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Applied Geochemistry 20 (2005) 13201356
www.elsevier.com/locate/apgeochem
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.
*
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 1321
sulphide province (Huelva, SW Spain) with a legacy of chemistry and metal loads; (3) mineralogical and chem-
abandoned mines and attendant spoil tips, including ical transformations taking place in the AMD-generat-
enormous sulphide-bearing waste rock piles, tailings ing mine sites; (4) processes favouring natural
and ooded pits. These mine wastes are continuing attenuation; and (5) GIS-based, basin-scale, hydrogeo-
sources of environmental contamination, mostly in the chemical mapping according to water quality criteria.
form of acid mine drainage (AMD). These acid mine This paper summarises the results obtained from
waters have caused severe pollution of the Odiel and February-2003 to May-2004, describing the main geo-
Tinto uvial systems, with transference of large amounts chemical features of the AMD systems, the mineralogi-
of acidity and dissolved metals (Fe, Al, Mn, Cu, Zn, Cd, cal and chemical characteristics of mine drainage
Pb), As and SO4 (see for example Van Geen et al., 1991, precipitates and eorescent sulphate salts, and the envi-
1997; Nelson and Lamothe, 1993; Elbaz-Poulichet et al., ronmental implications.
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- 2. Methodology and analytical techniques
tem and the Gulf of Cadiz). Acidity and metal concen-
trations of the AMD-aected streams have caused the 2.1. Sampling
loss of most forms of aquatic life, with the exception
of some types of microorganisms adapted to these ex- Field work was performed during several seasons
treme environments (Lopez-Archilla and Amils, 1999; through 2003 (FebruaryMarch, April, June, July, Sep-
Lopez-Archilla et al., 2001; Gonzalez-Toril et al., 2003; temberOctober, November) and 2004 (January, March,
Amaral Zettler et al., 2003). May) and included a comprehensive and detailed explo-
During the last decade, the Junta de Andaluca (Re- ration of the study area, with identication and sam-
gional Government) has made a considerable economic pling of the dierent acid mine euents and stream
contribution to various remediation and restoration at- waters, as well as sediments and precipitates naturally
tempts aimed at reducing the environmental impact of occuring in the AMD systems, and subsequent chemical
acid mine waters (e.g., Serrano et al., 1995). These ini- and mineralogical-diractometric analyses of the col-
tiatives have included the geotechnical stabilization and lected samples.
revegetation of waste piles, construction of rain water Water samples for chemical analyses of major ions
drainage systems and sealing of mine adits, as well as were taken with 60 ml-syringes and Millipore standard
passive treatments such as anoxic limestone drainage sampling equipment. All samples were ltered in the
(ALDs) and anaerobic compost wetlands (Vinas and eld with 0.45 lm cellulose acetate membrane lters,
Lopez Fernandez, 1994; AYESA, 1996). Unfortu- stored in 125 ml-polyethylene bottles, acidied down
nately, these attempts have been highly ineective to pH < 2 with concentrated HNO3, and refrigerated
due to chemical and climatic constraints (high acidity during transport. The polyethylene bottles were washed
and metal contents, seasonal variability of water with HNO3 for 12 h prior to sampling, and a trace metal
discharge). clean procedure was always employed during sample
A range of papers have been published on the eects collection.
of this mine-related pollution in the Tinto-Odiel estua- The solid samples (ferric crusts, sulphate eores-
rine system (see above), although unfortunately, very lit- cences) were directly stored in 125 ml-polyethylene bot-
tle work has been carried out to unravel the tles, while the ochreous, colloidal precipitates were
geochemistry of these acid mine waters in origin, their taken with 60 ml-syringes and/or by ltering acid water
seasonal chemical variations, their interaction with the using a manual suction kit.
stream waters, or the mineralogical and chemical com-
position of the AMD-related ochreous precipitates. 2.2. Field measurements
These questions are important not only from a theoret-
ical viewpoint, but also from a practical aspect, as they Field parameters such as pH, Eh, temperature (T),
are critical for the design of remediation/attenuation dissolved O2 (DO), and electric conductivity (EC), were
strategies. measured in situ with Hanna portable instruments
The Geological Survey of Spain (IGME) is investigat- (probe types HI 9025C, HI9033 and HI9025, respec-
ing the geochemistry of the AMD systems and their tively) properly calibrated on site against supplied cali-
interaction with fresh water courses in the Odiel river ba- bration standards (Hanna standard solutions HI 7004
sin, which receives the great majority of AMD discharge (pH 4.01) and HI 7007 (pH 7.01) for pH; Hanna stan-
from the IPB mines. This study includes the following dard solutions HI 7021 (240 mV) and 7022 (470 mV)
objectives: (1) physico-chemical characterization of for Eh). For Eh measurements, the mV reading obtained
AMD and its relation to geological, mineralogical and with the PtAg/AgCl electrode system was corrected for
hydrological factors; (2) seasonal variations of AMD 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 The detection limits for major cations (Na, K, Ca,
Nordstrom, 1977). Mg, Mn, Fe, Al) was <1 mg/L in all cases.
Flow rates have been calculated in all cases by con- Solid samples were analyzed using XRF (PHILIPS
ventional methods using digital ow meters (GLOBAL 1404) for the elements Si, Al, Fe, Ca, Ti, Mn, K, Mg
WATER) in previously dened stream sections. and P, elemental analyzer (Eltra CS-200) for total S,
Quantitative measurement of acidity, alkalinity and ICP-MS (after digestion with HNO3 and H2O2 follow-
Fe(III)/Fe(II) concentrations, were performed in situ ing the method described in USEPA 3050B) for Cd,
with Hach titration-based test kits using the digital titra- Co, Cr, Hg, Mo, Sb, Th, Tl, U, V, Zn, and AAS for
tion methods 8201 (bromophenol blue) and 8202 (phe- Na, Cu, As and Pb. A number of certied international
nolphthalein (total) acidity; AC-DT model), 8203 reference materials (BCS 175/2, BCS 302/1 and BCS 378,
(phenolphthalein (total) alkalinity using H2SO4; AL- from the British Chemical Standards; FER-1 and FER-2
DT model), and 8214 (citrate, sodium periodate and from the Canada Centre for Mineral and Energy Tech-
sulfosalicylic acid with TitraVer standard solution nology) were used to check the accuracy of the analytical
titration cartridge for Fe(III) and total Fe) reported by data. The detection limits for trace elements in solids
the Hach Instruments company. Titration tests for the were 10 ppm for Ni and Se, 2 ppm for Be, Co, Cu,
measurement of AMD acidity were performed at inter- Hg, Th, V and Zn, 1 ppm for Cr, 0.5 ppm for Mo and
mediate pH values of 3.7 and 5, and total acidity (pH 0.2 ppm for Cd, Sb and U.
8.3), with NaOH 1.6 N and continuous measurement The solid samples have been mineralogically charac-
of pH and the amount of base used in every step. terized by powder XRD using a PHILIPS PW 1710 dif-
For routine, semiquantitative estimations of Fe(II) fractometer with Cu Ka radiation (40 kV, 30 mA), and a
concentration, Merckoquant-type (MercK) Fe(II) diracted-beam monochromator. For routine XRD
strips were also used. Similar methods were occasionally inspections (for samples of sediment and sulphate salts),
applied for semiquantitative estimations of other ele- 060 2h scans were used with 0.5 s counting time per
ments such as SO2 4 ; Zn and Mn. step. For more detailed XRD proles (for the Fe colloi-
dal precipitates), slower counting times of 50 s per step
2.3. Laboratory analyses interval in 1080 2h scans, were selected.
All samples were analyzed in the IGME laboratories. 2.4. Geochemical modelling
Natural water samples were analyzed using diverse spec-
trometric techniques, such as spectrophotometry (ALLI- The PHREEQC code (version 2.0; Parkhurst and
ANCE Integral Plus) for SO4, NO3, Cl and PO4, AAS Appelo, 1999) was used for geochemical modelling,
(ame operation, VARIAN FS-220) for Na, K, Mg, including calculation of theoretical Eh (pe) values based
Ca and Fe, and ICP-MS (LECO Renaissance) for trace on the Fe(II)/Fe(III) redox couple, activity and chemical
metals. AMD samples were analyzed by AAS for Na, K, speciation of dissolved species, and saturation index of
Mg, Ca, Fe, Cu, Mn, Zn and Al, ICP-AES for Be, Ni analyzed minerals in the parent acid solutions. The ther-
and Se, and ICP-MS for Ag, As, Ba, Cd, Co, Cr, Hg, modynamic database of PHREEQC was enlarged with
Mo, Pb, Sb, Th, Tl, U and V. Sulphate was gravimetri- data from other geochemical codes (MINTEQA2,
cally measured as BaSO4, whereas Cl was analyzed titri- WATEQ4F (Ball and Nordstrom, 1991)) for the solubil-
metrically with AgNO3. The accuracy and precision of ity of schwertmannite and ferrihydrite.
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, 3. Geological and hydrological framework
APG) and others (e.g., internal samples of industrial
mine euents, control samples of the Water Research 3.1. Geology
Centres AQUACHECK international program) and
close agreement with certied values was achieved for The Odiel uvial system (1360 km in length) drains a
all metals. 115In was used as internal standard for cali- vast area of 2300 km2, crossing the Province of Huelva,
bration of the ICP-MS analyses. The detection limits from Sierra de Aracena in the North to the Huelva estu-
for trace elements in natural waters were 2.5 lg/L for ary in the South, and receives most of the acid mine
Se, 2 lg/L for Al, Be, Cr, Hg and Zn, 1 lg/L for Ni, euents emerging from IPB mines (Fig. 1).
and 0.5 lg/L for Ag, As, Ba, Cd, Co, Cu, Mn, Mo, The upper, northernmost part of the basin is under-
Sb, Tl, Th, U and V. The detection limits for trace ele- lain by plutonic and metamorphic rocks (sericitic schists,
ments in acid mine waters were 100 lg/L for Se and quartzites, granites, gneises, marbles and tus) of Upper
Ni, 10 lg/L for Be and Zn, 2 lg/L for Ag, Ba, Co, Cr, Precambrian to Devonian age. The middle and lower
Hg and Pb, 1 lg/L for U, 0.5 lg/L for V, 0.4 lg/L for basin is characterized by the Upper Devonian to Middle
As, Cd, Cu and Sb, and 0.2 lg/L for Mo, Tl and Th. 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 the southernmost area of the Odiel basin drains Miocene
quartzites, the volcanic-sedimentary complex (VSC), detrital materials (sands, silts, clays).
formed by shales, greywakes, acid to basic volcanic The IPB represents the largest concentration of mas-
and volcaniclastic rocks, and the Culm group, made of sive sulphide on Earth, and despite its long history of
a ysch-like sequence of shales and greywakes). Finally, 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, the summer), and consequently, acidity and metal loads
including 35 Mt Zn, 14.6 Mt Cu, 13 Mt Pb, 46,100 t Ag transported by AMD (see Section 5.3.1, Table 10), are
and 880 t Au (e.g., Leistel et al., 1998). From the North also very randomly distributed through the year, mak-
of Seville to the South of Lisbon, the IPB comprises ing the predictions and calculations neccessary for the
more than 80 mines, including historical deposits with design of any remediation/attenuation technique very
more than 100 Mt such as Ro Tinto, Tharsis, La Zarza, dicult.
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- 4. Results
doned waste piles (with a total volume of 107 Hm3) and
10 tailings dumps (42 Hm3) in the province of Huelva 4.1. Chemical characterization of stream waters
alone (IGME, 1998), which represents one of the
Worlds largest accumulations of pyritic mine wastes. With the aim of obtaining a chemical reference back-
The mineralization is dominated by pyrite (>90% in ground for stream water quality in the area, 12 samples
volume), with variable amounts of sphalerite, chalcopy- of natural stream waters collected from several locations
rite and galena. Other minor minerals are tetrahedrite- were chemically analyzed (Table 1). These samples in-
tennantite, arsenopyrite, pyrrhotite, cassiterite, cluded water courses close to or upstream of the mine
magnetite and hematite. Pyrite is texturally variable from sites, but always unaected by AMD discharge based
ne-grained (colloform, framboidal) to coarse-grained on EC, Eh and pH eld data. Six of these samples come
crystals (Velasco et al., 1998; Sanchez Espana, 2000). from streams draining unmineralized rocks of the miner-
Gangue minerals include abundant silicates (quartz, alization-hosting lithostratigraphic unit (VSC), and the
chlorite, sericite and feldspars), and minor amounts of rest come from streams draining undierentiated sedi-
carbonate and barite (Sanchez Espana, 2000). mentary rocks of the IPB (comprising shales, phyllites,
The chemical composition of the sulphide ores is quartzites and greywakes from the PQ and Culm
highly variable among the dierent deposits and ore fa- groups) and Sierra de Aracena (including sericitic
cies (massive, banded, stockwork). Whole-rock compo- schists, quartzites, granites, gneises, marbles and tus).
sitions of sulphide ores normally show ranges of Additionally, water alkalinity has been measured by
1842% S, 1157% Fe2O3, 020% SiO2, 05% Al2O3, titration-based tests performed in situ in 31 dierent
05% MgO, 01.5% MnO, 07% CaO, with element stream water samples to cover the whole basin (Table 2).
contents of 400305,000 ppm Zn, 30084,000 ppm Cu, The chemical composition of these waters shows
75230,000 ppm Pb, 5617,600 ppm As, 234500 ppm lower SO4 and Cl concentrations (632 mg/L SO2 4 ,
Sb, 7800 ppm Cd and 8612 ppm Co, among others 1226 mg/L Cl) with respect to bicarbonate content
(e.g., Sanchez Espana, 2000). (69 mg/L HCO 3 on average). There is no clear chemical
In short, the mineralogical and textural characteris- distinction between waters draining VSC materials and
tics of the IPB ores (namely, (1) dominantly pyritic, those draining undierentiated rocks (e.g., SO2 4 vs.
ne-grained, usually brecciated and fractured, highly pH; Fig. 3).
reactive sulphide grains and (2) a lack of carbonates to In all cases, natural stream waters are characterized
neutralize acidity), favour pyrite oxidation/dissolution by low redox potential (Eh = 250470 mV), circumneu-
and the subsequent formation of AMD. tral pH, low conductivity values (EC = 98578 lS/cm),
and very low metal concentrations. The correlations be-
3.2. Hydrology tween trace metals are poor and do not show any signif-
icant trend. The most signicant contents are those of Fe
The hydrological characteristics of the province of (26445 lg/L), Al (23253 lg/L), Mn (653 lg/L) and
Huelva are typical of a semi-arid, Mediterranean-type Ba (561 lg/L). The Cu and Zn contents are in the
climate. The average water ow at Gibraleon (near ranges of 17 and 112 lg/L, respectively. The concen-
the Odiel river mouth) has been estimated to be around trations of other trace elements such as Ag, Be, Cd,
320 Hm3/a (10 m3/s) for the period 19691997 (Confed- Co, Cr, Hg, Ni, Mo, Sb, Se, Th, Tl and U were always
eracion Hidrograca del Guadiana, unpublished data). close to or below the detection limit of the analytical
However, this is just an oversimplied calculation that technique (some of these elements have been conse-
masks a complex reality dened by marked variations quently omitted in Table 1). Such element concentra-
in water discharge and subsequent water ow rates tions are always below drinking-water standards
from summer (JuneSeptember) to winter, as well as (50 lg/L for As, Cu, Pb, Mn and Cr; 5 lg/L for Cd,
between dierent hydrologic years (Fig. 2). Rainfall 3 mg/L for Zn, 0.3 mg/L for Fe; EU Council Directive
discharge (up to 1070 mm/day in winter, approaching 75/440/EEC of 16 June 1975 concerning the quality re-
0 mm/day in summer; Fig. 2), evapotranspiration quired of surface water intended for the abstraction of
(<1 mm/day in winter, and up to 10 mm/day during drinking water in the Member States).
J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1325
90
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
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
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
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)
Mine AMD type AMD No. Sampling date Site position Field measurements
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
1329
1330
(continued on next page)
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)
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
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
35
57
100
65
801
35
14.7
18.7
1.5
4.6
1142
7925
696
624
3.2
2.7
Mar-04
Mar-04
960-104
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)
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)
In the IPB, these Fe(III) phases had not been stud- always trace to major amounts of detritic silicates such
ied in detail, being traditionally referred to under as quartz, feldspars or clay minerals which are cemented
ambiguous terms such as ochreous precipitates, by Fe oxyhydroxides, and always have high contents of
amorphous iron oxides, ferric hydroxides, or SiO2 and Al2O3.
poorly crystalline oxyhydroxides. Although the pres- The recent ochre precipitates show recognizable
ence of schwertmannite has been recently suggested in bands in the XRD proles (Fig. 7) and consist mainly
the Ro Tinto sediments (e.g., Hudson-Edwards et al., of schwertmannite (Fe8O8(SO4)(OH)6), either as a
1999), it has not been unequivocally recognized or monomineralic phase, or combined with jarosite (KFe3
characterized. (SO4)2(OH)6) and/or goethite (FeOOH).
In this work, the authors present preliminary miner- Schwertmannite is poorly crystallized in comparison
alogical and chemical characterization of the MDM usu- with jarosite and goethite. However, it is possible to rec-
ally found in the IPB (Tables 6 and 7; Figs. 7 and 8). ognize 8 bands at 1.46, 1.51, 1.66, 1.95, 2.28, 2.55, 3.39
These samples were collected from dierent deposits and 4.86 A in the XRD patterns (Fig. 7), in agreement
and included: (1) recent, ochreous, colloidal precipitates with other schwertmannite samples described in the lit-
directly taken from the AMD water column, (2) lm-like erature (e.g., Bigham et al., 1996; Williams et al., 2002;
thin Fe(III) layers oating on the water surface in low Dold, 2003). These results, coupled with pepH data
ow or stagnant AMD sites, (3) aged, hard Fe(III) (pe = 1215, pH 2.03.5) of parent acid solutions (as-
crusts, and (4) laminated Fe(III) formations formed by sumed to be in equilibrium with analyzed minerals),
the covering of streambed cobble by lamentous algae and chemical composition of these precipitates (averag-
and hydrous Fe oxyhydroxides. Also, two samples of ing 61% Fe2O3, 37% LOI, and (Fe/S)molar 5.3), are
synthetic precipitates formed during titration of conclusive evidence for schwertmannite identication
AMD solutions with NaOH 2 M to pH 4, have also (Table 7; Fig. 8).
been analyzed for comparison with the naturally occur- Additionally, 2 line-ferrihydrite (Fe5HO8 4H2O)
ring samples (Fig. 7). and an Al-bearing amorphous phase, have been
The older and more consistent samples (Fe(III) identied in a sample collected downstream of Con-
crusts, laminated formations) detailed in Table 6 show cepcion AMD discharge on the Odiel river (pH 7;
A 1,000,000
100,000
IPB
10,000 Iron Mountain
SO4 (mg/L)
1,000
100
10
1
-3.0 -1.0 1.0 3.0 5.0 7.0 9.0
pH
B 1,000,000
Fe+Cu+Zn (mg/L)
100,000
10,000
IPB
1,000 Iron Mountain
100
10
1
0
10 100 1,000 10,000 100,000 1,000,000
SO4 (mg/L)
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.
1338 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
TDS (mg/L)
white-coloured, Al-phase that could be basaluminite
(Al4(SO4)(OH)10 5H2O). 10 4
XRD results are in perfect agreement with pepH R2 =0.93
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- 10 3
where (Bigham et al., 1990, 1994, 1996). 10 3 10 4 10 5
The average chemical composition of monomineralic EC (S/cm)
schwertmannite includes minor amounts of SiO2 (0.4 10 5
3.8 wt%) and Al2O3 (0.73.0 wt%), which could suggest B
either (1) some silicate contamination of samples, and/
or (2) some degree of sorption/coprecipitation of Si
SO4 (mg/L)
and Al onto the schwertmannite colloidal particles. In 10 4
fact, the two mixed schwertmannite-basaluminite sam-
ples formed by titration of acid solutions (samples 959- R2 =0.95
16 and 938-102; Table 7), show also SiO2 contents of 10 3
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.
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
1341
1342 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
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
n.a.
n.a.
n.a.
186
Co
41
basin-scale.
18
Cd
35
39
25
35
<10
As
13
15
51
20
100.10
100.10
Total
99.67
99.48
99.52
78.92
75.68
79.20
77.19
78.13
0.19
0.08
0.31
0.19
0.28
8.88
8.14
8.56
7.99
8.04
<0.10
<0.10
<0.10
K2O
0.10
0.10
0.98
1.59
0.95
0.94
0.02
0.03
0.02
003
003
0.67
0.07
0.56
0.08
0.22
0.07
0.33
5.21
0.38
4.31
3.16
9.90
8.42
9.65
7.75
9.16
0.15
0.91
0.21
1.38
0.17
Hal
Pick, Hal
Hal, Pick
Pick, Hal
Pick, Sta
Major
Sep-03
Jun-03
Sep-03
Jun-03
Sep-03
T-5
T-7
T-7
T-9
T-9
Table 8 (continued)
Tintillo river
river
river
river
river
geology/mineralogy
Mine/river
Tintillo
Tintillo
Tintillo
Tintillo
100
90
Inc
80
r
eas nditi
Ferrous AMD
co
ing ons
70
Ox
Fe 2+ /Fe total (%)
idis
60
ing
50
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 namic constants (log K, DH) have been taken from the
between divalent and trivalent cations. Whereas triva- geochemical databases accompanying the program
lent cations (Fe3+, Al3+) would be essentially present PHREEQC (Parkhurst and Appelo, 1999), and from
as Al- and Fe-sulphate ionic species AlSO 4; Bigham et al. (1996).
AlSO4 2 ; FeSO
4 ; FeSO 4
2 , bivalent cations would Under the geochemical conditions normally found in
be present either as individual free ions (Fe2+, Cu2+) the AMD systems (pH 23.5, Eh = 640800 mV,
or sulphate species (e.g., FeSO4, CuSO4). Fet = 1007000 mg/L, Al = 252600 mg/L, SO4 = 2
24 g/L; Tables 3 and 4), the poorly crystalline Fe-phases
5.2. Mineralogy of the acid mine drainage solids (schwertmannite, jarosite), as well as the more crystal-
line (goethite, hematite) are always supersaturated
5.2.1. Solubility of the AMD-related mineral phases (SI > 0) in the acid solutions, therefore tending to pre-
Considering the measured values of Eh, pH, T, dis- cipitate (Table 9). On the other hand, ferrihydrite and
solved O2, and Fe, Al, SO4, Na and K concentrations, the amorphous to poorly crystalline Al-phases (bas-
along with available solubility products of Fe- and Al- aluminite, jurbanite, alunite, gibbsite) are mostly under-
bearing phases (schwertmannite, jarosite, ferrihydrite, saturated (SI < 0). This is well exemplied in Fig. 14,
goethite, hematite, basaluminite, jurbanite, gibbsite) where the SI values of schwertmannite and basaluminite
naturally occuring in AMD systems, it has been possible are plotted as a function of pH (considering the initial
to calculate the saturation indices (SI) of these minerals conditions of a representative sample such as 938-112;
in the AMD solutions (e.g., Table 9). All thermody- 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 schwertmannite and, to a lesser extent, jarosite are
Al-phases, the SI calculations performed on two AMD the dominant phases controlling Fe(III) solubility in
systems from Corta Atalaya (Ro Tinto mine) are shown the AMD solutions, whereas Al solubility would be
in Fig. 15. These plots show the evolution of the solubil- mainly controlled by amorphous to poorly crystalline
ity of several Fe- and Al-phases in km-scale proles Al-phases like basaluminite. Although goethite has
downstream from the discharge points, and include also been found in variable proportions in several
two possible scenarios of pH evolution, namely: (A) con- MDM samples (Table 7), and it has been proved to
stant pH around 2.7 and (B) pH drop of an aluminous precipitate coetaneously with schwertmannite, ferrihy-
AMD solution (pH 4.5) mixing with more acid, ferric drite and jarosite in AMD systems (e.g., Bigham
AMD (pH 2.7). The observed dierence between Fe et al., 1996), this mineral does not appear to play a
and Al solubility leads to spatial and temporal separa- relevant role in controlling the Fe(III) concentration
tion of precipitating phases of hydrolyzed Fe and Al. of acid solutions. Goethite is more commonly found
In all cases, the solubility calculations performed, in older Fe(III) deposits (e.g., Fe(III) crusts) at the
as well as kinetic considerations, clearly suggest that mine sites than in the fresh, recently precipitated
1346 J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
2000 9000
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)
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
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- solved load, would have been retained within the Odiel
tions have been performed considering two dierent sce- basin (Table 10). Thus, the great majority of metal loads
narios (winter and summer), as yearly average values for released from the mine sites and transported by the acid
chemical composition and ow rate are highly unrealis- mine waters to the streams and tributaries of the Odiel
tic, as discussed previously. river, should essentially remain in the water courses in
As can be deduced from Table 10, Tharsis and Ro the form of solid phases like schwertmannite, jarosite,
Tinto (Corta Atalaya) are, by far, the mine sites that ferrihydrite, basaluminite or eorescent sulphates.
most profusely contribute to AMD volume, and SO4 However, most of these minerals are unstable and can
and metal loads transferred to the Odiel uvial system, be either transported as colloids downstream during
followed by San Telmo and Sotiel-Almagrera. These 4 high ow conditions or, on the other hand, they can
mine districts can represent around from 70% (winter) be transformed to more stable minerals (e.g., goethite)
to 90% (summer) of the total SO4 and metal loads re- and form cemented and more permanent chemical
ceived by the Odiel river watershed from AMD sediments.
discharge. These results suggest that only 1% of the total Fe and
Also, from simple mass-balance calculations, it can As dissolved load, and around 2040% of the total Al,
be deduced that around 99% of the Fe and As, and from Mn, Cu, Zn, Cd, Pb and SO4 loads, would have been
60% to 80% of other metals (Al, Mn, Cu, Zn, Cd, Pb) transferred from the Odiel river basin to the Huelva
and SO4 transported by the acid mine euents as dis- 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
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
1351
1352
Summer
(continued on next page)
Table 10 (continued)
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
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 1353
5.3.2. Duration and future evolution of the acid mine dox chemistry of the AMD systems is basically dened
drainage by the oxidation of Fe(II), which seems to be strongly
Some of the studied acid emissions have been ema- catalyzed by acidophilic, Fe-oxidizing bacteria and is
nating from underground mines abandoned since the perfectly correlated with the electronic potential (Eh)
early 20th century (e.g., El Soldado and Campanario of the acid solutions.
in 1917, La Poderosa in 1924, Esperanza and Tinto- The acidity of AMD is not only given by the concen-
Sta Rosa in 1931, Aguas Tenidas and San Platon in tration of H+, but also by the content of Fe(III) and Al,
1934) and late 19th century (e.g., Descamisada in whose hydrolysis (around 2.7 and 4.5, respectively) re-
1876, Confesionarios in 1888; Pinedo Vara, 1963). These leases important amounts of additional acidity and pro-
remain very acid and have high SO4 and metal loads. vokes the buering of the AMD systems.
The antiquity of the AMD systems has led to signicant As a result of the rapid oxidation and subsequent
landscape transformations such as: (1) cemented layers hydrolysis of dissolved Fe, a number of meta-stable
and laminated, algal mat Fe(III) formations of consider- and poorly crystallized Fe mineral phases (mostly schw-
able thickness (1050 cm) which record hydrologic epi- ertmannite, with additional jarosite and/or goethite) are
sodes (wet/dry seasons) and (2) elevated terrace formed. The mineralogy of these mineral phases is
deposits formed by hydrous Fe oxides in the conuence strongly dependent on the water pH, so that it reects
between AMD and natural streams. the geochemical evolution of these acid sulphate waters.
At present, it is dicult to predict whether or not the Thus, schwertmannite ( jarosite goethite) precipi-
AMD chemistry is undergoing some kind of long-term tates in the vicinity of the discharge points at pH 24;
temporal evolution, which could result in an improve- when most of the Fe has been precipitated, amorphous
ment of stream water quality at the basin-scale. Unfor- to poorly crystalline Al-oxyhydroxysulphates form at
tunately, there is no historical record of water quality pH 4.5; nally, ferrihydrite is usually favoured to precip-
data for the cited mine discharges with which to com- itate at circumneutral pH in the stream courses. Among
pare the current chemical signatures, and therefore, it the solid phases forming in the AMD systems, schwert-
is not possible to decide if a signicant decrease in the mannite plays a major role: (1) in the control of Fe sol-
acidity and/or metal contents is taking place at a regio- ubility and (2) in the retention of trace elements (As, Pb,
nal scale. In this sense, several studies have reported lit- Cu).
tle chemical change of acid euents emanating for The evaporation of AMD causes the precipitation of
hundreds of years, whereas others state that poor drain- hydrated sulphate salts which are temporal reservoirs of
age quality may last only 2040 a (Demchak et al., acidity, SO4 and metals.
2004). From mass-balance calculations, it has been shown
In any case, further research on the studied AMD that the majority of the SO4 and metal loads released
discharges has to be performed in the forthcoming years from the mine sites by the acid euents would substan-
in order to obtain a realistic model of prediction for tially remain in solid form within the Odiel basin. How-
water quality evolution at the basin scale, which could ever, the remaining dissolved loadings that reach the
serve as a basis for future reclamation and/or restoration Huelva estuary still imply impressive metal amounts of
plans in the Odiel river basin. 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
6. Conclusions Atlantic Ocean.
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