855 167 0.02 1.5 3.1 41 646 13,200 30.3
2003 2 27 169325 4185855 167 4 1.8 8.5 85 641 8500 19.1
San Miguel Mine hole 938-121 2003 9 24 169336 4186144 174 0.2 2.2 0.2 3 552 5970 19.8
2003 6 19 169336 4186144 174 1.5 2.3 0.7 6 564 5710 19.3
2003 4 3 169336 4186144 174 10 2.3 0.0 0 613 6000 20.0
San Platon ALD outow 938-106 2004 3 12 176602 4186051 177 2.0 2.5 0.6 5 599 6030 19.0
2003 9 26 176602 4186051 177 0.2 2.7 2.1 25 558 5750 17.4
San Platon Mine adit 938-123 2004 3 12 176678 4186540 218 0.1 3.0 4.7 47 699 1690 14.6
2003 10 2 176678 4186540 218 0.1 3.1 8.8 100 786 1770 18.6
San Telmo Waste-rock pile leachate 937-104 2004 3 10 150048 4191059 273 2.0 2.5 0.4 4 636 13,810 21.6
2003 9 27 150048 4191059 273 0.4 2.5 0.4 5 647 10,480 24.2
2003 7 29 150048 4191059 273 2.6 2.1 26 625 11,950 24.4
2003 6 21 150048 4191059 273 1.5 2.3 0.4 5 619 13,270 24.0
San Telmo Waste-rock pile leachate 937-105 2004 3 10 150116 4191087 280 2.7 2.4 0.5 4 607 10,650 21.2
2003 9 27 150116 4191087 280 1.3 2.5 0.6 5 608 7660 21.4
2003 7 29 150116 4191087 280 2.4 0.9 11 605 9080 20.6
2003 6 21 150116 4191087 280 3.0 2.2 0.1 1 604 9850 21.1
San Telmo Pit lake outow 937-106 2004 3 10 150492 4191108 263 40 2.9 9.9 101 750 4050 15.2
2003 9 27 150492 4191108 263 0 2.8 8.3 100 782 4550 23.8
2003 7 29 150492 4191108 263 3 2.7 6.7 92 775 4430 30.4
2003 6 21 150492 4191108 263 5 2.5 7.1 92 779 4280 26.8
San Telmo Waste-rock pile leachates 937-107 2004 3 10 150703 4191494 278 38 3.2 8.2 93 629 3480 20.1
2003 9 27 150703 4191494 278 9 3.3 7.1 88 621 3250 24.5
2003 7 29 150703 4191494 278 3.2 7.6 99 615 3270 27.3
2003 6 21 150703 4191494 278 10 3.0 7.2 90 630 3150 26.7
San Telmo Waste-rock pile leachate 937-111 2004 3 10 149942 4191151 282 0.5 2.7 8.8 89 722 12,550 14.9
2003 9 27 149942 4191151 282 0.7 2.8 6.7 80 725 12,240 21.1
2003 7 29 149942 4191151 282 2.7 5.7 70 719 12,230 22.5
Sotiel-Almagrera Ore dump leachate 960-102 2003 4 8 160171 4173540 315 0 1.8 6.7 79 713 5650 23.5
Sotiel-Almagrera Ore dump leachate 960-110 2004 5 10 160171 4173540 315 1.5 2.7 3.5 40 546 6470 18.0

1329
 1330
(continued on next page)

J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

Table 3 (continued)
Mine AMD type AMD No. Sampling date Site position Field measurements

Year Month Day X-utm Y-utm Altitudea Q pH DO DO Eh EC T

(L/s) (mg/L) (%) (mV) (ls/cm) (C)

Sotiel-Almagrera Ore dumps outow 960-5 2003 11 13 162584 4172286 83 80 2.8 9.9 101 642 2200 14.2
Sotiel-Almagrera Ore dumps outow 960-5 2004 5 10 162584 4172286 83 130 7.9 9.0 101 325 3200 21.0
Tharsis Waste-rock pile leachate 959-101 2003 3 4 138400 4168773 250 0.5 3.1 9.3 95 697 3800 20.7
Tharsis Pit lake 959-103 2003 6 20 136192 4168648 252 0.0 2.2 790 3950 26.8
Tharsis Waste-rock pile leachate 959-104 2004 3 11 138752 4168503 203 0.3 2.9 8.3 86 616 4940 15.1
2003 9 29 138752 4168503 203 0.1 2.5 7.4 81 723 6030 22.0
Tharsis Waste-rock pile leachate 959-105 2004 3 11 138332 4167778 216 2.3 0.2 2 636 16,670 16.7
2003 9 29 138332 4167778 216 0.4 2.3 0.7 9 658 23,900 26.0
Tharsis Mine adit 959-106 2004 3 11 136336 4167549 242 3.3 2.0 1.5 15 615 6010 17.4
2003 9 29 136336 4167549 242 0.4 2.6 0.4 3 609 4030 20.7
Tharsis Waste-rock pile leachate DB-1 2003 4 7 135355 4169059 236 1 2.4 8.2 87 800 2870 17.4
Tharsis Waste-rock pile leachate DB-2.1 2003 9 29 135347 4168661 249 0.5 2.5 0.3 4 628 8440 20.2
2003 7 31 135347 4168661 249 2.5 1.9 22 434 8300 20.6
2003 6 20 135347 4168661 249 1.5 2.3 0.0 0 639 6710 18.6
2003 4 7 135347 4168661 249 4 2.2 0.0 0 663 5560 18.6
Tharsis Waste-rock pile leachate 959-107 2004 5 13 138231 4169650 226 15 2.7 3.0 40 609 15,330 28.7
Tharsis Waste-rock pile leachate 959-108 2004 5 13 138431 4169298 234 0.5 2.2 4.9 63 614 22,700 22.7
Tharsis Waste-rock pile leachate 959-110 2004 5 13 138495 4168461 243 2.9 6.3 72 728 3700 19.3
Tinto-Sta Rosa Mine adit 960-100 2003 6 23 164566 4172338 120 1.8 3.3 6.7 71 560 3500 21.0
2003 3 3 164566 4172338 120 0.6 3.4 7.1 78 522 3630 21.5
Tinto-Sta Rosa Mine adit 960-101 2003 6 23 164591 4172420 116 0.5 3.3 0.3 4 604 1750 19.2
2004 3 11 164591 4172420 116 3.3 0.0 0 599 1830 12.4
Tinto-Sta Rosa Waste-rock pile leachate 960-102 2003 6 23 164575 4172420 110 1.0 5.7 8.8 90 428 539 19.8
2004 3 11 164575 4172420 110 0.6 5.5 9.4 96 447 685 14.7
Trincheron Mine adit/ALD outow 960-104 2004 3 12 161590 4162444 162 0.3 3.2 1.5 15 692 1142 14.7
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1331

Table 4
Chemical composition of AMD discharges in the IPB (Odiel river watershed)

Abbreviations: b.l., below detection limit; n.a., not analyzed.

 1332
Table 5
Fe2+ and Fe3+ concentrations, and acidity (measured at pH values of 3.7, 5.0 and 8.3) of the AMD discharges in the IPB (Odiel river watershed)

Mine site Sample Sampling Field measurements Iron content (mg/L) Fe2+/Fet (%) Acidity (mg/L CaCO3 eq.)
No. date 2+ 3+
Q pH Eh (mV) EC DO DO T (C) Fe Fe Fet pH 3.7 pH 5.0 pH 8.3
(L/s) (lS/cm) (mg/L) (%)

Campanario 960-109 Mar-04 1 2.6 593 3970 0.8 9 19.2 755 85 840 90 1120 1410 1970
Concepcion 938-105 Mar-04 2.8 2.3 707 4560 6.1 66 16.4 80 517 597 13 1450 2520 3060
Confesionarios 937-16 Feb-04 15 2.5 672 4500 7.0 70 14.0 60 1455 1515 4 3330 6,540
Confesionarios 937-113 Mar-04 7 2.0 645 18,250 6.2 68 20.0 n.d. n.d. 7730 14,800 24,100 29,450
Cueva de la Mora 938-107 Mar-04 3.5 3.3 572 4190 1.3 14 20.7 575 45 620 93 600 1090 2090

J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

Cueva de la Mora 938-51 Feb-04 15 3.2 679 1850 9.3 91 12.0 50 n.d. n.d. 830 1150 1770
Descamisada 960-106 Mar-04 0.2 3.6 442 2740 0.3 4 19.2 750 22 772 97 940 1310 1780
El Carpio 937-110 Mar-04 1.6 2.8 667 2980 6.3 75 24.8 175 252 427 41 880 1290 1620
Esperanza 938-122 Mar-04 2.2 2.7 603 4470 0.4 4 20.3 830 135 965 86 1330 2090 2660
La Poderosa 938-114 Mar-04 4.5 1.7 622 13,000 0.0 0 21.0 2100 560 2660 79 5500 7480 8100
La Zarza 937-108 Mar-04 0.8 2.9 490 7450 2.1 27 29.0 2200 90 2290 96 3290 4660 6320
La Zarza 937-109 Mar-04 0.8 3.6 614 2470 4.4 47 18.5 27 28 55 49 110 390 790
Rio Tinto 938-102 Mar-04 1 2.3 671 10,050 5.0 57 21.0 1300 2760 4060 32 5700 8690 11,300
(Corta Atalaya)
Rio Tinto 938-112 Mar-04 2 2.6 574 17,200 0.5 6 24.7 1949 121 2070 94 5100 11,470 15,150
(Corta Atalaya)
Rio Tinto 938-124 Mar-04 21 2.8 827 7700 9.3 97 17.0 5 334 339 1 1160 4010 5660
(Corta Atalaya)
Rio Tinto 938-125 Mar-04 6 2.5 626 13,500 0.0 0 21.0 850 775 1625 52 3800 10,400 13,690
(Corta Atalaya)
Rio Tinto 938-126 Mar-04 10 2.4 647 10,200 0.0 0 17.5 588 462 1050 56 2450 6210 8700
(Corta Atalaya)
Rio Tinto 938-127 Mar-04 1 4.2* 400 7000 0.0 0 20.0 1270 0 1270 100 1550 1900 2750
(Corta Atalaya)
Rio Tinto 938-128 Mar-04 <0.5 2.6 752 9400 9.1 95 16.0 0 0 0 0
(Corta Atalaya)
Rio Tinto 938-129 Mar-04 13 3.8* 481 5850 8.5 93 19.0 910 0 910 100 1120 1480 2100
(Corta Atalaya)
Rio Tinto 938-48 Mar-04 48 4.0 637 2200 9.8 99 15.0 0 0 0 0 0 100 200
(Corta Atalaya)
Rio Tinto B-2 Mar-04 15 2.6 742 8900 9.2 100 19.0 0 730 730 0
(Corta Atalaya)
Rio Tinto T-1 Mar-04 28 2.6 608 17,100 5.9 68 22.0 1400 585 1985 71 8130 12,200 16,730
(Corta Atalaya)
San Platon 938-106 Mar-04 2 2.5 603 6030 0.6 5 19.0 1535 245 1780 86 2630 3790 4840
San Platon 938-123 Mar-04 0.5 3.0 703 1690 4.7 47 14.6 10 28 38 26 44 120 231
San Telmo 937-104 Mar-04 2 2.5 640 13,810 0.4 4 21.6 1185 1040 2225 53 4370 9390 12,750
San Telmo 937-105 Mar-04 2.7 2.4 611 10,650 0.5 4 21.2 2070 520 2590 80 4360 7740 10,400
San Telmo 937-106 Mar-04 40 2.9 754 4050 9.9 101 15.2 10 182 192 5 550 1160 1860
San Telmo 937-107 Mar-04 38 3.2 633 3480 8.2 93 20.1 100 46 146 68 150 630 1060
Sotiel-Almagrera 960-110 May-04 1.5 2.7 346 6470 3.5 40 18.0 1085 90 1175 92 1450 2130 3750
Tharsis 959-104 Mar-04 0.3 2.9 620 4940 8.3 86 15.1 400 185 585 68 1090 2350 3520
Tharsis 959-105 Mar-04 5 2.3 640 16,670 0.2 2 16.7 2050 2620 4670 44 9010 16,950 23,160
Tharsis 959-106 Mar-04 3.3 2.0 612 6010 8.1 17.4 985 230 1215 81 2120 3110 3670
Tharsis 959-107 May-04 15 2.7 607 15,330 3.0 40.0 28.7 1540 830 2370 65 4000 8030 10,910
Tharsis 959-108 May-04 0.5 2.2 613 22,700 4.9 63.0 22.7 3140 1270 4410 71 7490 11,100 14,500
Tharsis 959-110 May-04 2.9 728 3700 6.3 71.6 19.3 187 10 197 95
Tharsis 959-16 Feb-04 0.15 2.7 480 11,500 9.3 92.8 14.2 860 872 1732 50 3900 8600 11,350
Tharsis 959-17 Jan-04 11 2.9 774 3500 10.6 96 9.0 3 n.d. n.d. 430 1730
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1333

in these acid waters (maximum values of 17 mg/L As,

470

262
6803
8 mg/L Cd, 48 mg/L Co, 17 mg/L Ni, and 725 lg/L
Pb). Also, U and Th, with peak values around 1100
and 400 lg/L, respectively (sample T-1 from Corta Ata-
laya waste pile, Ro Tinto, Table 4) are unusually con-
260

167
5237

centrated. On the other hand, other trace elements

such as Ag, Be, Hg, Mo, Sb or Se were always close to
or below the detection limits (these elements are not in-
2885
51
140

cluded in Table 4).

In general, these AMD compositions indicate con-
centrations of total dissolved solids (sulphate and met-
als) which are comprised within the ranges normally
77

35
57

reported for VMS-type deposits (Fig. 5) (see Plumlee

et al., 1999, for a comprehensive revision).
1494
172

100

The higher SO4 and metal concentrations are usually

found in the acid leachates from the huge waste piles of
Additional eld data at the moment of sampling (including water ow (Q), pH, dissolved O2 (DO), Eh, electric conductivity (EC), and temperature (T)) are also provided.

Corta Atalaya (Ro Tinto) and Filon Norte (Tharsis),

and indicate an important oxidation and subsequent dis-
476
39

65

solution of pyrite and the accompaning sulphides (chal-

copyrite, sphalerite, galena, arsenopyrite).
An excellent correlation (r = 0.97 for n = 72;
133

801
35

p < 0.01) has been found between electric conductivity

(EC) of these waters and (1) total dissolved solids (Fig.
6A) and (2) dissolved SO4 (Fig. 6B), which conrms con-
12.4

14.7
18.7

ductivity as a good indicator of the degree of contamina-

tion of the stream waters by AMD, especially when
coupled with pH/Eh measurements.
15
48
0

4.4. Mineralogy and chemistry of iron precipitates

0.0

1.5
4.6

Probably, the most widespread feature of the study

area is the ubiquitous presence of yellow to reddish-
1830

1142
7925

brown sediments in the banks of the rivers aected by

AMD. These so-called ochre precipitates consist of
Fe-phases precipitated from the Fe dissolved in AMD
and coming from pyrite oxidation in the mine sites.
603

696
624

However, and in contrast to other well crystallized prod-

ucts of pyrite oxidation such as hematite or goethite, the
ne-grain size and low crystallinity of these chemical
3.3

3.2
2.7

sediments make their mineralogical characterization dif-

cult. To date, these mine drainage minerals (MDM;
Murad et al., 1994) have been well characterized in
0.3

many mine districts all over the world by a combination

of dierent techniques (XRD, electron microscopy, dif-
Mar-04

Mar-04
Mar-04

ferential dissolution with ammonium oxalate, Fe/Smolar

ratio) and have been proved to consist of extremely small
particle size (from <10 nm to 510 lm in diameter),
960-101

960-104

poorly crystallized oxyhydroxides and oxyhydroxysul-

phates of brous to spherical morphology such as fer-
rihydrite and schwertmannite, in addition to jarosite
and goethite (Carlson and Schwertmann, 1981; Bigham
Average IPB AMD

et al., 1990, 1994, 1996; Murad et al., 1994; Nordstrom

Trincheron

and Alpers, 1999a; Yu et al., 1999; Kawano and Tomita,

Tinto-Sta

2001; Williams et al., 2002; Dold, 2003; Fukushi et al.,

Rosa

2003; Regenspurg et al., 2004; Majzlan et al., 2004).

1334 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

Fig. 4. Photographs of several mine sites in the IPB showing the typical eld aspect of some relevant acid mine euents. (A) The
Tintillo acid river (front), which is formed by dierent acid leachates (pH  2.7, Fet  2 g/L) emanating from the base of large waste-
rock piles in the surroundings of the Corta Atalaya open pit (Rio Tinto mine). The laminated, yellowish brown to orange formations
deposited on the stream bed are composed of a mixture of hydrous Fe oxide precipitates (mainly schwertmannite, jarosite and goethite)
with plant debris and lamentous algae. (B) AMD discharge (pH  3, Fet  300 mg/L) in the Lomero-Poyatos mine adit (ochre
deposits include jarosite and schwertmannite). (C) AMD discharge emanating from the Perrunal mine adit (pH  3.1, Fet  2.6 g/L).
(D) Acid leachate (pH  2.5, Fet  500 mg/L) from the waste-rock piles situated around Filon Centro open pit (Tharsis mine). The
AMD stream is profusely collonized by green lamentous algae, and surrounded by eorescent sulphate salts (halotrichite,
pickeringite, hexahydrite). (E) AMD discharge (pH  2.3, Fet  4 g/L) and associated eorescent sulphates in a mine adit close to
Corta Atalaya (Rio Tinto). (F) Partial view of the Santa Barbara pit lake (San Telmo mine) showing the water inow (formed by acid
leachates emanating from several waste-rock piles, and their related eorescent salts). (G) Acid sulphate waters (pH  2.5) in the Filon
Norte open pit.
Table 6
Mineralogical and chemical composition of sediments found in dierent AMD discharges and streams receiving AMD in the Odiel river basin

Mine/river site Sample No. Sampling Mineralogy (XRD) Major oxides (%) Trace metals (ppm)
date
Major Minor SiO2 Al2O3 Fe2O3 CaO TiO2 MnO K2O MgO Na2O P2O5 LOI Total As Cr Cu Pb V Zn

Bco. Las Vinas P-937-19 Apr-03 Al-comp Gyp 72.44 7.30 9.65 0.10 0.51 0.00 2.08 0.10 1.07 0.02 6.81 100.08 66 10 25 11 29 54
Confesionarios P-937-101 Feb-03 Qtz, Jar Alb, Ms, Fe-ox 48.57 5.52 24.70 0.10 0.23 0.00 1.58 0.10 1.00 0.01 18.34 100.15 373 1 31 34 16 <2
Confesionarios P-937-19 Feb-03 Qtz K-feld, Ms, Jar 72.44 7.30 9.65 0.10 0.51 0.00 2.08 0.10 1.07 0.02 6.81 100.08 66 10 25 11 29 54
(Las Vinas)
Corta Atalaya P-938-32 Feb-03 Schw Jar, Qtz 4.76 1.73 61.45 0.10 0.20 0.04 0.34 0.10 0.11 0.13 31.16 100.12 1134 9 657 316 42 107
(ro Tintillo)
Corta Atalaya P-938-34 Feb-03 Schw Jar, Qtz 5.53 3.38 52.62 0.11 0.50 0.06 0.37 0.35 0.90 0.14 36.05 100.01 734 6 462 374 26 312
(ro Tintillo)

J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

Corta Atalaya P-T-1 Apr-03 Goet, Jar Qtz 5.30 1.74 60.31 0.15 0.32 0.06 0.26 0.25 0.14 0.21 31.04 99.76 860 11 1107 406 42 442
(ro Tintillo)
Corta Atalaya P-T-2 Apr-03 Schw 1.78 1.35 58.40 0.11 0.41 0.06 0.10 0.21 <0.1 0.20 37.34 99.96 709 14 421 297 38 383
(ro Tintillo)
Corta Atalaya P-T-3 Apr-03 Schw Qtz 3.83 2.47 55.33 0.17 0.24 0.08 0.28 0.52 <0.1 0.22 37.00 100.14 1114 10 393 222 42 418
(ro Tintillo)
Corta Atalaya P-T-4 Apr-03 Schw Qtz 3.40 1.82 58.36 0.11 0.20 0.06 0.26 0.15 <0.1 0.14 35.81 100.30 818 12 435 236 48 286
(ro Tintillo)
Corta Atalaya P-T-6 Apr-03 Qtz, Ms, Jar 2.82 1.50 63.95 0.10 0.11 0.05 0.18 <0.10 <0.1 0.15 31.14 99.99 794 13 814 107 75 212
(ro Tintillo)
Corta Atalaya P-T-6-II Apr-03 Goet Schw, Qtz 4.45 1.96 60.35 0.07 0.10 0.04 0.47 <0.10 0.34 0.11 32.38 100.25 1369 7 930 386 35 122
(ro Tintillo)
Dehesa Boyal P-DB-8 Apr-03 Schw, Qtz 33.38 24.91 4.92 0.83 0.75 0.08 1.00 0.85 1.04 0.18 32.07 100.00 37 2249 149 40 402
La Torerera P-959-11 Feb-03 Qtz Mic, Alb, 45.31 14.17 18.34 0.10 0.53 0.04 2.43 0.41 0.55 0.08 18.07 100.03 2969 24 337 1810 31 159
Jar, Cl
La Zarza P-937-8 Feb-03 Schw Jar 1.07 0.73 60.68 0.18 0.03 0.05 0.15 0.10 0.08 0.15 36.83 100.04 742 4 91 9 83 71
Lomero-Poyatos P-937-102 Feb-03 Jar, Schw Qtz, Ms, 4.86 2.39 47.40 1.22 0.15 0.05 0.26 1.99 0.33 0.14 41.25 100.04 2221 25 236 1080 88 447
Cl, Gyp
Mina el Soldado P-938-119 Apr-03 Goet Qtz, Schw 1.35 1.12 59.16 0.05 0.02 0.02 0.11 <0.10 <0.1 0.06 38.22 100.10 1147 <2 282 14 9 5
Ro Odiel P-938-43 Apr-03 Qtz, Alb, Ms, Ka 23.65 19.15 25.86 0.91 0.33 0.09 0.67 0.90 0.47 0.40 27.69 100.12 135 21 4127 78 56 18,766
Ro Odiel P-960-2 Apr-03 Schw Qtz 61.23 12.27 12.06 1.28 1.16 0.08 2.05 1.04 1.74 0.09 7.01 100.00 95 30 248 61 62 108
(Est. 54)
Rivera de P-937-1 Apr-03 Qtz, Fe-ox Alb 23.92 10.05 30.45 0.38 0.38 0.09 1.60 1.12 0.39 0.11 31.31 99.81 226 12 508 38 19 944
la Panera
Rivera P-938-7 Apr-03 Qtz, Jar Ms 67.94 8.50 9.98 0.10 0.37 0.01 1.34 0.10 2.64 0.01 9.08 100.07 172 1 111 677 7 8
Olivargas
Sotiel P-960-8 Feb-03 Qtz Ms, Schw 52.75 20.50 10.45 0.18 0.59 0.02 1.57 0.47 0.31 0.06 13.11 100.00 278 33 90 180 50 173
Tharsis P-959-2 Feb-03 Schw Qtz, Ms, Cl 26.25 8.46 35.26 0.16 0.37 0.12 1.24 0.85 0.53 0.36 26.41 99.99 4729 42 537 221 179 887
Tharsis P-DB-1 Apr-03 Jar Goet, Qtz 37.28 13.55 28.56 0.07 0.61 0.03 2.30 0.12 0.20 0.10 16.79 99.62 717 20 299 1015 24 142
(Dehesa Boyal)
Tharsis P-DB-3 Apr-03 Qtz, Schw Ms, K-feld, 8.80 4.75 52.32 0.13 0.12 0.06 0.41 0.29 0.11 0.19 33.12 100.30 351 19 537 127 26 182
(Dehesa Boyal) Jar
Tharsis P-DB-5 Apr-03 Qtz, Schw Ms 20.07 10.52 34.34 0.35 0.26 0.14 1.07 0.95 0.49 0.14 32.70 101.02 164 36 803 65 38 392
(Dehesa Boyal)
Tharsis P-DB-7 Apr-03 Qtz, Ms Ms, Schw 15.75 9.12 40.45 0.19 0.23 0.07 0.88 0.17 0.49 0.14 32.70 100.18 68 42 546 101 14 73
(Dehesa Boyal)
Tharsis P-959-7 Feb-03 Schw Jar, Goet 2.18 1.21 60.21 0.10 0.06 0.04 0.45 0.10 0.14 0.20 35.37 100.05 3189 7 299 426 96 223
(Aguas Agrias)
Tintillo P-T-7 Apr-03 Qtz, Schw Goet, Ms 40.09 7.53 28.38 0.42 0.43 0.07 1.09 0.70 0.39 0.13 20.61 99.84 884 14 226 129 30 60
Tintillo P-T-8 Apr-03 Schw, Qtz 21.45 5.61 43.75 0.36 0.45 0.05 0.81 0.25 0.39 0.22 26.45 99.78 1043 12 697 799 30 341
Tinto-Sta Rosa P-960-9 Feb-03 Qtz, Ms, Cl 31.20 30.18 3.62 0.36 0.20 0.06 0.82 0.49 0.23 0.03 32.80 100.00 168 7 16,956 243 8 637

1335
Abbreviations: Qtz, quartz; K-feld, potassium feldspar; Alb, albite; Ms, muscovite; Cl, chlorite; Gyp, gypsum; Al-comp, amorphous aluminium compounds; Fe-ox, undierentiated iron oxides; Jar, jarosite; Goet, goethite; Schw,
schwertmannite; Ka, kaolinite.
 1336
Table 7
Mineralogical and chemical composition of mine drainage minerals (MDM) found in dierent mine sites of the IPB (Odiel river basin)

J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

Abbreviations: Jar, jarosite; Goet, goethite; Schw, schwertmannite; Ferr-2L, two line-ferrihydrite; Bas, basaluminite; Qtz, quartz; Ms, muscovite; Cl, chlorite; n.a., not analyzed; n.d., not detected. The provided eld data (pH and Eh in mV)
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
In the IPB, these Fe(III) phases had not been stud-
ied in detail, being traditionally referred to under
ambiguous terms such as ochreous precipitates,
amorphous iron oxides, ferric hydroxides, or
poorly crystalline oxyhydroxides. Although the pres-
ence of schwertmannite has been recently suggested in
the Ro Tinto sediments (e.g., Hudson-Edwards et al.,
1999), it has not been unequivocally recognized or
characterized.
In this work, the authors present preliminary miner-
alogical and chemical characterization of the MDM usu-
ally found in the IPB (Tables 6 and 7; Figs. 7 and 8).
These samples were collected from dierent deposits
and included: (1) recent, ochreous, colloidal precipitates
directly taken from the AMD water column, (2) lm-like
thin Fe(III) layers oating on the water surface in low
ow or stagnant AMD sites, (3) aged, hard Fe(III)
crusts, and (4) laminated Fe(III) formations formed by
the covering of streambed cobble by lamentous algae
and hydrous Fe oxyhydroxides. Also, two samples of
synthetic precipitates formed during titration of
AMD solutions with NaOH 2 M to pH  4, have also
been analyzed for comparison with the naturally occur-
ring samples (Fig. 7).
The older and more consistent samples (Fe(III)
crusts, laminated formations) detailed in Table 6 show
A 1,000,000
100,000
10,000
SO4 (mg/L)
1,000
100
10
1
-3.0
B 1,000,000
Fe+Cu+Zn (mg/L)
100,000
10,000
1,000
100
10
1
0
10
Fig. 5. (A) SO4 vs. pH diagram and (B) (Fe + Cu + Zn) vs. SO4 diagram, for AMD discharges in the IPB (Odiel river watershed). For
comparison purposes, the chemical data available for AMD waters from dierent types of deposits (compiled in Plumlee et al., 1999,
see references therein) have been also plotted.
1337
always trace to major amounts of detritic silicates such
as quartz, feldspars or clay minerals which are cemented
by Fe oxyhydroxides, and always have high contents of
SiO2 and Al2O3.
The recent ochre precipitates show recognizable
bands in the XRD proles (Fig. 7) and consist mainly
of schwertmannite (Fe8O8(SO4)(OH)6), either as a
monomineralic phase, or combined with jarosite (KFe3
(SO4)2(OH)6) and/or goethite (FeOOH).
Schwertmannite is poorly crystallized in comparison
with jarosite and goethite. However, it is possible to rec-
ognize 8 bands at 1.46, 1.51, 1.66, 1.95, 2.28, 2.55, 3.39
and 4.86 A in the XRD patterns (Fig. 7), in agreement
with other schwertmannite samples described in the lit-
erature (e.g., Bigham et al., 1996; Williams et al., 2002;
Dold, 2003). These results, coupled with pepH data
(pe = 1215, pH 2.03.5) of parent acid solutions (as-
sumed to be in equilibrium with analyzed minerals),
and chemical composition of these precipitates (averag-
ing 61% Fe2O3, 37% LOI, and (Fe/S)molar  5.3), are
conclusive evidence for schwertmannite identication
(Table 7; Fig. 8).
Additionally, 2 line-ferrihydrite (Fe5HO8 4H2O)
and an Al-bearing amorphous phase, have been
identied in a sample collected downstream of Con-
cepcion AMD discharge on the Odiel river (pH  7;
IPB
Iron Mountain
-1.0 1.0 3.0 5.0 7.0 9.0
pH
IPB
Iron Mountain
100 1,000 10,000 100,000 1,000,000
SO4 (mg/L)
1338 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
(Fe/S)molar = 12.1). The articially obtained phases after
titration of AMD samples from Ro Tinto (sample 938-
102) and Tharsis (sample 959-16) are composed of a
mixture of schwertmannite and an XRD-amorphous,
white-coloured, Al-phase that could be basaluminite
(Al4(SO4)(OH)10 5H2O).
XRD results are in perfect agreement with pepH
data and chemical analyses of these oxyhydroxysul-
phates. Most samples plot within their respective theo-
retical stability elds in a pepH diagram (Fig. 8) and
show (Fe/S)molar ratios similar to those reported else-
where (Bigham et al., 1990, 1994, 1996).
The average chemical composition of monomineralic
schwertmannite includes minor amounts of SiO2 (0.4
3.8 wt%) and Al2O3 (0.73.0 wt%), which could suggest
either (1) some silicate contamination of samples, and/
or (2) some degree of sorption/coprecipitation of Si
and Al onto the schwertmannite colloidal particles. In
fact, the two mixed schwertmannite-basaluminite sam-
ples formed by titration of acid solutions (samples 959-
16 and 938-102; Table 7), show also SiO2 contents of
0.41.5%, which strengthens the second possibility, and
agrees with the results of Carlson and Schwertmann
(1981), who found Si contents of 2.54.5% in AMD pre-
cipitates (in this case, consisting of ferrihydrite) from
Finland.
Average compositions of the analyzed Fe minerals
also include signicant trace element contents
(2312,770 ppm As, 804800 ppm Cu, 56230 ppm Zn,
21080 ppm Pb, 4274 ppm Co, 4452 ppm Ni,
131 ppm Cd; Table 7). This suggests variable sorption
of dissolved trace metals onto schwertmannite, ferrihy-
drite, jarosite and goethite mineral surfaces. Other trace
metals (Ag, Be, Hg, Mo, U, Th) were always below the
detection limit.
4.5. Mineralogy and chemistry of eorescent sulphate
salts
In addition to the hydrous Fe oxide phases, a number
of sulphate eorescences from dierent mines (e.g.,
Corta Atalaya-Ro Tinto, Tharsis, La Zarza, San
Telmo, Lomero-Poyatos, San Miguel) were collected
during the dry season (June and September; Fig. 4D
F). These minerals are formed by evaporation of the
acid mine waters, being ubiquitous around waste piles,
taillings and river banks during this season (evaporation
rates of about 510 mm/day were calculated during eld
experiments conducted in September 2003). These salts
have also been mineralogically identied by XRD and
chemically analyzed for major and trace element con-
tents (Table 8).
These soluble metal sulphate salts are usually found
as botryiodal (colliform-like) eorescences of variable
colour (white, greenish blue, pale green, yellow, or-
ange, dark reddish), being normally zoned from the in-
10 5
A
TDS (mg/L)
10 4
R2 =0.93
10 3
10 3 10 4 10 5
EC (S/cm)
10 5
B
SO4 (mg/L)
10 4
R2 =0.95
10 3
10 2
10 2 10 3 10 4 10 5
EC (S/cm)
Fig. 6. Binary plots showing the correlation between electrical
conductivity (EC) eld measurements and (A) total dissolved
solids (TDS) and (B) SO2

4 , for the studied AMD discharges in
the IPB (Odiel river watershed).
ner to the outer zones of the AMD sources and
streams, and suggesting a paragenetic sequence of sul-
phates with distinct solubilities and degrees of dehy-
dration. They are rarely found as monomineralic
phases, and most commonly consist in mixtures of
MgFeAl hydrated sulphates such as epsomite, hexa-
hydrite, pickeringite, melanterite, szomolnokite, roze-
nite, halotrichite, copiapite or rhomboclase. Most of
these phases have been indentied in other mining dis-
tricts (e.g., Iron Mountain; Alpers et al., 1994; Nord-
strom, 1999; Nordstrom and Alpers, 1999b) and
have also been recently recognized and analyzed by
Buckby et al. (2003) in the adjacent Tinto river.
Among these sulphates, the Fe(II)-rich salts (melante-
rite, szomolnokite, rozenite, halotrichite) are dominant
at the discharge points of the more acidic and Fe(II)-
rich acid waters, whereas the Fe(III)-rich (copiapite,
coquimbite) and Mg-rich (epsomite, hexahydrite) min-
erals are typical of the banks of most streams aected
by AMD. Gypsum is also frequent as acicular crystals
in mine adits and waste piles. Stalactites composed of
gypsum copiapite jarosite are commonly observed
at the AMD discharge points.
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1339

Fig. 7. Selected XRD proles for the mine drainage minerals (MDM) studied in the IPB mine sites. These diractometric patterns
include, 4 examples of schwertmannite found in several AMD discharges at pH of 2.53.5 (left), two cases of schwertmannite-bearing
precipitates obtained during titration of AMD solutions at pH about 4.0 (center), one sample of jarositeschwertmannite from the
Tinto river (pH 2.1; upper right), and a ferrihydrite sample taken from the Odiel river and occurring at neutral pH (lower right). As an
example, in sample 937-8, the d-spacing (A ) of the identied reections are indicated. See Table 7 for a detailed sampling site
description and chemical composition of these Fe precipitates.

Chemical analyses of mixtures of these sulphates re- 5. Discussion

veal metal contents (e.g., average values of 2800 ppm
Cu and 9000 ppm Zn, with local Zn values of several
percent; Table 8) which are signicantly higher than
those corresponding to analyzed schwertmannite, fer-
rihydrite, jarosite and goethite (810 ppm Cu and
750 ppm Zn on average; Table 7). On the other hand,
As contents of the sulphates are very low in comparison
with those of schwertmannite (195 and 1700 ppm,
respectively), whereas Co, Ni and Cd show average val-
ues of 240, 155 and 30 ppm, respectively. Other trace ele-
ments (Ag, Be, Hg, Sb and Th) were always below their
respective detection limits.
The environmental signicance of sulphate minerals
precipitated during AMD evaporation has been pro-
fusely documented (e.g., Alpers et al., 1994; Nord-
strom and Alpers, 1999b). The large accumulation of
these salts in the mine sites plays an important role
in the transient storage of metals and acidity, which
can be easily redissolved and incorporated in the water
courses during rainfall episodes.
5.1. Geochemistry of the acid mine drainage
5.1.1. Eh and Fe(II)/Fe(III) redox chemistry
The eld Eh data are well correlated with the Fe(II)/
Fetotal ratio, which means that the redox potential of the
acid mine waters is basically governed by the oxidation of
Fe(II) (Fig. 9). The observed variation of Eh with Fe(II)/
Fetotal allows the quantitative estimation of the Fe(II) to
Fe(III) ratio of the acid mine waters from Eh measure-
ments. An approximate Eh value of  640 mV dierenti-
ates the dominantly Fe(II) (>50% Fe(II)) from the
dominantly Fe(III) (<50% Fe(II)) acid drainage (Fig. 9).
Additionally, theoretical Eh values for the AMD
solutions (calculated with PHREEQC from Fe(II)
and Fe(III) concentrations) are highly correlated
(r = 0.88 for n = 34) with the Eh values measured on
site for all Fe molal concentrations (10
710
1 mol;
Fig. 10). These data reinforce the validity of Eh as
indicator of the Fe oxidation state in AMD.
1340 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
Fig. 8. pepH diagram for the studied hydrous Fe oxides
(oxyhydroxysulphates). The pe (Eh (mV)/59.2) and pH data
correspond to the ambient conditions measured in the parent
AMD solutions from which the samples were taken, at the
moment of sampling. Field boundaries for stability of the
dierent mineral phases are taken from Bigham et al. (1996).
The shaded areas represent the expansion of the K-jarosite and
ferrihydrite stability elds if lower solubility products are
selected (Bigham et al., 1996). Abbreviations: Jt, K-jarosite; Sh,
schwertmannite; Fh, ferrihydrite; Gt, goethite; Py, pyrite; Diss.
Spec., dissolved species.
5.1.2. The bacterial oxidation of Fe(II)
The oxidation of Fe(II) is very fast, and therefore, the
AMD waters evolve geochemically downstream in a
short distance (often on a m-scale) as they become equil-
ibrated with atmospheric O2. The hydrolysis of Fe(III)
also occurs rapidly, and precipitation of hydrous Fe oxi-
des takes place at a few meters from the discharge
points.
From detailed eld work at selected mine sites (e.g.,
La Zarza-Perrunal and Tharsis mine portals, unpub-
lished data) it has been calculated that the eld rate
for Fe(II) oxidation is between 1 and 20 mmol L
1 h
1
(depending on the concentration of bacterial cells, as
well as on temperature). These rates are comparable to
other reaction rates reported for bacterially catalyzed
Fe oxidation in AMD environments (Nordstrom,
1985; Williamson et al., 1992; Kirby and Elder Brady,
1998; Kirby et al., 1999), and about 106 times faster than
published laboratory abiotic rates (Stumm and Lee,
1961; Singer and Stumm, 1970).
These data suggest that bacterial activity is playing a
critical role in the geochemical evolution of the acid
mine waters, catalyzing the oxidation of Fe(II). This
idea is conrmed by several eld observations like the
biologically induced, laminated Fe(III) formations,
which are present in most of the studied mine sites. In
fact, several microbiological studies (Waddell, 1978;
Ahonen and Tuovinen, 1989) have conrmed that the
ambient conditions commonly found in these mine-
drainage environments (pH  3, T  2030 C) are opti-
mum for Acidithiobacillus ferrooxidans (which have been
observed at pH 1.34.5 and T = 437 C; Waddell,
1978). A number of chemolithotrophic microorganisms,
including Fe- and S-oxidizing bacteria (e.g., Acidithioba-
cillus ferrooxidans, Acidithiobacillus thiooxidans, or
Leptospirillum ferrooxidans) have been described in the
acidic Odiel and Tinto rivers (Lopez-Archilla et al.,
2001; Gonzalez-Toril et al., 2003). Additional studies
have addressed the importance of these bacteria not only
in the oxidation of Fe(II), but also in the nucleation and
growth of hydrous Fe oxide particles (e.g., schwertman-
nite) on their cell surfaces (e.g., Kawano and Tomita,
2001).
5.1.3. Acidity and the role of Fe(III) and Al(III) as
buering species of AMD systems
The high acidity values reported in Table 5 are fa-
voured by the scarcity of carbonates to neutralize the
acidity released during pyrite oxidation. Although some
aluminosilicates (muscovite, albite, K-feldspar) can also
neutralize acidity, these minerals are much less ecient
as acidity-neutralizers than carbonate dissolution
(Stumm and Morgan, 1981). Furthermore, whereas the
dissolution rate of carbonates (10
510
6 mol m
2 s
1)
is faster than that of pyrite (10
810
10 mol m
2 s
1),
aluminosilicates show signicantly slower rates of disso-
lution (10
1110
13 mol m
2 s
1; Banwart and Malm-
strom, 2001). Consequently, without the presence of
abundant carbonate, the existing aluminosilicates can-
not neutralise the acidity released during the abundant
pyrite oxidation. On the contrary, aluminosilicate disso-
lution releases important amounts of dissolved Al (in
addition to Fe(II) in the case of chlorite) which can also
be hydrolized and provide additional acidity.
The maximum contents of Ca (529 mg/L), Na
(206 mg/L), K (36 mg/L), Mg (2894 mg/L), and Cl
(580 mg/L) found in the analyzed AMD (Table 4),
suggest an eective dissolution of the abundant alumi-
nosilicates (especially chlorite, in addition to sericite,
K-feldspar and albite) and rare carbonates (calcite,
dolomite, ankerite) at the mine sites.
To achieve a more accurate interpretation of the
acidity potential of the acid mine drainage, detailed
titration tests have been performed on selected AMD
samples (n = 40). The acidity data are reported in Table
5, and some examples of titration curves are shown in
Fig. 12.
The data given in Table 5 show two relevant features:
(1) total acidity is very variable over the range 200
30,000 mg/L CaCO3 eq. among the dierent mine eu-
ents and (2) acidity is excellently correlated with the
Fe and Al contents (R2 = 0.910.95; Fig. 11).
Table 8
Mineralogical and chemical composition of eorescent sulphate salts found in the mine sites and water courses comprised in the Odiel river basin

Mine/river Sample Sampling Mineralogy (XRD) Major oxides (%) Trace metals (ppm)
site No. date
Major Minor SiO2 A12O3 Fe2O3 CaO TiO2 MnO K2O MgO Na2O LOI Total As Cd Co Cu Ni Pb U V Zn

Angostura 938-110 Jun-03 Pick, Hal 2.26 9.77 2.87 0.08 0.03 0.13 0.10 6.92 0.27 77.68 100.10 <10 5 152 4351 55 n.a. 3 1 921
La Zarza 937-109 Jun-03 Sta Gyp 2.36 1.79 0.43 6.50 0.02 1.48 0.10 15.53 0.53 64.37 93.10 <10 2 274 333 452 22 1 1 2683
Lomero- 937-103 Jun-03 Eps Hex, Hal, 4.55 7.09 5.23 0.26 0.08 0.41 0.10 9.98 1.36 71.05 100.10 22 13 21 993 18 33 2 14 2674
Poyatos Kal
Lomero- 937-103b Jun-03 Sta Pent, Gyp, 2.29 4.19 6.28 0.68 0.04 0.39 0.10 12.82 0.40 72.91 100.10 88 9 28 609 22 6 1 5 4212
Poyatos Anh
Lomero- 937-103c Jun-03 Hex Pick, Hal, 0.94 4.43 6.35 0.18 0.03 0.36 0.10 14.77 1.36 71.68 100.20 <10 7 31 504 18 19 1 1 4916
Poyatos Kal

J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

Oraque E-959-1 Jul-03 Sta, Roz Pick 0.70 7.48 0.71 0.45 001 0.94 0.10 11.58 3.20 65.44 90.61 <10 80 398 2460 211 5 9 2 30,300
river
Poderosa 938-1 14-A Sep-03 Eps Alun, Bass 0.85 5.42 21.96 0.32 0.03 0.06 0.16 1.19 0.26 69.73 99.97 260 36 n.a. 7173 n.a. 6 n.a. n.a. 6268
Poderosa 938-1 14-B Sep-03 Rom Szo 0.69 3.76 19.45 4.83 0.02 0.05 0.15 1.22 0.19 62.72 93.08 194 27 n.a. 7766 n.a. 10 n.a. n.a. 5898
Rio Tinto RT-1 Jun-03 Cop, Hal 0.10 6.05 17.16 0.13 0.01 0.41 0.10 4.77 0.16 71.30 100.19 417 38 219 7449 60 1 1 3 5810
Mg-Cop
San Miguel 938-108 Jun-03 Cop, Coq 3.82 4.57 19.77 0.13 0.04 0.23 0.08 1.93 0.09 69.32 99.99 344 4 86 1506 37 17 1 5 494
Mg-Cop
San Miguel 938-121-B Sep-03 Szo Gyp, Rom, 2.41 5.57 20.10 0.70 0.04 0.47 0.15 4.34 0.20 66.03 97.24 28 6 n.a. 443 n.a. 5 n.a. n.a. 1406
Eps
San Miguel 938-121-P Sep-03 Pick Szo, Hal 0.69 3.93 18.06 0.25 0.02 0.39 <0.10 3.73 0.08 72.85 99.23 2 3 n.a. 502 n.a. 2 n.a. n.a. 1222
San Telmo 937-105a Jun-03 Szo Hal, Pick 0.42 6.51 17.97 0.19 0.01 0.55 0.58 6.30 0.27 67.13 99.93 1480 26 54 114 46 19 3 10 3497
San Telmo 937-105b Jun-03 Cop Rom 0.48 2.35 26.26 0.13 0.02 0.07 0.11 0.37 0.07 70.18 100.03 625 19 53 6580 27 11 2 2 3174
San Telmo 937-105c Jun-03 Pick Hal, Kie 4.60 6.94 2.71 0.25 0.05 1.58 0.10 11.84 0.43 71.57 100.07 <10 41 57 9592 100 41 3 34 12,676
San Telmo 937-2 Jun-03 Cop, Kie, Hal 2.92 5.84 13.25 0.11 0.06 0.74 0.14 7.36 0.07 69.59 100.06 102 21 106 2995 107 n.a. 3 7 6883
Mg-Cop
San Telmo 937-106 Jun-03 Pick Roz, Sta, 2.29 6.79 3.14 0.08 009 1.09 0.10 8.66 0.07 77.66 99.89 <10 26 125 3018 80 n.a. 6 1 8592
(pit lake) Hal
San Telmo 937-104 Jun-03 Gyp Jar, Qtz 8.39 1.45 2.18 29.35 0.04 0.03 0.19 1.37 0.14 23.54 66.67 15 3 8 190 7 29 <0.2 3 440
(waste pile)
Tharsis 959-104 Sep-03 Pick, Hal Sta <0.10 8.81 0.11 0.06 0.03 4.62 <0.10 9.22 0.34 76.77 100.15
Tharsis 959-7 Jun-03 Pick, Hal 2.44 9.82 1.04 0.25 0.03 1.10 0.10 9.84 0.61 74.87 100.10 <10 43 266 4255 159 n.a. 6 1 8400
(Aguas Agrias)
Tharsis E-959-7A Jul-03 Sta, Hex Hal, Pick 0.35 5.24 6.95 0.15 0.02 0.62 0.10 9.69 0.07 76.89 100.07 534 73 845 2012 550 14 7 36 33,400
(Aguas Agrias)
Tharsis E-959-7B Jul-03 Sta, Cop, Roz 0.10 5.50 6.57 0.10 0.01 0.62 0.10 10.10 0.15 76.99 100.23 172 87 832 2107 540 1 8 10 32,200
(Aguas Agrias) Pick
Tharsis E-959-7C Jul-03 Sta, Cop, Kal 0.87 7.17 5.79 0.13 0.01 0.68 0.10 9.25 0.30 75.80 100.09 176 94 829 2579 482 79 8 11 35,800
(Aguas Agrias) Pick
Tharsis DB-2.1 Jun-03 Pick, Hal 0.98 10.10 5.34 0.18 0.02 0.94 0.10 5.26 0.07 77.18 100.16 <10 15 214 4285 139 n.a. 1 2 3893
(Dehesa Boyal)
Tharsis P-DB-6 Apr-03 Hex, Gyp Jar 16.16 5.60 39.76 0.30 0.23 0.10 0.45 1.71 0.39 37.85 102.55 117 1 n.a. 604 n.a. 71 <1 26 219
(Dehesa Boyal)
Tintillo river 938-112 Sep-03 Gyp Cop 1.40 2.97 18.50 4.58 0.19 0.31 0.12 2.95 0.08 48.76 80.01 72 6 n.a. 486 n.a. 4 n.a. n.a. 6184
Tintillo river 938-112a Jun-03 Pick Hal, Kie 1.20 8.43 4.42 0.12 0.02 1.11 0.10 9.77 0.07 74.93 100.17 <10 36 178 3110 115 10 6 0 8389
Tintillo river 938-112b Jun-03 Sta Hal, Roz, 1.22 6.37 7.31 0.11 0.02 0.96 0.10 8.31 0.07 75.70 100.17 <10 34 158 2625 101 12 5 1 7929
Pick
Tintillo river 938-112c Jun-03 Sta Hal, Pick 1.08 5.76 8.82 0.11 0.03 0.88 0.10 8.48 0.07 74.79 100.10 29 28 189 2738 108 7 4 1 12,873
Tintillo river E-T-9 Jul-03 Sta Pick 0.20 8.27 3.55 0.18 0.01 0.83 0.10 8.95 0.27 77.75 100.11 20 113 600 4001 310 n.a. 11 4 27,600
Tintillo river T-1 Sep-03 Hex, Pick Hal O.10 7.32 5.45 0.40 0.01 0.99 <0.10 8.72 <0.065 77.05 99.93 72 6 n.a. 486 n.a. 4 n.a. n.a. 6184
Tintillo river T-1-A Sep-03 Sta, Pick Roz, Hal 0.74 8.35 4.68 0.23 0.03 0.97 <0.10 8.35 0.09 76.50 99.10 2 32 n.a. 1990 n.a. <2 n.a. n.a. 6823
Tintillo river T-1-B Sep-03 Pick, Sta Hal 0.38 9.08 4.20 0.19 0.02 1.03 <0.10 7.08 0.08 77.93 99.54 <2 36 n.a. 2189 n.a. <2 n.a. n.a. 6163
Line missing

1341
1342 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

The titration curves are clearly marked by two sharp

(continued on next page)

7241

7312
7869
6513
6509
7487

Zn
slope breaks at pH  2.7 and around 4.04.5, which
indicate strong resistance of the acid solutions to pH in-

n.a.

n.a.

n.a.
n.a.

1
crease during titration (Fig. 12), being the result of the

n.a.

n.a.

n.a.
hydrolysis of dissolved Fe(III) and Al(III) ionic species.
n.a.

4
Additionally, Fe(II) hydrolysis causes slope breaks at

<2

<2

<2
Pb
pH  7.08.0 in the Fe(II)-rich samples that were not
<2

1
oxidized with H2O2 before titration (e.g., Fig. 12A, C
n.a.

n.a.

n.a.
n.a.

Ni

96

21
and F). Although some hydrolysis of dissolved Fe(II)
at circumneutral conditions occasionally occurs in the
1476

1442

3940
2612
3765
3222
Cu

eld (e.g., La Poderosa and San Miguel mines), this pro-

n.a.

cess rarely takes place under natural conditions at the

Trace metals (ppm)

n.a.

n.a.

n.a.
186
Co

41

basin-scale.
18

Cd

These gures reect that Fe(III) and Al(III) hydroly-

30

35
39
25
35

sis concurrently can represent around 70% on average of

<2

<10
As

13

15
51
20

the total acidity potential of the aqueous acid solutions.

In other words, Fe and Al dissolved in AMD act as
100.00

100.10

100.10
Total

99.67

99.48

99.52

chemical buers, stabilizing the AMD systems at pH

values around about 2.7 and 4.5, respectively. This buf-
79.69

78.92

75.68
79.20
77.19
78.13

fering is evident in the Odiel river mouth, which shows

LOI

an average pH of between 2.5 and 3.5 (with a well-de-

<0.065

ned median value of 2.7 in the summer months) over

Na2O

0.19

0.08
0.31
0.19
0.28

the period 19902001 (Confederacion Hidrograca del

10.57

Guadiana, unpublished data).

MgO

8.88

8.14
8.56
7.99
8.04
<0.10

5.1.4. Seasonal variation of the AMD chemistry

<0.10

<0.10

<0.10
K2O

0.10

0.10

As is clearly shown in Tables 3 and 4, AMD compo-

0.64

sitions are not chemically constant throughout the

MnO

hydrologic year 20032004. On the contrary, they show

1.55

0.98
1.59
0.95
0.94
0.02

marked chemical variations between the winter and

TiO2

summer seasons. Flow rate is strongly lowered and pH

0.03

0.03

0.02
003

003
0.67

tends to decrease during the dry period, but changes in

SO4 and metal concentrations do not show a clear trend.
CaO

0.07

0.56
0.08
0.22
0.07

Further, the variability in metal contents is not propor-

4.65

tional among the dierent mine euents.

Fe2O3

0.33

5.21
0.38
4.31
3.16

This suggests that factors, other than simple dilution

3.75

Major oxides (%)

by fresh groundwater input after rainfall episodes,

A12O3

9.90

8.42
9.65
7.75
9.16

determine the variations in element concentrations. Spe-

<0.10

cically, several geological, hydrogeological and miner-

SiO2

0.15

0.91
0.21
1.38
0.17

alogical aspects are involved in these chemical changes.

For example, the dissolution of eorescent sulphates
Jar, Ferr
Sta

previously formed during the dry period in partly

Minor
Mineralogy (XRD)

ooded galleries, could provoke local increases of the

Hal

Hal
Pick, Hal

SO4 and metal contents, as described in other mine dis-

Sta, Pick,

Hal, Pick

Pick, Hal

tricts like Iron Mountain, California (Alpers et al., 1994)

Pick, Sta

Pick, Sta
Major

or St. Kevin Gulch, Colorado (Kimball, 1999). Also,

Roz

mineralogical dierences between the mineralization

Sep-03

being oxidized (pyritic to base metal-rich complex ore)

Sampling

Sep-03

Jun-03
Sep-03
Jun-03
Sep-03

and host rocks (chloritic to sericitic volcaniclastic rocks,

date

silicied vitric tus, black shales, etc.) could be responsi-

T-1-C

ble for the dierential dissolution of some elements.

Sample
No.

T-5

T-7
T-7
T-9
T-9
Table 8 (continued)

5.1.5. Relation between AMD chemistry and deposit

Tintillo river

Tintillo river

river
river
river
river

geology/mineralogy
Mine/river

Tintillo
Tintillo
Tintillo
Tintillo

Fig. 5 shows that the IPB acid mine waters are

site

more acid and metal-enriched than many of those

 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1343

100
90

Inc
80

r
eas nditi
Ferrous AMD

co
ing ons
70

Ox
Fe 2+ /Fe total (%)

idis
60

ing
50

>95% Fe2+ => Eh~570 mV

>95% Fe3+ => Eh~720 mV

40

Eh~640 mV
30
Ferric AMD
20
10 (r=-0.92, 5%-95% range)

0
400 500 600 700 800 900
Eh (mV)
Fig. 9. Diagram showing the relation between the Fe(II) to total Fe ratio (Fe2+/Fetotal) and the redox potential (Eh) of the analyzed
AMD. An approximate reference value of about 640 mV allows dierentiation of the Fe(III) (>50% Fe3+) from the Fe(II) (>50% Fe2+)
acid mine waters in the IPB.

reported in the literature. Only the extreme cases re- to the average ratio of the IPB ore mineralization (Zn/
ported for Iron Mountain (with negative pH values Cu = 2.3; see Leistel et al., 1998).
and Fe, Al, Zn and Cu contents of tens of grams Another interesting feature of the AMD chemical
per litre; Nordstrom and Alpers, 1999a) show clearly composition is the high U and Th contents. The good
more extreme conditions than the IPB acid drainage. correlations found between U and elements such as:
Chemical composition of the studied AMD always (1) Al (r = 0.92), Mg (r = 0.90), Mn (r = 0.91) and (2)
shows high contents of Zn and Cu (and to a lesser de- Zn (r = 0.90), Cd (r = 0.82) together with SO4
gree, As, Pb, Cd, Co and Ni), which is a common (r = 0.89), suggest that U could be derived from the dis-
feature of mine waters draining massive sulphide solution of: (1) some aluminosilicates such as Mg-chlo-
deposits (Ball and Nordstrom, 1989; Goldfarb et al., rite and/or K-feldspars (present in the acid volcanic
1996; Plumlee et al., 1999; Nordstrom and Alpers, and vocanoclastic lithologies such as rhyolite and dacite)
1999a). and/or (2) other phases related with sphalerite-rich com-
However, the most remarkable observation that can plex ores. Uranium concentrations ranging from 1 to 9
be made on the AMD chemistry is its dependence on and from 0.3 to 2.3 ppm have been measured in rhyolites
the deposit geology and mineralogy, so that a strong and polymetallic to complex ores from the IPB, respec-
geologic control on AMD composition is suggested. tively (Marcoux, 1998). The Th contents of the IPB vol-
Thus, the increasing contents of Zn, Cu, Mn, As, Cd, canic and sedimentary rocks (225 ppm on average;
Co, Ni or Pb with increasing SO4 content (Fig. 13) Sanchez Espana, 2000) suggest that these lithologies
indicate a progressive dissolution of pyritic and poly- are the most probable sources of this element.
metallic (complex) ores (containing abundant sphal-
erite, chalcopyrite, galena, arsenopyrite and 5.1.6. Metal speciation
tetrahedrite-tenantite) at the mine sites. The observed Geochemical calculations performed with the PHRE-
Al, Mg, Na, K and Ca concentrations are indicative EQC code reveal dierent dissolved metal species in the
of dissolution of the accompanying gangue minerals acid solutions (Table 9). The geochemical predictions
(mainly chlorite, sericite and feldspars). Also, a good indicate that the dissolved metals in the acid mine waters
correlation of r = 0.96 (p < 0.05; n = 9) has been ob- are likely present in the form of either individual free
tained between the Zn/Cu ratio of acid mine waters ions (Cu2+, Zn2+, Mn2+) or as a number of dierent


and that of the drained mineralization (only taking into sulphate ionic species e:g:; FeSO 4 ; FeSO4 2 ;
2
account the cases of mine adits with AMD discharges FeHSO4 . Additionally, other ionic species in the form
for which both chemical data for water and metal of hydroxide (e.g., Fe(OH)2+) and/or chloride (e.g.,
grades for mineralization are available). In fact, the CdCl+) complexes, could be locally present, although
average Zn/Cu ratio of AMD in the IPB is 2.7, similar they would be quantitatively very minor.
1344 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

850
A
800

750
Ehcalculated (mV) R2=0.82
700

650

600

550

500
300 400 500 600 700 800 900
Ehmeasured (mV)

0.6
B
Ehmeasured -Eh calculated (Volts)

0.4

0.2

-0.2
Fe2+ <5% Fet
Fe2+ >95% Fet
-0.4
-8 -6 -4 -2 0
Log Total Dissolved Iron, molality
Fig. 10. Correlation between measured and calculated electronic potential (Eh in mV). The measured Eh values were obtained in the
eld with a Pt electrode, whereas the theoretical Eh was computed with PHREEQC v. 2.0, by introducing measured Fe(II) and Fe(III)
concentrations (modied from Nordstrom, 2000).

A signicant dierence is predicted by PHREEQC
between divalent and trivalent cations. Whereas triva-
lent cations (Fe3+, Al3+) would be essentially present
as Al- and Fe-sulphate ionic species AlSO 4;
AlSO4
2 ; FeSO
4 ; FeSO 4

2 , bivalent cations would
be present either as individual free ions (Fe2+, Cu2+)
or sulphate species (e.g., FeSO4, CuSO4).
5.2. Mineralogy of the acid mine drainage solids
5.2.1. Solubility of the AMD-related mineral phases
Considering the measured values of Eh, pH, T, dis-
solved O2, and Fe, Al, SO4, Na and K concentrations,
along with available solubility products of Fe- and Al-
bearing phases (schwertmannite, jarosite, ferrihydrite,
goethite, hematite, basaluminite, jurbanite, gibbsite)
naturally occuring in AMD systems, it has been possible
to calculate the saturation indices (SI) of these minerals
in the AMD solutions (e.g., Table 9). All thermody-
namic constants (log K, DH) have been taken from the
geochemical databases accompanying the program
PHREEQC (Parkhurst and Appelo, 1999), and from
Bigham et al. (1996).
Under the geochemical conditions normally found in
the AMD systems (pH 23.5, Eh = 640800 mV,
Fet = 1007000 mg/L, Al = 252600 mg/L, SO4 = 2
24 g/L; Tables 3 and 4), the poorly crystalline Fe-phases
(schwertmannite, jarosite), as well as the more crystal-
line (goethite, hematite) are always supersaturated
(SI > 0) in the acid solutions, therefore tending to pre-
cipitate (Table 9). On the other hand, ferrihydrite and
the amorphous to poorly crystalline Al-phases (bas-
aluminite, jurbanite, alunite, gibbsite) are mostly under-
saturated (SI < 0). This is well exemplied in Fig. 14,
where the SI values of schwertmannite and basaluminite
are plotted as a function of pH (considering the initial
conditions of a representative sample such as 938-112;
see Tables 3, 4 and 9).
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1345

10,000
A

Acidity (pH=3.7)
1,000

R2=0.91

100

10
10 100 1,000 10,000

Fe3+ (mg/L)

10,000
B
Acidity (pH 3.7-5.0)

1,000
R2=0.95

100

10
10 100 1,000 10,000
3+
Al (mg/L)
Fig. 11. Binary diagrams showing the correlation between (A) the Fe(III) dissolved in the AMD samples with acidity measured at a
reference pH value of 3.7 and (B) the Al dissolved in the AMD samples with acidity measured at the pH range of 3.75.0. Acidity is
given in mg/L CaCO3 eq. and has been calculated by titration with NaOH 1.6 N.

To illustrate the solubility behaviour of these Fe- and
Al-phases, the SI calculations performed on two AMD
systems from Corta Atalaya (Ro Tinto mine) are shown
in Fig. 15. These plots show the evolution of the solubil-
ity of several Fe- and Al-phases in km-scale proles
downstream from the discharge points, and include
two possible scenarios of pH evolution, namely: (A) con-
stant pH around 2.7 and (B) pH drop of an aluminous
AMD solution (pH  4.5) mixing with more acid, ferric
AMD (pH  2.7). The observed dierence between Fe
and Al solubility leads to spatial and temporal separa-
tion of precipitating phases of hydrolyzed Fe and Al.
In all cases, the solubility calculations performed,
as well as kinetic considerations, clearly suggest that
schwertmannite and, to a lesser extent, jarosite are
the dominant phases controlling Fe(III) solubility in
the AMD solutions, whereas Al solubility would be
mainly controlled by amorphous to poorly crystalline
Al-phases like basaluminite. Although goethite has
also been found in variable proportions in several
MDM samples (Table 7), and it has been proved to
precipitate coetaneously with schwertmannite, ferrihy-
drite and jarosite in AMD systems (e.g., Bigham
et al., 1996), this mineral does not appear to play a
relevant role in controlling the Fe(III) concentration
of acid solutions. Goethite is more commonly found
in older Fe(III) deposits (e.g., Fe(III) crusts) at the
mine sites than in the fresh, recently precipitated
1346 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

2000 9000

Acidity (mg/L CaCO3)

Acidity (mg /L CaCO3 )

A Sample 938-4
1800 Sample 938-51 8000 D
1600 17% 7000
1400 6000
1200 Fe2+ hydrolysis
5000
1000 15%
Al3+ hydrolysis 4000 52%
800
3000 Al3+ hydrolysis
600
400 2000
3+
200 26% Fe hydrolysis 1000 11% Fe3+ hydrolysis
0 0
2 3 4 5 6 7 8 9 2 3 4 5 6 7 8 9
pH pH
7000 12000
Acidity (mg/L CaCO3)

B Sample 937-16 E Sample 959-16

Acidity (mg/L CaCO3)

6000 10000
5000
8000
4000 26%
Al3+ hydrolysis 6000 35%
3000 Al3+ hydrolysis

2000 4000
35% 2000 22%
1000 Fe3+ hydrolysis
Fe3+ hydrolysis
0 0
2 3 4 5 6 7 8 9 2 3 4 5 6 7 8 9
pH pH
6000 3000
C Sample 937-108 Sample 938-127
Acidity (mg/L CaCO3)

F
Acidity (mg/L CaCO3)

5000 2500
Fe2+
4000 2000
3000

H 2 itio
H 2 itio

1500

ad
ad

Fe2+

O2 n
O2 n

d
d

2000 1000
Fe3+
1000 Fe3+
500
0 0
2 3 4 5 6 7 8 2 3 4 5 6 7 8 9 10
pH pH

Fig. 12. Several examples of titration curves obtained after titration with NaOH of the acid mine water samples. The respective Fe and
Al contents of these samples are given in Table 4. In cases A, B, D and E, the relative importance of the hydrolysis of Fe and Al in the
total acidity is indicated. In C and F, the eect caused in the titration curves by the addition of H2O2 (over 5 min) to completely oxidize
Fe(II), is also illustrated.

colloidal particulates. This suggests that goethite comes stable only at negative pH values, and gibbsite
should be best considered as a product of mineralogi- is usually unstable at pH < 5.5 (depending on sulphate
cal transformation of metastable Fe(III) phases (schw- activity), being rare in acid-sulphate environments
ertmannite, ferrihydrite, jarosite) than a mineral (Nordstrom, 1982; Nordstrom et al., 1984; Nordstrom
directly precipitated from the AMD solutions. In fact, and Alpers, 1999a). Jurbanite is the most stable mineral
both goethite and hematite show much slower growth and thermodynamically favoured to precipitate at pH
kinetics than schwertmannite, ferrihydrite and jarosite below 4, although it rarely appears as an AMD precip-
(Nordstrom and Alpers, 1999a). Therefore, although itate. On the other hand, basaluminite is the more wide-
the geochemical calculations predict the precipitation spread mineral phase known to precipitate from AMD
of goethite and hematite (Table 9; Fig. 15), they seem solutions at pH values of 5 or above (Nordstrom
to require more stable conditions and a longer time to et al., 1984; Nordstrom and Alpers, 1999a).
form. In summary, and in agreement with previous works
Although the Al-phases have not been identied by in other mine districts (e.g., Bigham et al., 1996; Lee
XRD, basaluminite is the mineral that best explains et al., 2002), a good correlation has been found between
the Al behaviour of acid solutions, and is the authors
pH and mineralogy of the MDM at the watershed
preferred option to account for the control of Al concen- scale, with ferrihydrite precipitating at pH values
tration at the critical pH range of 45. Alunogen be- above 6, amorphous Al-oxyhydroxysulphate (probably
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1347

3,000 Table 9
A Theoretical metal speciation in a typical AMD solution from
2,500 Al
0)
the IPB (exemplied by sample 938-112, see Tables 35 for a
Zn 0.9 detailed chemical composition), and calculations of the satura-
(r=
2,000 Cu Al
tion indices (SI) of selected Fe and Al mineral phases with
mg/L

1,500
respect to this AMD uid
) Element Species Molality mol%
=0.87
1,000 Zn (r 3+
Al 6.72E
02
500 AlSO4
4.04E
02 60
Cu (r=0.70) 2
AlSO4 2.09E
02 31
0 3+
Al 5.86E
03 9
0 10 20 30 40 50
SO4= (g/L) Fe3+ 2.23E
03
FeSO4 1.49E
03 67
10,000
B FeSO4
2 5.35E
04 24
9,000 3+
Fe 1.08E
04 5
8,000
As Fe(OH)2+ 7.23E
05 3
7,000 0 ) FeHSO2 1.61E
05 1
0.2 Mn 4
6,000 (r=
g/L

As Cd
Fe2+ 3.60E
02
5,000
Fe2+ 2.11E
02 59
4,000
FeSO4 1.46E
02 40
3,000 .76)
Cd (r=
0
FeHSO4 2.23E
04 1
2,000
1,000 Mn (mg/L; r=0.83)
Mg2+ 9.92E
02
0 MgSO4 4.93E
02 50
0 10 20 30 40 50 Mg2+ 5.00E
02 50
SO4= (g/L)
Mn2+ 4.93E
03
Fig. 13. Binary plots with regresion lines and correlation Mn2+ 2.90E
03 59
(Pearson-Product moment) values of SO2
with dierent MnSO4 1.99E
03 40
4
dissolved metals: (A) Al, Zn, Cu and (B) As, Mn, Cd. MnCl+ 3.79E
05 1
Ca2+ 7.33E
03
basaluminite) at pH > 4, and a mineralogical assemblage CaSO4 3.27E
03 45
of schwertmannitejarositegoethite found in AMD Ca2+ 4.02E
03 55
with pH between 2 and 4.
Cu2+ 2.61E
03
CuSO4 1.18E
03 45
5.2.2. Iron precipitates and eorescent sulphates as trace
Cu2+ 1.43E
03 55
metal sorbents
Iron colloidal precipitates such as schwertmannite or Cd2+ 2.02E
05
ferrihydrite have been found to act as sorbents for trace CdSO4 7.25E
06 36
metal removal in AMD systems, with a high pH-depen- Cd2+ 5.86E
06 29
dence of metal sorption (e.g., Smith, 1999). Sorption of CdSO4 2

2 5.16E
06 26
the less soluble elements like As or Pb on these mineral CdCl+ 1.86E
06 9
phases can occur at pH around 4.55, whereas 100% Zn2+ 6.94E
03
sorption of other cations like Cu, Zn or Cd only occurs Zn2+ 3.04E
03 44
in circumneutral conditions (e.g., Smith, 1999; Lee et al., ZnSO4 2.53E
03 36
2002). ZnSO4 2

2 1.34E
03 19
The analyzed mineral samples collected from AMD
sites showing a schwertmannitejarositegoethite min- Saturation indices
eral paragenesis always have As, Cu, Pb and Zn concen- Phase Formula log K SI
trations in the range of tens to a few thousand ppm Dissolving minerals
(Table 7). These values are higher than those observed Al(OH)3(a) Al(OH)3 11.06
5.90
for the samples dominated by quartz and aluminosili- Alunite KAl3(SO4)2(OH)6
1.34
0.61
cates (chlorite, feldspar, mica; Table 6), and suggest that Basaluminite Al4(OH)10SO4 22.70
9.41
Gibbsite Al(OH)3 8.34
3.17
the high specic surface area of the Fe precipitates
Jurbanite AlOHSO4
3.23
0.76
would have favoured metal sorption. Fe(OH)3(a) Fe(OH)3 4.89
1.68
Titration experiments conducted in AMD samples Ferrihydrite Fe5HO8 4H2O 5.00
1.79
from the area (unpublished data) have shown virtually Gypsum CaSO4 2H2O
4.58
0.16
total As removal from solution during schwertmannite (continued on next page)
1348 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

Table 9 (continued) ing the evaporative processes taking place in extremely

Phase Formula log K SI concentrated AMD pools. However, these sulphates
are only temporal sinks and can release high quantities
Precipitating minerals
Hematite Fe2O3
3.70 10.12
of acidity, SO4 and metals again to the water courses
Goethite FeOOH 0.64 2.56 during rainfall, causing a rapid pH decrease and a high
K-Jarosite KFe3(SO4)2(OH)6
14.49 6.66 increase in dissolved solids, as described in other mine
Na-Jarosite NaFe3(SO4)2(OH)6
10.84 5.16 districts (e.g., Alpers et al., 1994; Kimball, 1999; Nord-
Schwertmannite Fe8O8(SO4)(OH)6 18.00 11.30 strom, 1999). This process was observed during a eld
Relative abundances of the dierent ionic species in molal visit performed on 1st October 2003, when the rst rain-
percentage. The log K values used for the SI calculation are fall discharge after the dry season dissolved in a few
indicated for each mineral phase. hours around 5090% (varying among the mine sites)
of the salts formed during the summer. This salt dissolu-
tion provoked signicant pH decreases and conductivity
precipitation at pH 3.5. This is in agreement with the increases in the studied streams.
high As contents found in the naturally occurring schw-
ertmannite (1700 ppm As on average; Table 7). Addi- 5.3. Environmental implications
tional mass-balance calculations performed in the
Odiel river (unpublished data) suggest a considerable 5.3.1. Eects on water quality and calculation of metal
retention of Zn and a practically complete removal of loads
Pb and Cu at pH  8. This trace metal retention would It has been estimated that 29% (390 of 1360 km) of
have resulted from adsorption by the abundant Fe and the total length of streams and water courses in the Odiel
Al colloidal phases produced after the mixing of the river watershed are aected to a variable degree by
Odiel river with several AMD discharges. AMD pollution (Fig. 16). This mine-related contamina-
These results are in agreement with available data of tion, which aects about 85% of the Odiel river main
metal sorption on hydrous Fe(III) oxide in AMD sys- course (104 of 122 km), is evident in the Odiel river
tems (e.g., Webster et al., 1998; Smith, 1999; Lee et al., mouth, where pH values of 3.0 0.5, and average (med-
2002; Fukushi et al., 2003), and indicate that trace metal ian) metallic contents of 16 mg/L Fe, 12 mg/L Mn, 7 mg/
retention by sorption onto Fe and Al colloidal precipi- L Cu, 20 mg/L Zn and 66 lg/L Cd, are usually measured
tates can be an eective mechanism for natural attenua- (data from the period 19902001; COCA network; Con-
tion of dissolved metal loads. federacion Hidrograca del Guadiana, unpublished
With regard to the chemistry of the salts, chemical report).
analyses of SO4 eorescences show that these phases Based on measured chemical compositions and water
can contain very high Zn and Cu concentrations (Table ow of the AMD discharges, SO4 and metal loads have
8). These metals are sorbed and/or co-precipitated dur- been calculated for the studied mining districts in the

Fig. 14. Variation of the solubility of schwertmannite and basaluminite with pH. The saturation index (SI), dened as SI = log (IAP/
Ksp), where IAP is the ion activity product of the dissolved mineral constituents, and Ksp is the solubility product for the mineral, has
been calculated with PHREEQC v. 2.0 (Parkhurst and Appelo, 1999), considering the initial conditions of sample 938-112 (Tables 3
5). The shaded areas correspond to the approximate pH ranges for the typical ferric and aluminous AMD. See text for explanation.
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1349

20
A Iron phases Schw
15 Aluminium phases pH=2.7 Hem

10 K-Jar
Na-Jar
5 Goet

SI 0 Ferr
Gib
-5 Basal

-10
-15
-20
0 2 4 6 8 10 12
Distance (km)
10
B
5

0 Basal
SI

-5 mixing Jur

Gib
-10
pH=4.5 pH=2.7 Alun
-15

-20
0 2 4 6 8 10 12
Distance (km)

Fig. 15. Variation of the solubility (given by the saturation index, SI) of several Fe and Al mineral phases in AMD with distance. Both
proles are plotted in a downstream direction from the respective discharge points of AMD. (A) Acid leachate from a waste-rock pile
in Corta-Atalaya; (B) outow from embalse del Cobre (Rio Tinto mines). In (A), the SI proles of the Fe phases are plotted as solid
lines, whereas the aluminous phases are plotted as dashed lines. The dotted line of SI = 0 separates the elds of precipitation (SI > 0)
and dissolution (SI < 0). In (B), the abrupt change in the SI is due to mixing of the AMD with a more acid (pH 2.7) AMD stream.
Calculations performed with PHREEQC v. 2.0 (Parkhurst and Appelo, 1999) from chemical analysis of sucessive sampling points at
each AMD discharge. See text for explanation. Abbreviations: Schw, schwertmannite; Jar, jarosite; Ferr, ferrihydrite; Goet, goethite;
Hem, hematite; Basal, basaluminite; Gib, gibssite; Alun, alunite; Jur, jurbanite.

IPB for the period 20032004 (Table 10). These estima-
tions have been performed considering two dierent sce-
narios (winter and summer), as yearly average values for
chemical composition and ow rate are highly unrealis-
tic, as discussed previously.
As can be deduced from Table 10, Tharsis and Ro
Tinto (Corta Atalaya) are, by far, the mine sites that
most profusely contribute to AMD volume, and SO4
and metal loads transferred to the Odiel uvial system,
followed by San Telmo and Sotiel-Almagrera. These 4
mine districts can represent around from 70% (winter)
to 90% (summer) of the total SO4 and metal loads re-
ceived by the Odiel river watershed from AMD
discharge.
Also, from simple mass-balance calculations, it can
be deduced that around 99% of the Fe and As, and from
60% to 80% of other metals (Al, Mn, Cu, Zn, Cd, Pb)
and SO4 transported by the acid mine euents as dis-
solved load, would have been retained within the Odiel
basin (Table 10). Thus, the great majority of metal loads
released from the mine sites and transported by the acid
mine waters to the streams and tributaries of the Odiel
river, should essentially remain in the water courses in
the form of solid phases like schwertmannite, jarosite,
ferrihydrite, basaluminite or eorescent sulphates.
However, most of these minerals are unstable and can
be either transported as colloids downstream during
high ow conditions or, on the other hand, they can
be transformed to more stable minerals (e.g., goethite)
and form cemented and more permanent chemical
sediments.
These results suggest that only 1% of the total Fe and
As dissolved load, and around 2040% of the total Al,
Mn, Cu, Zn, Cd, Pb and SO4 loads, would have been
transferred from the Odiel river basin to the Huelva
estuary. However, given the water volumes implied in
1350 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

Fig. 16. Metal-aected map of the Odiel river basin. The total length of streams aected by AMD pollution, and the respective
dissolved metal loadings reported in Table 10 for the dierent sub-basins are indicated. Daily metal loadings represent the situation
observed in winter 2003. See text for explanation.

this uvial system, this still represents impressive metal 0.5 kg of As, would have been daily transferred as dis-
uxes. Thus, during the winter months of 2003, an aver- solved load to the estuarine system. If added to the sum-
age of around 4 t of Al, 9 t of Mg, 0.9 t of Mn, 1.4 t of mer loads, these data imply a total yearly load of about
Zn, 0.6 t of Cu, 0.2 t of Fe, 9 kg of Cd, 6 kg of Pb and 3760 t of dissolved metals for 20032004.
Table 10
Calculation of sulphate and metal loads transferred by AMD discharge from the mine sites of the IPB to the stream waters of the Odiel river basin

Mine district Season Q (L/s) Sulphate and metal loads

SO4 Fe Al Mg Mn Cu Zn As Cd Pb
(Tn/day) (kg/day) (kg/day) (kg/day) (kg/day) (kg/day) (kg/day) (g/day) (g/day) (g/day)

Upper Odiel 184 9759 10,731 14,711 1845 2022 3213 7723 23,425 4274
Angostura Winter 0.4 0.2 4 2 3 0.1 0.7 0.2 0.1 1.6 1
Summer 0.2 0.1 2 1 2 0.1 0.4 0.1 0.1 1 0.6
Concepcion Winter 12 1.1 160 57 18 1.3 5 3 16 21 10
Summer 4 0.8 93 48 21 3 3 48 10 10 7
Corta Atalaya (Rio Tinto) Winter 350 172 6760 10,200 14,370 1820 1872 3100 6020 23,000 4200

J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

Summer 50 61.2 3240 3167 1776 825 570 1110 280 3730 40
El Soldado Winter 2.5 0.2 33 7 7 0.2 1.1 2 7 9 19
Summer* 0.9 0.1 14 3 3 0.1 0.5 0.9 3 4 8
Esperanza Winter 2 0.7 159 29 19 0.6 7 5 3 9 12
Summer 0.6 0.2 64 10 14 0.3 2 1 20 4 2
La Poderosa Winter 8 3.6 960 138 36 0.7 104 52 600 330 2
Summer 2 1.1 295 45 16 1 28 17 630 70 3
San Miguel Winter 11 5.2 1420 255 243 21 20 12 870 0.7 27
Summer 0.8 0.1 42 6 3 0.8 0.2 6 13 1 0.7
San Platon Winter 2 1.0 263 43 15 1 12 39 207 54 3
Summer 0.2 0.1 35 4 2 0.2 0.5 4 19 7 0.2

Lower-middle Odiel 41 1821 305 479 98 55 147 2556 69 12

Campanario Winter 1 0.2 67 5 8 2 1 5 976 4 2

Summer
Castillo-Buitron Winter* 2 0.5 190 26 10 2 10 14 n.a. n.a. n.a.
Summer 0.7 0.2 79 11 4 1 4 6 n.a. n.a. n.a.
Descamisada Winter 4 0.6 267 21 33 31 3 9 600 22 6
Summer 0.2 0.02 6 0.5 1 0.7 0.1 0.3 21 0.5 0.2
Gloria Winter* 0.3 0.02 5 1 1 0.2 2 0.1 2 0.2 0.1
Summer 0.1 0.01 2 0.4 0.4 0.05 0.7 0.03 0.7 0.07 0.03
La Torerera Winter 1 0.05 2 1 3 0.8 0.2 0.6 13 1 3
Summer
Sotiel-Almagrera Winter 125 38 1040 230 350 43 32 90 n.a. n.a. n.a.
Summer 20 3 43 10 14 2 1 4 n.a. n.a. n.a.
Tincheron Winter 2 0.3 20 4 30 5 0.5 0.5 15 1 1
Summer 0.3 0.05 4 0.7 6 1 0.1 0.1 3 0.2 0.2
Tinto-Sta Rosa Winter 5 1 230 17 44 14 7 27 950 41 1
Summer 3 0.5 45 5 25 8 4 15 398 17 0.1

Olivargas 3 670 105 88 15 13 156 397 349 4001

Aguas Tenidas Winter 3 0.2 52 12 16 2 4 16 73 60 43

Summer
Cueva de la Mora Winter 3.5 1.1 208 38 47 5 4 132 n.d. 260 3950
Summer 1.6 0.4 71 17 25 3 0.4 17 n.d. n.d. n.d.
La Zarza Winter 2 1.4 410 55 25 8 5 8 324 29 8
Summer 0.5 0.1 114 13 19 4 1 2.5 103 7 1
Monte Romero Winter
Line missing

1351
 1352
Summer
(continued on next page)
Table 10 (continued)

J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356

Mine district Season Q (L/s) Sulphate and metal loads

SO4 Fe Al Mg Mn Cu Zn As Cd Pb
(Tn/day) (kg/day) (kg/day) (kg/day) (kg/day) (kg/day) (kg/day) (g/day) (g/day) (g/day)

Oraque 64 10,842 2802 5582 563 395 1310 38,063 3334 950

Confesionarios Winter 15 5.2 1950 233 242 14 2 6 700 240 10

Summer* 3 1.3 507 61 63 4 0.5 2 180 62 3
El Carpio Winter 1.6 0.3 41 10 14 1 5 3 69 12 2
Summer
El Perrunal Winter 1 0.16 1.1 5.3 14 4 0.3 0.7 4 1 1
Summer 0.3 0.23 1 1.5 6 1 0.1 0.2 0.5 0.4 0.5
Lomero-Poyatos Winter 6 3.0 360 52 323 7 4 12 200 20 400
Summer 2.5 0.9 115 17 109 2 1 3 50 8 140
San Telmo Winter 363 12.1 1966 385 820 120 76 263 650 1000 200
Summer 3 1.0 32 31 118 11 5 22 3 40 13
Tharsis Winter 50 433 6523 2117 4169 417 307 1024 36,440 2061 337
Summer 10 13 1960 631 1225 125 89 306 11,032 610 93

Meca 12 1973 275 540 63 50 97 5550 1779 6463

Tharsis Winter 25 12.01 1973 275 540 63 50 97 5550 1779 6463

Summer 2 1 392 127 235 21 15 53 1700 122 19
Total AMD 20032004 Winter 671 303 25,064 14,218 21,399 2584 2535 4922 54289 28,956 15,700
Summer 106 85 7157 4210 3687 1014 726 1618 14,466 4694 331
Odiel outlet at Gibraleon (pH 4.2) Winter 2700a 96 224 4043 8986 900 642 1350 450 9435 5616
20032004 (pH 3.3) Summer 450a 24 77 1080 2565 350 156 430 156 2020
Dissolved metal loads retained in Basin (%) 20032004 Winter 68 99 72 58 65 75 73 99 67 64
Summer 72 99 74 30 65 79 73 99 57

Two dierent scenarios (winter and summer seasons) are considered. These calculations have been performed considering the chemical data provided in Tables 3 and 4 from all the mine sites studied in the present work, and are subdivided into
dierent sub-basins (Upper and lower-middle Odiel, Olivargas, Oraque, Meca). In order to evaluate the rate of basin-scale retention of sulphate and metals dissolved in AMD, the total amount of metal and sulphate loadings provided by
 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
5.3.2. Duration and future evolution of the acid mine
drainage
Some of the studied acid emissions have been ema-
nating from underground mines abandoned since the
early 20th century (e.g., El Soldado and Campanario
in 1917, La Poderosa in 1924, Esperanza and Tinto-
Sta Rosa in 1931, Aguas Tenidas and San Platon in
1934) and late 19th century (e.g., Descamisada in
1876, Confesionarios in 1888; Pinedo Vara, 1963). These
remain very acid and have high SO4 and metal loads.
The antiquity of the AMD systems has led to signicant
landscape transformations such as: (1) cemented layers
and laminated, algal mat Fe(III) formations of consider-
able thickness (1050 cm) which record hydrologic epi-
sodes (wet/dry seasons) and (2) elevated terrace
deposits formed by hydrous Fe oxides in the conuence
between AMD and natural streams.
At present, it is dicult to predict whether or not the
AMD chemistry is undergoing some kind of long-term
temporal evolution, which could result in an improve-
ment of stream water quality at the basin-scale. Unfor-
tunately, there is no historical record of water quality
data for the cited mine discharges with which to com-
pare the current chemical signatures, and therefore, it
is not possible to decide if a signicant decrease in the
acidity and/or metal contents is taking place at a regio-
nal scale. In this sense, several studies have reported lit-
tle chemical change of acid euents emanating for
hundreds of years, whereas others state that poor drain-
age quality may last only 2040 a (Demchak et al.,
2004).
In any case, further research on the studied AMD
discharges has to be performed in the forthcoming years
in order to obtain a realistic model of prediction for
water quality evolution at the basin scale, which could
serve as a basis for future reclamation and/or restoration
plans in the Odiel river basin.
6. Conclusions
The acid mine waters produced by the oxidation of
pyritic mine wastes and massive mineralizations in the
mines of the IPB show marked seasonal variations in
ow rate and chemical composition, in response to cli-
matic, hydrogeological, geological, and mineralogical
factors. This variability in the AMD hydrogeochem-
istry allows recognition of very dierent conditions of
pH, Eh, DO, oxidation rate of Fe(II) and metal con-
tent among the studied acid euents. This fact has
strong implications as it introduces additional dicul-
ties into the design of corrective measures at the mine
sites.
Iron is several orders of magnitude more abundant
than any other redox species (such as As(III)/As(V) or
O2/H2O) in the acid mine waters. Consequently, the re-
1353
dox chemistry of the AMD systems is basically dened
by the oxidation of Fe(II), which seems to be strongly
catalyzed by acidophilic, Fe-oxidizing bacteria and is
perfectly correlated with the electronic potential (Eh)
of the acid solutions.
The acidity of AMD is not only given by the concen-
tration of H+, but also by the content of Fe(III) and Al,
whose hydrolysis (around 2.7 and 4.5, respectively) re-
leases important amounts of additional acidity and pro-
vokes the buering of the AMD systems.
As a result of the rapid oxidation and subsequent
hydrolysis of dissolved Fe, a number of meta-stable
and poorly crystallized Fe mineral phases (mostly schw-
ertmannite, with additional jarosite and/or goethite) are
formed. The mineralogy of these mineral phases is
strongly dependent on the water pH, so that it reects
the geochemical evolution of these acid sulphate waters.
Thus, schwertmannite ( jarosite goethite) precipi-
tates in the vicinity of the discharge points at pH 24;
when most of the Fe has been precipitated, amorphous
to poorly crystalline Al-oxyhydroxysulphates form at
pH 4.5; nally, ferrihydrite is usually favoured to precip-
itate at circumneutral pH in the stream courses. Among
the solid phases forming in the AMD systems, schwert-
mannite plays a major role: (1) in the control of Fe sol-
ubility and (2) in the retention of trace elements (As, Pb,
Cu).
The evaporation of AMD causes the precipitation of
hydrated sulphate salts which are temporal reservoirs of
acidity, SO4 and metals.
From mass-balance calculations, it has been shown
that the majority of the SO4 and metal loads released
from the mine sites by the acid euents would substan-
tially remain in solid form within the Odiel basin. How-
ever, the remaining dissolved loadings that reach the
Huelva estuary still imply impressive metal amounts of
several thousand tonnes (specially the most soluble met-
als such as Mn, Zn, Cd and Cu) which are being yearly
transferred to the estuarine system, and nally, to the
Atlantic Ocean.
Acknowledgements
We sincerely thank Juan Antonio Martn Rub,
from the IGME laboratory, for his attention dedicated
during the XRD analyses. Ron Fuge, K. Hudson-Ed-
wards and an anonimous reviewer are thanked for their
helpful comments on an earlier version of this manu-
script. This project has been nantially supported with
funds from the CICYT Project No. REN2003-09590-C
O4-04, and from the Junta de Andaluca (Consejera de
Empleo y Desarrollo Tecnologico). The authors dedi-
cate this work to the loving memory of the 192 people
killed by the terrorist bombings in Madrid on 11-
March 2004.
1354 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
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