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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, suggesting 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 ) and metal content 4 (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 hydrolysis 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 commonly associated with AMD. In addition, the mineralogy and chemistry of the Fe precipitates (schwertmannite, jarosite, 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, schwertmannite at pH 24, basaluminite at pH 45, and ferrihydrite at pH > 6). Schwertmannite appears to be the most important 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. E-mail address: j.sanchez@igme.es (J. Sanchez Espana).
A long history of metalliferous mining (currently exhausted) 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
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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; Achterberg 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 concentrations 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 (Regional Government) has made a considerable economic contribution to various remediation and restoration attempts aimed at reducing the environmental impact of acid mine waters (e.g., Serrano et al., 1995). These initiatives 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). Unfortunately, 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 estuarine system (see above), although unfortunately, very little 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 composition of the AMD-related ochreous precipitates. These questions are important not only from a theoretical 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 investigating the geochemistry of the AMD systems and their interaction with fresh water courses in the Odiel river basin, 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
chemistry and metal loads; (3) mineralogical and chemical transformations taking place in the AMD-generating mine sites; (4) processes favouring natural attenuation; and (5) GIS-based, basin-scale, hydrogeochemical mapping according to water quality criteria. This paper summarises the results obtained from February-2003 to May-2004, describing the main geochemical features of the AMD systems, the mineralogical and chemical characteristics of mine drainage precipitates and eorescent sulphate salts, and the environmental implications.
2. Methodology and analytical techniques 2.1. Sampling Field work was performed during several seasons through 2003 (FebruaryMarch, April, June, July, SeptemberOctober, November) and 2004 (January, March, May) and included a comprehensive and detailed exploration of the study area, with identication and sampling 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 collected 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 eorescences) were directly stored in 125 ml-polyethylene bottles, 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, respectively) properly calibrated on site against supplied calibration standards (Hanna standard solutions HI 7004 (pH 4.01) and HI 7007 (pH 7.01) for pH; Hanna standard 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
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of the standard hydrogen electrode (see Method in Nordstrom, 1977). Flow rates have been calculated in all cases by conventional 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 titration methods 8201 (bromophenol blue) and 8202 (phenolphthalein (total) acidity; AC-DT model), 8203 (phenolphthalein (total) alkalinity using H2SO4; ALDT 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 intermediate 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 elements such as SO2 ; Zn and Mn. 4 2.3. Laboratory analyses All samples were analyzed in the IGME laboratories. Natural water samples were analyzed using diverse spectrometric techniques, such as spectrophotometry (ALLIANCE 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 gravimetrically measured as BaSO4, whereas Cl was analyzed titrimetrically with AgNO3. The accuracy and precision of the analytical methods were veried against certied reference 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 Centres AQUACHECK international program) and close agreement with certied values was achieved for all metals. 115In was used as internal standard for calibration 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 elements 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 following 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 Technology) 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 characterized by powder XRD using a PHILIPS PW 1710 diffractometer 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 colloidal 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 thermodynamic database of PHREEQC was enlarged with data from other geochemical codes (MINTEQA2, WATEQ4F (Ball and Nordstrom, 1991)) for the solubility 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 estuary 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 underlain 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
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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 massive sulphide on Earth, and despite its long history of extensive mining (dating from the Chalcolitic age, 3 ka
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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 abandoned 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 Worlds largest accumulations of pyritic mine wastes. The mineralization is dominated by pyrite (>90% in volume), with variable amounts of sphalerite, chalcopyrite and galena. Other minor minerals are tetrahedritetennantite, 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 facies (massive, banded, stockwork). Whole-rock compositions 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 characteristics 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, making 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 background for stream water quality in the area, 12 samples of natural stream waters collected from several locations were chemically analyzed (Table 1). These samples included 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 mineralization-hosting lithostratigraphic unit (VSC), and the rest come from streams draining undierentiated sedimentary 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 on average). There is no clear chemical 3 distinction between waters draining VSC materials and those draining undierentiated rocks (e.g., SO2 vs. 4 pH; Fig. 3). In all cases, natural stream waters are characterized by low redox potential (Eh = 250470 mV), circumneutral pH, low conductivity values (EC = 98578 lS/cm), and very low metal concentrations. The correlations between trace metals are poor and do not show any significant 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 concentrations 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 consequently omitted in Table 1). Such element concentrations 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 required of surface water intended for the abstraction of drinking water in the Member States).
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Rainfall discharge (mm/day)
90 80 70 60 50 40 30 20 10 0
Diary rainfall discharge Odiel waterheads 2003
0.6
A
2000 1800 1600 1400
Frequency
0.4
0.2
Jan Feb Mar Apr May Jun
Jul
Aug Sep Oct
Nov Dec
Months
0 0 4 8 12 16 20 24 28 32 36 40 44 48 52 56 60
Flow rate (Hm /year)
Daily Water Flow (m 3/s)

Yearly Flow Rate Odiel outlet 1969-1997
1200 1000 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 geochemical viewpoint, the IPB stream waters of unmined areas do not show any signicant chemical signature, with water quality standards akin to water courses draining siliciclastic rocks. Another important chemical feature of the stream waters is their relatively low alkalinity values (Table 2). Alkalinity of these waters is basically determined by the concentration of HCO ions, being therefore very 3 variable between dierent lithological areas. Thus, water alkalinity is in the range 120240 mg/L CaCO3 eq. in the upper basin (which drains Precambrian to Devonian metamorphic and plutonic rocks of the Sierra de Aracena), and between 10 and 115 mg/L CaCO3 eq. in the middle and lower basin, characterized by volcanic and
sedimentary rocks of the IPB (PQ, VSC and Culm units). In general, these data indicate a limited acid-neutralizing capacity for most stream waters in the area, which has drastic environmental consequences (the potential acidity of the acid mine euents is about 23 orders of magnitude higher than alkalinity of stream waters see below , and therefore, they cause a rapid pH decrease of the natural water courses, even when AMD volumes are low in relation to stream water volumes). 4.2. Location and description of acid mine euents By May-2004, 64 AMD discharges from 25 dierent mines of the IPB have been studied. AMD-generating
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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, water ow rate; DO, dissolved O2; EC, electric conductivity; n.a., not analysed.
Table 1 Field parameters and chemical composition of natural stream waters of the Odiel river watershed
mine sites include, in decreasing order of importance, 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 represent, 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 composition 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, La Torerera, San Platon, Esperanza, El Soldado, Angostura) always show very low water volumes. Many acid leachates from waste rock piles (e.g., Monte Romero, Confesionarios) are ephemeral, being active only after rainfall episodes. 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 uniform. In fact, they can be dierentiated in terms of seasonal 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.), redox conditions (Eh = 400800 mV; pe = 6.713.5), electric conductivity (EC = 100024,000 lS/cm), dissolved O2 content (from totally anoxic to O2-saturated), dissolved 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) ferrous/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 reddishcoloured), 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 Table 2 Alkalinity values (mg/L CaCO3 eq.) for stream waters in the Odiel river basin Sample No. 959-3 981-5 937-11 959-3 937-18 937-14 959-8 937-5 937-12 960-11 960-6 938-52 937-9 959-9 938-26 960-12 959-19 938-45 938-5 937-12 937-5 938-55 938-54 917-1 938-28 917-3 917-2 938-8 938-1 917-4 918-1 River/creek Aserrador Ayo. San Bartolome Ayo. Sepultura Aserrador Bco. Ovejeros Tallisca Chapinero Escalada Fresnera Palanco Carrasco Bco. Hocino Tamujoso Cascabelero Rivera Seca Rivera del Villar Vega del Almendro Olivargas Olivargas (before reservoir) Fresnera Rivera Pelada Valdehornos Bco. del Perro Acebuche Escalada (before San Miguel) Casares Almonaster Santa Eulalia Odiel Linares Jabuguillo Lithostratigraphic unit Miocene, PQ, VSC Miocene, PQ, VSC Culm Culm Culm Culm Culm Culm, Pulo de Lobo, VSC Culm, Pulo de Lobo, VSC VSC VSC VSC, Culm VSC, Culm VSC, Culm VSC, Granites, PQ VSC, PQ VSC, PQ PQ PQ, Culm Pulo de Lobo, PQ Pulo de Lobo, PQ, VSC Pulo de Lobo, Culm Pulo de Lobo, Culm Pulo de Lobo, Sierra de Aracena Maassif Sierra de Aracena Maassif Sierra de Aracena Maassif Sierra de Aracena Maassif Sierra de Aracena Maassif Sierra de Aracena Maassif Sierra de Aracena Maassif Sierra de Aracena Maassif Sampling date May-04 May-04 May-04 Nov-03 May-04 May-04 May-04 May-04 May-04 May-04 May-04 May-04 May-04 May-04 May-04 May-04 May-04 Nov-03 Jan-04 May-04 Nov-03 May-04 May-04 May-04 May-04 May-04 May-04 May-04 May-04 May-04 May-04 pH 7.4 7.3 7.4 7.0 7.4 7.2 7.3 7.1 6.5 6.9 7.8 7.8 7.4 7.8 7.4 7.8 8.4 7.7 9.0 6.5 6.8 7.4 8.8 8.4 8.3 8 8.1 8.4 8.7 8.5 8.1 EC 557 578 168 460 266 388 270 131 123 322 331 220 370 302 135 353 433 162 165 123 166 98 161 211 275 235 324 300 335 383 472
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Alkalinitya 146 157 58 66 69 100 104 21 11 94 114 88 68 83 39 107 113 34 65 11 18 20 65 80 121 135 137 143 148 197 236
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.
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white-coloured). This distinction is only valid at the source points (mine adits, waste pile leachates), as the oxidation and hydrolysis of Fe at pH $ 2.53 in these waters is very fast after their contact with atmospheric O2 (see Section 5.1.2), and provokes the transition from Fe(II)/anoxic to Fe(III)/suboxic and, when mixed with stream waters, aluminous/O2-saturated facies, in a very short distance. Type 2 (ferric/suboxic) AMD is, by far, the most common and volumetrically important among the acid emissions in the IPB, with ferrous and aluminous euents being scarce and always having very low water volumes (Table 3). The chemical composition of these waters include extreme concentrations of dissolved SO4 (up to 44 g/L) and metals (up to 7.7 g/L Fe, 2.6 g/L Al, 2.9 g/L Mg, 1.4 g/L Zn, 435 mg/L Cu and 440 mg/L Mn; Tables 4 and 5). Trace elements are also signicantly enriched
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VSC rocks Undifferentiated rocks
SO4 (mg/L)
25 20 15 10 5 0 5 6 7 8
pH
Fig. 3. SO2 vs. pH diagram for natural stream waters in the 4 Odiel river basin. Waters draining dierent types of rocks (siliceous volcanic and sedimentary rocks of the volcanicsedimentary complex (VSC), and undierentiated rocks from other lithostratigraphic units of the IPB such as the Culm, PQ 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 Year Aguas Tenidas Angostura Angostura Angostura Campanario Campanario Castillo Buitron Concepcion Confesionarios Confesionarios Confesionarios Cueva de la Mora Descamisada Descamisada El Carpio Mine hole Mine adit Mine hole ALD outow Waste-rock pile leachate Mine hole ALD inow Waste-rock pile leachate Waste-rock pile leachate Waste-rock pile leachate Waste-rock pile leachate Mine adit Mine adit/ALD outow Mine hole Mine adit 938-109 938-110 938-11 OB 938-111 960-105 960-109 960-108 938-105 937-101 937-113 937-114 938-107 960-106 960-107 937-110 2003 2003 2003 2003 2003 2003 2003 2003 2003 2004 2003 2004 2003 2003 2004 2004 2004 2003 2004 2003 2003 2004 2003 2003 2003 2004 2003 2003 2003 2003 2004 2003 2003 2003 2004 2003 2003 2004 2003 2003 2004 2003 2003 2004 2003 2003 2003 2003 2003 Month 6 2 6 3 6 3 6 3 7 3 9 3 9 2 3 3 3 9 3 7 7 3 9 7 4 3 6 6 9 3 3 9 6 4 3 4 3 3 9 6 3 9 6 3 9 6 2 2 4 Day 19 28 19 1 19 1 19 1 30 12 25 12 26 27 18 18 10 27 12 30 30 10 27 29 1 12 19 23 23 6 18 23 18 1 6 1 3 10 28 21 10 28 21 13 27 21 28 28 1 Site position X-utm 160425 160425 172771 172771 172771 172771 172976 172976 162318 162182 167621 176582 176582 157912 157875 157592 165893 165893 161488 161488 161557 149233 149233 149233 178259 175738 175738 165708 177782 177896 177028 177028 177028 177028 177028 177861 156170 159407 159407 159407 159961 159961 159961 154380 154380 154380 154380 166209 181556 Y-utm 4188518 4188518 4186494 4186494 4186494 4186494 4186597 4186597 4162098 4162073 4171913 4187684 4187684 4190185 4189355 4189631 4187971 4187971 4162711 4162711 4162741 4192241 4192241 4192241 4185728 4185620 4185620 4172769 4183954 4184244 4184430 4184430 4184430 4184430 4184430 4184226 4168339 4180411 4180411 4180411 4180148 4180148 4180148 4191826 4191826 4191826 4191826 4188237 4183015 Altitudea 305 305 276 276 276 276 324 324 166 167 139 224 224 344 311 314 254 254 145 145 151 289 289 289 339 248 248 130 258 298 241 241 241 241 241 289 85 229 229 229 198 198 198 348 348 348 348 264 306 Field measurements Q (L/s) 0 2 0.1 0.2 0 0 0.1 0.2 0 1 0.7 2.8 2.4 2 15 7 3.5 1.6 0.2 3 1 1.56 0 0 2 2.2 2.3 0.1 0.2 0 4.5 0.3 1.6 3.5 3.7 0.05 1 2.0 0.5 0.6 0.9 0.3 0.5 0.5 0.4 5.0 8 0.1 pH 2.5 3.1 2.7 2.7 2.2 2.2 3.2 3.0 3.4 2.6 2.5 2.3 2.5 2.0 2.6 2.0 3.3 3.2 3.9 4.2 2.4 2.8 2.1 2.6 2.5 2.7 2.8 2.8 1.9 3.2 1.7 1.6 1.4 1.6 1.7 5.4 3.1 2.9 3.2 2.9 3.6 3.4 3.5 2.8 3.2 2.7 3.0 2.8 2.7 DO (mg/L) 1.6 0.0 8.7 7.4 2.2 2.2 1.3 0.0 1.7 0.8 0.2 6.1 4.1 0.0 8.9 6.2 1.3 4.6 0.3 1.1 1.7 6.3 1.5 3.4 6.5 0.4 0.0 4.5 2.9 3.5 0.0 0.1 0.6 1.7 0.3 8.2 9.5 2.1 1.4 0.7 4.4 2.2 2.7 8.3 4.3 3.2 3.6 8.2 7.4 DO (%) 17 2 95 77 20 17 17 0 20 9 2 66 45 0 100 68 14 52 4 14 21 75 19 47 73 4 0 53 32 38 0 1 7 19 3 87 96 27 18 10 47 25 32 89 53 38 45 82 75 Eh (mV) 704 604 655 678 636 653 521 563 495 589 616 703 733 733 633 648 565 548 438 360 687 663 643 641 661 599 551 673 659 633 618 632 595 614 599 501 683 486 513 491 610 618 615 648 591 612 571 693 621 EC (ls/cm) 1950 2240 1945 3750 3150 2140 2000 3720 3970 1010 4560 3050 5700 12,500 18,230 4190 3790 2740 2050 3080 2980 4700 4660 1800 4470 3580 1970 5040 5500 13,000 9540 10,080 16,000 15,200 2200 1200 7450 7230 7750 2470 1990 2820 4510 4770 4880 6000 1150 7300 T (C) 25.5 20.0 18.9 17.0 20.5 15.0 24.3 15.6 21.2 19.2 19.5 16.4 22.0 20.0 21.0 20.0 20.7 20.7 19.2 22.0 24.0 24.8 27.0 32.0 20.9 20.3 21.6 24.0 21.1 20.0 21.0 21.3 20.4 24.0 22.0 20.9 16.0 29.0 27.9 31.1 18.5 20.8 21.2 17.8 24.3 22.7 25.5 15.6 15.7
El Soldado Esperanza Gloria La Poderosa La Poderosa La Poderosa
Mine adit Mine adit Mine adit Waste-rock pile leachate Mine adit Mine adit
938-119 938-122 960-103 938-103 938-113 938-114
La Poderosa La Torerera La Zarza-Perrunal
Waste-rock pile leachate Waste-rock pile leachate Mine adit
938-118 959-100 937-108
La Zarza-Perrunal
Mine adit
937-109
Lomero-Poyatos
Mine adit
937-102
Monte Romero Rio Tinto
Waste-rock pile leachate Ore dump leachate
938-101 938-116
Rio Tinto Rio Tinto (embalse del Cobre) Rio Tinto (Corta Atalaya)
Ore dump leachate Water reservoir outow Mine adit
938-117 938-48 938-102
Rio Tinto (Corta Atalaya)
Waste-rock pile leachate
T-1
Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya)
Waste-rock pile leachate Waste-rock pile leachate
938-112 938-124
938-125
938-126
Rio Rio Rio San
Tinto (Corta Atalaya) Tinto (Corta Atalaya) Tinto (Corta Atalaya) Miguel
Waste-rock pile leachate Ore dump leachate Waste-rock pile leachate Waste-rock pile leachate Mine hole
938-127 938-128 938-129 938-108 938-121
San Miguel
San Platon San Platon San Telmo
ALD outow Mine adit Waste-rock pile leachate
938-106 938-123 937-104
San Telmo
937-105
San Telmo
Pit lake outow
937-106
San Telmo
Waste-rock pile leachates
937-107
San Telmo
937-111
Sotiel-Almagrera Sotiel-Almagrera
Ore dump leachate Ore dump leachate
960-102 960-110
2003 2004 2003 2004 2003 2003 2004 2003 2003 2003 2003 2003 2004 2004 2003 2004 2004 2003 2004 2004 2003 2004 2004 2004 2003 2003 2003 2003 2003 2004 2003 2004 2003 2004 2003 2003 2003 2004 2003 2003 2003 2004 2003 2003 2003 2004 2003 2003 2003 2004 2003 2003 2003 2004
4 3 4 3 9 7 3 7 6 3 6 4 3 1 11 3 1 11 3 1 11 3 3 3 9 2 9 6 4 3 9 3 10 3 9 7 6 3 9 7 6 3 9 7 6 3 9 7 6 3 9 7 4 5
1 18 5 16 23 29 16 29 17 5 17 1 16 15 13 16 15 13 16 15 13 17 17 17 24 27 24 19 3 12 26 12 2 10 27 29 21 10 27 29 21 10 27 29 21 10 27 29 21 10 27 29 8 10
181215 183632 183632 180507 180507 180507 181427 181427 181427 181427 181429 181429 180135 180135 180135 182091 182091 182091 180607 180607 180607 181473 181527 181360 169325 169325 169336 169336 169336 176602 176602 176678 176678 150048 150048 150048 150048 150116 150116 150116 150116 150492 150492 150492 150492 150703 150703 150703 150703 149942 149942 149942 160171 160171
4182846 4182736 4182736 4180177 4180177 4180177 4179918 4179918 4179918 4179918 4179951 4179951 4180482 4180482 4180482 4180510 4180510 4180510 4179004 4179004 4179004 4181168 4181164 4181323 4185855 4185855 4186144 4186144 4186144 4186051 4186051 4186540 4186540 4191059 4191059 4191059 4191059 4191087 4191087 4191087 4191087 4191108 4191108 4191108 4191108 4191494 4191494 4191494 4191494 4191151 4191151 4191151 4173540 4173540
339 370 370 221 221 221 270 270 270 270 328 328 331 331 331 290 290 290 277 298 167 167 174 174 174 177 177 218 218 273 273 273 273 280 280 280 280 263 263 263 263 278 278 278 278 282 282 282 315 315
0.05 48 220 1 <0.5 <0.5 28 10 15 90 1 2 21 25 20 6 20 15 10 17 5 <0.5 1 13 0.02 4 0.2 1.5 10 2.0 0.2 0.1 0.1 2.0 0.4 1.5 2.7 1.3 3.0 40 0 3 5 38 9 10 0.5 0.7 0 1.5
2.6 4.0 4.6 2.3 2.2 2.4 2.6 3.0 2.8 2.7 2.6 2.5 2.8 2.5 2.5 2.5 2.7 2.4 2.3 1.7 2.6 4.2 3.8 1.5 1.8 2.2 2.3 2.3 2.5 2.7 3.0 3.1 2.5 2.5 2.6 2.3 2.4 2.5 2.4 2.2 2.9 2.8 2.7 2.5 3.2 3.3 3.2 3.0 2.7 2.8 2.7 1.8 2.7
8.7 9.8 9.5 5.0 7.7 5.0 0.5 0.9 0.8 0.0 0.4 1.1 9.3 0.0 4.2 0.0 0.0 4.4 9.1 0.0 8.5 3.1 8.5 0.2 0.7 0.0 0.6 2.1 4.7 8.8 0.4 0.4 2.1 0.4 0.5 0.6 0.9 0.1 9.9 8.3 6.7 7.1 8.2 7.1 7.6 7.2 8.8 6.7 5.7 6.7 3.5
92 99 102 57 91 60 6 11 10 0 4 12 97 60 0 7 48 0 0 46 95 0 93 41 85 3 6 0 5 25 47 100 4 5 26 5 4 5 11 1 101 100 92 92 93 88 99 90 89 80 70 79 40
689 633 478 667 799 762 570 537 544 614 622 655 823 848 622 636 620 643 636 656 748 396 477 646 641 552 564 613 599 558 699 786 636 647 625 619 607 608 605 604 750 782 775 779 629 621 615 630 722 725 719 713 546
6100 2200 1240 10,050 12,370 9760 17,200 17,120 15,330 16,000 19,400 10,500 7700 6850 18,000 13,500 14,300 14,200 10,200 11,850 8300 9400 7000 5850 13,200 8500 5970 5710 6000 6030 5750 1690 1770 13,810 10,480 11,950 13,270 10,650 7660 9080 9850 4050 4550 4430 4280 3480 3250 3270 3150 12,550 12,240 12,230 5650 6470
16.7 15.0 19.1 21.0 13.4 22.2 24.7 25.9 24.8 24.0 30.8 16.5 17.0 16.8 16.2 21.0 21.0 21.0 17.5 17.0 17.6 16.0 20.0 19.0 30.3 19.1 19.8 19.3 20.0 19.0 17.4 14.6 18.6 21.6 24.2 24.4 24.0 21.2 21.4 20.6 21.1 15.2 23.8 30.4 26.8 20.1 24.5 27.3 26.7 14.9 21.1 22.5 23.5 18.0
J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 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 Year Sotiel-Almagrera Sotiel-Almagrera Tharsis Tharsis Tharsis Tharsis Tharsis Tharsis Tharsis Ore dumps outow Ore dumps outow Waste-rock pile leachate Pit lake Waste-rock pile leachate Waste-rock pile leachate Mine adit Waste-rock pile leachate Waste-rock pile leachate 960-5 960-5 959-101 959-103 959-104 959-105 959-106 DB-1 DB-2.1 2003 2004 2003 2003 2004 2003 2004 2003 2004 2003 2003 2003 2003 2003 2003 2004 2004 2004 2003 2003 2003 2004 2003 2004 2004 Month 11 5 3 6 3 9 3 9 3 9 4 9 7 6 4 5 5 5 6 3 6 3 6 3 3 Day 13 10 4 20 11 29 11 29 11 29 7 29 31 20 7 13 13 13 23 3 23 11 23 11 12 Site position X-utm 162584 162584 138400 136192 138752 138752 138332 138332 136336 136336 135355 135347 135347 135347 135347 138231 138431 138495 164566 164566 164591 164591 164575 164575 161590 Y-utm 4172286 4172286 4168773 4168648 4168503 4168503 4167778 4167778 4167549 4167549 4169059 4168661 4168661 4168661 4168661 4169650 4169298 4168461 4172338 4172338 4172420 4172420 4172420 4172420 4162444 Altitudea 83 83 250 252 203 203 216 216 242 242 236 249 249 249 249 226 234 243 120 120 116 116 110 110 162 Field measurements Q (L/s) 80 130 0.5 0.0 0.3 0.1 0.4 3.3 0.4 1 0.5 1.5 4 15 0.5 1.8 0.6 0.5 1.0 0.6 0.3 pH 2.8 7.9 3.1 2.2 2.9 2.5 2.3 2.3 2.0 2.6 2.4 2.5 2.5 2.3 2.2 2.7 2.2 2.9 3.3 3.4 3.3 3.3 5.7 5.5 3.2 DO (mg/L) 9.9 9.0 9.3 8.3 7.4 0.2 0.7 1.5 0.4 8.2 0.3 1.9 0.0 0.0 3.0 4.9 6.3 6.7 7.1 0.3 0.0 8.8 9.4 1.5 DO (%) 101 101 95 86 81 2 9 15 3 87 4 22 0 0 40 63 72 71 78 4 0 90 96 15 Eh (mV) 642 325 697 790 616 723 636 658 615 609 800 628 434 639 663 609 614 728 560 522 604 599 428 447 692 EC (ls/cm) 2200 3200 3800 3950 4940 6030 16,670 23,900 6010 4030 2870 8440 8300 6710 5560 15,330 22,700 3700 3500 3630 1750 1830 539 685 1142 T (C) 14.2 21.0 20.7 26.8 15.1 22.0 16.7 26.0 17.4 20.7 17.4 20.2 20.6 18.6 18.6 28.7 22.7 19.3 21.0 21.5 19.2 12.4 19.8 14.7 14.7
Tharsis Tharsis Tharsis Tinto-Sta Rosa Tinto-Sta Rosa Tinto-Sta Rosa Trincheron
Waste-rock pile leachate Waste-rock pile leachate Waste-rock pile leachate Mine adit Mine adit Waste-rock pile leachate Mine adit/ALD outow
959-107 959-108 959-110 960-100 960-101 960-102 960-104

Table 4 Chemical composition of AMD discharges in the IPB (Odiel river watershed)
1331
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 No. Sampling date Field measurements Q (L/s) 1 2.8 15 7 3.5 15 0.2 1.6 2.2 4.5 0.8 0.8 1 2 21 6 10 1 <0.5 13 48 15 28 2 0.5 2 2.7 40 38 1.5 0.3 5 3.3 15 0.5 0.15 11 pH 2.6 2.3 2.5 2.0 3.3 3.2 3.6 2.8 2.7 1.7 2.9 3.6 2.3 2.6 2.8 2.5 2.4 4.2* 2.6 3.8* 4.0 2.6 2.6 2.5 3.0 2.5 2.4 2.9 3.2 2.7 2.9 2.3 2.0 2.7 2.2 2.9 2.7 2.9 Eh (mV) 593 707 672 645 572 679 442 667 603 622 490 614 671 574 827 626 647 400 752 481 637 742 608 603 703 640 611 754 633 346 620 640 612 607 613 728 480 774 EC (lS/cm) 3970 4560 4500 18,250 4190 1850 2740 2980 4470 13,000 7450 2470 10,050 17,200 7700 13,500 10,200 7000 9400 5850 2200 8900 17,100 6030 1690 13,810 10,650 4050 3480 6470 4940 16,670 6010 15,330 22,700 3700 11,500 3500 DO (mg/L) 0.8 6.1 7.0 6.2 1.3 9.3 0.3 6.3 0.4 0.0 2.1 4.4 5.0 0.5 9.3 0.0 0.0 0.0 9.1 8.5 9.8 9.2 5.9 0.6 4.7 0.4 0.5 9.9 8.2 3.5 8.3 0.2 8.1 3.0 4.9 6.3 9.3 10.6 DO (%) 9 66 70 68 14 91 4 75 4 0 27 47 57 6 97 0 0 0 95 93 99 100 68 5 47 4 4 101 93 40 86 2 40.0 63.0 71.6 92.8 96 T (C) 19.2 16.4 14.0 20.0 20.7 12.0 19.2 24.8 20.3 21.0 29.0 18.5 21.0 24.7 17.0 21.0 17.5 20.0 16.0 19.0 15.0 19.0 22.0 19.0 14.6 21.6 21.2 15.2 20.1 18.0 15.1 16.7 17.4 28.7 22.7 19.3 14.2 9.0 Iron content (mg/L) Fe
2+
Fe2+/Fet (%) Fet 840 597 1515 7730 620 n.d. 772 427 965 2660 2290 55 4060 2070 339 1625 1050 1270 0 910 0 730 1985 1780 38 2225 2590 192 146 1175 585 4670 1215 2370 4410 197 1732 n.d. 90 13 4 93 97 41 86 79 96 49 32 94 1 52 56 100 0 100 0 0 71 86 26 53 80 5 68 92 68 44 81 65 71 95 50
Acidity (mg/L CaCO3 eq.) pH 3.7 1120 1450 3330 14,800 600 830 940 880 1330 5500 3290 110 5700 5100 1160 3800 2450 1550 1120 0 8130 2630 44 4370 4360 550 150 1450 1090 9010 2120 4000 7490 3900 430 12,200 3790 120 9390 7740 1160 630 2130 2350 16,950 3110 8030 11,100 8600 1480 100 16,730 4840 231 12,750 10,400 1860 1060 3750 3520 23,160 3670 10,910 14,500 11,350 1730 pH 5.0 1410 2520 24,100 1090 1150 1310 1290 2090 7480 4660 390 8690 11,470 4010 10,400 6210 1900 2100 200 pH 8.3 1970 3060 6,540 29,450 2090 1770 1780 1620 2660 8100 6320 790 11,300 15,150 5660 13,690 8700 2750
Fe
3+
Campanario Concepcion Confesionarios Confesionarios Cueva de la Mora Cueva de la Mora Descamisada El Carpio Esperanza La Poderosa La Zarza La Zarza Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya) San Platon San Platon San Telmo San Telmo San Telmo San Telmo Sotiel-Almagrera Tharsis Tharsis Tharsis Tharsis Tharsis Tharsis Tharsis Tharsis
960-109 938-105 937-16 937-113 938-107 938-51 960-106 937-110 938-122 938-114 937-108 937-109 938-102 938-112 938-124 938-125 938-126 938-127 938-128 938-129 938-48 B-2 T-1 938-106 938-123 937-104 937-105 937-106 937-107 960-110 959-104 959-105 959-106 959-107 959-108 959-110 959-16 959-17
Mar-04 Mar-04 Feb-04 Mar-04 Mar-04 Feb-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 Mar-04 May-04 Mar-04 Mar-04 Mar-04 May-04 May-04 May-04 Feb-04 Jan-04
755 80 60 n.d. 575 50 750 175 830 2100 2200 27 1300 1949 5 850 588 1270 0 910 0 0 1400 1535 10 1185 2070 10 100 1085 400 2050 985 1540 3140 187 860 3
85 517 1455 n.d. 45 n.d. 22 252 135 560 90 28 2760 121 334 775 462 0 0 0 0 730 585 245 28 1040 520 182 46 90 185 2620 230 830 1270 10 872 n.d.
1333
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.
in these acid waters (maximum values of 17 mg/L As, 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 concentrated. 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 included in Table 4). In general, these AMD compositions indicate concentrations of total dissolved solids (sulphate and metals) which are comprised within the ranges normally reported for VMS-type deposits (Fig. 5) (see Plumlee et al., 1999, for a comprehensive revision). The higher SO4 and metal concentrations are usually found in the acid leachates from the huge waste piles of Corta Atalaya (Ro Tinto) and Filon Norte (Tharsis), and indicate an important oxidation and subsequent dissolution of pyrite and the accompaning sulphides (chalcopyrite, sphalerite, galena, arsenopyrite). An excellent correlation (r = 0.97 for n = 72; 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 conductivity as a good indicator of the degree of contamination of the stream waters by AMD, especially when coupled with pH/Eh measurements.
470
262 167 35 100 65 14.7 15 35 51
260
77
133
12.4
48
18.7
801
476
39
1494
172
57
2885
140
5237
6803
0.0
1.5
4.6
4.4. Mineralogy and chemistry of iron precipitates Probably, the most widespread feature of the study area is the ubiquitous presence of yellow to reddishbrown 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. However, and in contrast to other well crystallized products of pyrite oxidation such as hematite or goethite, the ne-grain size and low crystallinity of these chemical sediments make their mineralogical characterization difcult. To date, these mine drainage minerals (MDM; Murad et al., 1994) have been well characterized in many mine districts all over the world by a combination of dierent techniques (XRD, electron microscopy, differential 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), poorly crystallized oxyhydroxides and oxyhydroxysulphates of brous to spherical morphology such as ferrihydrite and schwertmannite, in addition to jarosite and goethite (Carlson and Schwertmann, 1981; Bigham et al., 1990, 1994, 1996; Murad et al., 1994; Nordstrom and Alpers, 1999a; Yu et al., 1999; Kawano and Tomita, 2001; Williams et al., 2002; Dold, 2003; Fukushi et al., 2003; Regenspurg et al., 2004; Majzlan et al., 2004).
1830
1142 696 3.2 0.3 Mar-04 960-104
603
3.3
Mar-04
960-101
Average IPB AMD
Tinto-Sta Rosa Trincheron
Mar-04
2.7
624
7925
1334
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 wasterock 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 date Apr-03 Feb-03 Feb-03 Feb-03 Feb-03 Apr-03 Apr-03 Apr-03 Apr-03 Apr-03 Apr-03 Apr-03 Feb-03 Feb-03 Feb-03 Apr-03 Apr-03 Apr-03 Apr-03 Apr-03 Feb-03 Feb-03 Apr-03 Apr-03 Apr-03 Apr-03 Feb-03 Apr-03 Apr-03 Feb-03 Mineralogy (XRD) Major Al-comp Qtz, Jar Qtz Schw Schw Goet, Jar Schw Schw Schw Qtz, Ms, Jar Goet Schw, Qtz Qtz Schw Jar, Schw Goet Qtz, Alb, Ms, Ka Schw Qtz, Fe-ox Qtz, Jar Qtz Schw Jar Qtz, Schw Qtz, Schw Qtz, Ms Schw Qtz, Schw Schw, Qtz Qtz, Ms, Cl Minor Gyp Alb, Ms, Fe-ox K-feld, Ms, Jar Jar, Qtz Jar, Qtz Qtz Qtz Qtz Schw, Qtz Mic, Alb, Jar, Cl Jar Qtz, Ms, Cl, Gyp Qtz, Schw Qtz Alb Ms Ms, Schw Qtz, Ms, Cl Goet, Qtz Ms, K-feld, Jar Ms Ms, Schw Jar, Goet Goet, Ms Major oxides (%) SiO2 72.44 48.57 72.44 4.76 5.53 5.30 1.78 3.83 3.40 2.82 4.45 33.38 45.31 1.07 4.86 1.35 23.65 61.23 23.92 67.94 52.75 26.25 37.28 8.80 20.07 15.75 2.18 40.09 21.45 31.20 Al2O3 7.30 5.52 7.30 1.73 3.38 1.74 1.35 2.47 1.82 1.50 1.96 24.91 14.17 0.73 2.39 1.12 19.15 12.27 10.05 8.50 20.50 8.46 13.55 4.75 10.52 9.12 1.21 7.53 5.61 30.18 Fe2O3 9.65 24.70 9.65 61.45 52.62 60.31 58.40 55.33 58.36 63.95 60.35 4.92 18.34 60.68 47.40 59.16 25.86 12.06 30.45 9.98 10.45 35.26 28.56 52.32 34.34 40.45 60.21 28.38 43.75 3.62 CaO 0.10 0.10 0.10 0.10 0.11 0.15 0.11 0.17 0.11 0.10 0.07 0.83 0.10 0.18 1.22 0.05 0.91 1.28 0.38 0.10 0.18 0.16 0.07 0.13 0.35 0.19 0.10 0.42 0.36 0.36 TiO2 0.51 0.23 0.51 0.20 0.50 0.32 0.41 0.24 0.20 0.11 0.10 0.75 0.53 0.03 0.15 0.02 0.33 1.16 0.38 0.37 0.59 0.37 0.61 0.12 0.26 0.23 0.06 0.43 0.45 0.20 MnO 0.00 0.00 0.00 0.04 0.06 0.06 0.06 0.08 0.06 0.05 0.04 0.08 0.04 0.05 0.05 0.02 0.09 0.08 0.09 0.01 0.02 0.12 0.03 0.06 0.14 0.07 0.04 0.07 0.05 0.06 K2O 2.08 1.58 2.08 0.34 0.37 0.26 0.10 0.28 0.26 0.18 0.47 1.00 2.43 0.15 0.26 0.11 0.67 2.05 1.60 1.34 1.57 1.24 2.30 0.41 1.07 0.88 0.45 1.09 0.81 0.82 MgO 0.10 0.10 0.10 0.10 0.35 0.25 0.21 0.52 0.15 <0.10 <0.10 0.85 0.41 0.10 1.99 <0.10 0.90 1.04 1.12 0.10 0.47 0.85 0.12 0.29 0.95 0.17 0.10 0.70 0.25 0.49 Na2O 1.07 1.00 1.07 0.11 0.90 0.14 <0.1 <0.1 <0.1 <0.1 0.34 1.04 0.55 0.08 0.33 <0.1 0.47 1.74 0.39 2.64 0.31 0.53 0.20 0.11 0.49 0.49 0.14 0.39 0.39 0.23 P2O5 0.02 0.01 0.02 0.13 0.14 0.21 0.20 0.22 0.14 0.15 0.11 0.18 0.08 0.15 0.14 0.06 0.40 0.09 0.11 0.01 0.06 0.36 0.10 0.19 0.14 0.14 0.20 0.13 0.22 0.03 LOI 6.81 18.34 6.81 31.16 36.05 31.04 37.34 37.00 35.81 31.14 32.38 32.07 18.07 36.83 41.25 38.22 27.69 7.01 31.31 9.08 13.11 26.41 16.79 33.12 32.70 32.70 35.37 20.61 26.45 32.80 Total 100.08 100.15 100.08 100.12 100.01 99.76 99.96 100.14 100.30 99.99 100.25 100.00 100.03 100.04 100.04 100.10 100.12 100.00 99.81 100.07 100.00 99.99 99.62 100.30 101.02 100.18 100.05 99.84 99.78 100.00 Trace metals (ppm) As 66 373 66 1134 734 860 709 1114 818 794 1369 Cr 10 1 10 9 6 11 14 10 12 13 7 37 24 4 25 <2 21 30 12 1 33 42 20 19 36 42 7 14 12 7 Cu 25 31 25 657 462 1107 421 393 435 814 930 2249 337 91 236 282 4127 248 508 111 90 537 299 537 803 546 299 226 697 16,956 Pb 11 34 11 316 374 406 297 222 236 107 386 149 1810 9 1080 14 78 61 38 677 180 221 1015 127 65 101 426 129 799 243 V 29 16 29 42 26 42 38 42 48 75 35 40 31 83 88 9 56 62 19 7 50 179 24 26 38 14 96 30 30 8 Zn 54 <2 54 107 312
Bco. Las Vinas Confesionarios Confesionarios (Las Vinas) Corta Atalaya (ro Tintillo) Corta Atalaya (ro Tintillo) Corta Atalaya (ro Tintillo) Corta Atalaya (ro Tintillo) Corta Atalaya (ro Tintillo) Corta Atalaya (ro Tintillo) Corta Atalaya (ro Tintillo) Corta Atalaya (ro Tintillo) Dehesa Boyal La Torerera La Zarza Lomero-Poyatos Mina el Soldado Ro Odiel Ro Odiel (Est. 54) Rivera de la Panera Rivera Olivargas Sotiel Tharsis Tharsis (Dehesa Boyal) Tharsis (Dehesa Boyal) Tharsis (Dehesa Boyal) Tharsis (Dehesa Boyal) Tharsis (Aguas Agrias) Tintillo Tintillo Tinto-Sta Rosa
P-937-19 P-937-101 P-937-19 P-938-32 P-938-34 P-T-1 P-T-2 P-T-3 P-T-4 P-T-6 P-T-6-II P-DB-8 P-959-11 P-937-8 P-937-102 P-938-119 P-938-43 P-960-2 P-937-1 P-938-7 P-960-8 P-959-2 P-DB-1 P-DB-3 P-DB-5 P-DB-7 P-959-7 P-T-7 P-T-8 P-960-9
442 383 418 286 212 122 402 159 71 447 5 18,766 108 944 8 173 887 142 182 392 73 223 60 341 637
2969 742 2221 1147 135 95 226 172 278 4729 717 351 164 68 3189 884 1043 168
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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.
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Table 7 Mineralogical and chemical composition of mine drainage minerals (MDM) found in dierent mine sites of the IPB (Odiel river basin)

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)
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In the IPB, these Fe(III) phases had not been studied in detail, being traditionally referred to under ambiguous terms such as ochreous precipitates, amorphous iron oxides, ferric hydroxides, or poorly crystalline oxyhydroxides. Although the presence 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 mineralogical and chemical characterization of the MDM usually 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 occurring samples (Fig. 7). The older and more consistent samples (Fe(III) crusts, laminated formations) detailed in Table 6 show
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 recognize 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 literature (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 (assumed to be in equilibrium with analyzed minerals), and chemical composition of these precipitates (averaging 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;
A 1,000,000
100,000
IPB Iron Mountain
SO4 (mg/L)
10,000 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 1,000 100 10 1 0 10 100 1,000 10,000 100,000 1,000,000
IPB
Iron Mountain
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.
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10 5
(Fe/S)molar = 12.1). The articially obtained phases after titration of AMD samples from Ro Tinto (sample 938102) 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 oxyhydroxysulphates. Most samples plot within their respective theoretical stability elds in a pepH diagram (Fig. 8) and show (Fe/S)molar ratios similar to those reported elsewhere (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 samples formed by titration of acid solutions (samples 95916 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 precipitates (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, ferrihydrite, 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 contents (Table 8). These soluble metal sulphate salts are usually found as botryiodal (colliform-like) eorescences of variable colour (white, greenish blue, pale green, yellow, orange, dark reddish), being normally zoned from the in-
TDS (mg/L)
10 4 R2 =0.93
10 3 10 3 10 5
EC (S/cm)
B
10 4
10 5
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 , for the studied AMD discharges in 4 the IPB (Odiel river watershed).
ner to the outer zones of the AMD sources and streams, and suggesting a paragenetic sequence of sulphates with distinct solubilities and degrees of dehydration. They are rarely found as monomineralic phases, and most commonly consist in mixtures of MgFeAl hydrated sulphates such as epsomite, hexahydrite, pickeringite, melanterite, szomolnokite, rozenite, halotrichite, copiapite or rhomboclase. Most of these phases have been indentied in other mining districts (e.g., Iron Mountain; Alpers et al., 1994; Nordstrom, 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 (melanterite, 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) minerals 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.
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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 reveal 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, ferrihydrite, 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 values of 240, 155 and 30 ppm, respectively. Other trace elements (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 profusely documented (e.g., Alpers et al., 1994; Nordstrom 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. Discussion 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 measurements. An approximate Eh value of $ 640 mV dierentiates 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 (107101 mol; Fig. 10). These data reinforce the validity of Eh as indicator of the Fe oxidation state in AMD.
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fact, several microbiological studies (Waddell, 1978; Ahonen and Tuovinen, 1989) have conrmed that the ambient conditions commonly found in these minedrainage environments (pH $ 3, T $ 2030 C) are optimum 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., Acidithiobacillus 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., schwertmannite) on their cell surfaces (e.g., Kawano and Tomita, 2001).
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 equilibrated with atmospheric O2. The hydrolysis of Fe(III) also occurs rapidly, and precipitation of hydrous Fe oxides 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, unpublished data) it has been calculated that the eld rate for Fe(II) oxidation is between 1 and 20 mmol L1 h1 (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
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 favoured 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 (105106 mol m2 s1) is faster than that of pyrite (1081010 mol m2 s1), aluminosilicates show signicantly slower rates of dissolution (10111013 mol m2 s1; Banwart and Malmstrom, 2001). Consequently, without the presence of abundant carbonate, the existing aluminosilicates cannot neutralise the acidity released during the abundant pyrite oxidation. On the contrary, aluminosilicate dissolution 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 aluminosilicates (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 euents 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 site Angostura La Zarza LomeroPoyatos LomeroPoyatos LomeroPoyatos Oraque river Poderosa Poderosa Rio Tinto San Miguel San Miguel San San San San San Miguel Telmo Telmo Telmo Telmo Sample No. 938-110 937-109 937-103 937-103b 937-103c E-959-1 938-1 14-A 938-1 14-B RT-1 938-108 938-121-B 938-121-P 937-105a 937-105b 937-105c 937-2 937-106 937-104 959-104 959-7 E-959-7A E-959-7B E-959-7C DB-2.1 P-DB-6 938-112 938-112a 938-112b 938-112c E-T-9 T-1 T-1-A T-1-B Sampling date Jun-03 Jun-03 Jun-03 Jun-03 Jun-03 Jul-03 Sep-03 Sep-03 Jun-03 Jun-03 Sep-03 Sep-03 Jun-03 Jun-03 Jun-03 Jun-03 Jun-03 Jun-03 Sep-03 Jun-03 Jul-03 Jul-03 Jul-03 Jun-03 Apr-03 Sep-03 Jun-03 Jun-03 Jun-03 Jul-03 Sep-03 Sep-03 Sep-03 Mineralogy (XRD) Major Pick, Hal Sta Eps Sta Hex Sta, Roz Eps Rom Cop, Mg-Cop Cop, Mg-Cop Szo Pick Szo Cop Pick Cop, Mg-Cop Pick Gyp Pick, Hal Pick, Hal Sta, Hex Sta, Cop, Pick Sta, Cop, Pick Pick, Hal Hex, Gyp Gyp Pick Sta Sta Sta Hex, Pick Sta, Pick Pick, Sta Minor Gyp Hex, Hal, Kal Pent, Gyp, Anh Pick, Hal, Kal Pick Alun, Bass Szo Hal Coq Gyp, Rom, Eps Szo, Hal Hal, Pick Rom Hal, Kie Kie, Hal Roz, Sta, Hal Jar, Qtz Sta Hal, Pick Roz Kal Jar Cop Hal, Kie Hal, Roz, Pick Hal, Pick Pick Hal Roz, Hal Hal Major oxides (%) SiO2 2.26 2.36 4.55 2.29 0.94 0.70 0.85 0.69 0.10 3.82 2.41 0.69 0.42 0.48 4.60 2.92 2.29 8.39 <0.10 2.44 0.35 0.10 0.87 0.98 16.16 1.40 1.20 1.22 1.08 0.20 O.10 0.74 0.38 A12O3 9.77 1.79 7.09 4.19 4.43 7.48 5.42 3.76 6.05 4.57 5.57 3.93 6.51 2.35 6.94 5.84 6.79 1.45 8.81 9.82 5.24 5.50 7.17 10.10 5.60 2.97 8.43 6.37 5.76 8.27 7.32 8.35 9.08 Fe2O3 2.87 0.43 5.23 6.28 6.35 0.71 21.96 19.45 17.16 19.77 20.10 18.06 17.97 26.26 2.71 13.25 3.14 2.18 0.11 1.04 6.95 6.57 5.79 5.34 39.76 18.50 4.42 7.31 8.82 3.55 5.45 4.68 4.20 CaO 0.08 6.50 0.26 0.68 0.18 0.45 0.32 4.83 0.13 0.13 0.70 0.25 0.19 0.13 0.25 0.11 0.08 29.35 0.06 0.25 0.15 0.10 0.13 0.18 0.30 4.58 0.12 0.11 0.11 0.18 0.40 0.23 0.19 TiO2 0.03 0.02 0.08 0.04 0.03 001 0.03 0.02 0.01 0.04 0.04 0.02 0.01 0.02 0.05 0.06 009 0.04 0.03 0.03 0.02 0.01 0.01 0.02 0.23 0.19 0.02 0.02 0.03 0.01 0.01 0.03 0.02 MnO 0.13 1.48 0.41 0.39 0.36 0.94 0.06 0.05 0.41 0.23 0.47 0.39 0.55 0.07 1.58 0.74 1.09 0.03 4.62 1.10 0.62 0.62 0.68 0.94 0.10 0.31 1.11 0.96 0.88 0.83 0.99 0.97 1.03 K2O 0.10 0.10 0.10 0.10 0.10 0.10 0.16 0.15 0.10 0.08 0.15 <0.10 0.58 0.11 0.10 0.14 0.10 0.19 <0.10 0.10 0.10 0.10 0.10 0.10 0.45 0.12 0.10 0.10 0.10 0.10 <0.10 <0.10 <0.10 MgO 6.92 15.53 9.98 12.82 14.77 11.58 1.19 1.22 4.77 1.93 4.34 3.73 6.30 0.37 11.84 7.36 8.66 1.37 9.22 9.84 9.69 10.10 9.25 5.26 1.71 2.95 9.77 8.31 8.48 8.95 8.72 8.35 7.08 Na2O 0.27 0.53 1.36 0.40 1.36 3.20 0.26 0.19 0.16 0.09 0.20 0.08 0.27 0.07 0.43 0.07 0.07 0.14 0.34 0.61 0.07 0.15 0.30 0.07 0.39 0.08 0.07 0.07 0.07 0.27 <0.065 0.09 0.08 LOI 77.68 64.37 71.05 72.91 71.68 65.44 69.73 62.72 71.30 69.32 66.03 72.85 67.13 70.18 71.57 69.59 77.66 23.54 76.77 74.87 76.89 76.99 75.80 77.18 37.85 48.76 74.93 75.70 74.79 77.75 77.05 76.50 77.93 Total 100.10 93.10 100.10 100.10 100.20 90.61 99.97 93.08 100.19 99.99 97.24 99.23 99.93 100.03 100.07 100.06 99.89 66.67 100.15 100.10 100.07 100.23 100.09 100.16 102.55 80.01 100.17 100.17 100.10 100.11 99.93 99.10 99.54 Trace metals (ppm) As <10 <10 22 88 <10 <10 260 194 417 344 28 2 1480 625 <10 102 <10 15 Cd 5 2 13 9 7 80 36 27 38 4 6 3 26 19 41 21 26 3 Co 152 274 21 28 31 398 n.a. n.a. 219 86 n.a. n.a. 54 53 57 106 125 8 Cu 4351 333 993 609 504 2460 7173 7766 7449 1506 443 502 114 6580 9592 2995 3018 190 Ni 55 452 18 22 18 211 n.a. n.a. 60 37 n.a. n.a. 46 27 100 107 80 7 Pb n.a. 22 33 6 19 5 6 10 1 17 5 2 19 11 41 n.a. n.a. 29 U 3 1 2 1 1 9 n.a. n.a. 1 1 n.a. n.a. 3 2 3 3 6 <0.2 V 1 1 14 5 1 2 n.a. n.a. 3 5 n.a. n.a. 10 2 34 7 1 3 Zn 921 2683 2674 4212 4916
30,300 6268 5898 5810 494 1406 1222 3497 3174 12,676 6883 8592 440
San Telmo (pit lake) San Telmo (waste pile) Tharsis Tharsis (Aguas Agrias) Tharsis (Aguas Agrias) Tharsis (Aguas Agrias) Tharsis (Aguas Agrias) Tharsis (Dehesa Boyal) Tharsis (Dehesa Boyal) Tintillo river Tintillo river Tintillo river Tintillo Tintillo Tintillo Tintillo Tintillo river river river river river
<10 534 172 176 <10 117 72 <10 <10 29 20 72 2 <2
43 73 87 94 15 1 6 36 34 28 113 6 32 36
266 845 832 829 214 n.a. n.a. 178 158 189 600 n.a. n.a. n.a.
4255 2012 2107 2579 4285 604 486 3110 2625 2738 4001 486 1990 2189
159 550 540 482 139 n.a. n.a. 115 101 108 310 n.a. n.a. n.a.
n.a. 14 1 79 n.a. 71 4 10 12 7 n.a. 4 <2 <2
6 7 8 8 1 <1 n.a. 6 5 4 11 n.a. n.a. n.a.
1 36 10 11 2 26 n.a. 0 1 1 4 n.a. n.a. n.a.
8400 33,400 32,200 35,800 3893 219 6184 8389 7929 12,873 27,600 6184 6823 6163
Line missing
1341
1342 (continued on next page)

7487 Zn
10.57
MgO
<0.10
8.88
8.14 8.56 7.99 8.04
The titration curves are clearly marked by two sharp slope breaks at pH $ 2.7 and around 4.04.5, which indicate strong resistance of the acid solutions to pH increase during titration (Fig. 12), being the result of the hydrolysis of dissolved Fe(III) and Al(III) ionic species. Additionally, Fe(II) hydrolysis causes slope breaks at pH $ 7.08.0 in the Fe(II)-rich samples that were not oxidized with H2O2 before titration (e.g., Fig. 12A, C and F). Although some hydrolysis of dissolved Fe(II) at circumneutral conditions occasionally occurs in the eld (e.g., La Poderosa and San Miguel mines), this process rarely takes place under natural conditions at the basin-scale. These gures reect that Fe(III) and Al(III) hydrolysis concurrently can represent around 70% on average of the total acidity potential of the aqueous acid solutions. In other words, Fe and Al dissolved in AMD act as chemical buers, stabilizing the AMD systems at pH values around about 2.7 and 4.5, respectively. This buffering is evident in the Odiel river mouth, which shows an average pH of between 2.5 and 3.5 (with a well-dened median value of 2.7 in the summer months) over the period 19902001 (Confederacion Hidrograca del Guadiana, unpublished data). 5.1.4. Seasonal variation of the AMD chemistry As is clearly shown in Tables 3 and 4, AMD compositions are not chemically constant throughout the hydrologic year 20032004. On the contrary, they show marked chemical variations between the winter and summer seasons. Flow rate is strongly lowered and pH tends to decrease during the dry period, but changes in SO4 and metal concentrations do not show a clear trend. Further, the variability in metal contents is not proportional among the dierent mine euents. This suggests that factors, other than simple dilution by fresh groundwater input after rainfall episodes, determine the variations in element concentrations. Specically, several geological, hydrogeological and mineralogical aspects are involved in these chemical changes. For example, the dissolution of eorescent sulphates previously formed during the dry period in partly ooded galleries, could provoke local increases of the SO4 and metal contents, as described in other mine districts like Iron Mountain, California (Alpers et al., 1994) or St. Kevin Gulch, Colorado (Kimball, 1999). Also, mineralogical dierences between the mineralization being oxidized (pyritic to base metal-rich complex ore) and host rocks (chloritic to sericitic volcaniclastic rocks, silicied vitric tus, black shales, etc.) could be responsible for the dierential dissolution of some elements. 5.1.5. Relation between AMD chemistry and deposit geology/mineralogy Fig. 5 shows that the IPB acid mine waters are more acid and metal-enriched than many of those
7241 n.a. n.a. <2 n.a. 1442 n.a. 30 13 99.67 78.92 0.19 <0.10 1.55 0.03 0.07 0.33 9.90 0.15 Sep-03 T-5 Tintillo river Hal
n.a.
n.a.
<2
Pb
n.a.
1476
Ni
n.a.
Trace metals (ppm)
Cu
18
Cd
Co
<2
100.00
As
79.69
Total
<0.065
Na2O
LOI
0.64
MnO
K2O
0.02
TiO2
0.67
CaO
4.65
Fe2O3
3.75
Major oxides (%)
A12O3
<0.10
SiO2
Mineralogy (XRD)
Pick, Hal
Minor
Sep-03
Sampling date
Major
T-1-C
Sample No.
Table 8 (continued)
Tintillo river
Mine/river site
Tintillo Tintillo Tintillo Tintillo
river river river river
T-7 T-7 T-9 T-9
Jun-03 Sep-03 Jun-03 Sep-03
Sta, Pick, Roz Hal, Pick Pick, Sta Pick, Hal Pick, Sta
Jar, Ferr Hal
Sta
0.91 0.21 1.38 0.17
8.42 9.65 7.75 9.16
5.21 0.38 4.31 3.16
0.56 0.08 0.22 0.07
0.03 003 0.02 003
0.98 1.59 0.95 0.94
0.10 <0.10 0.10 <0.10
0.08 0.31 0.19 0.28
75.68 79.20 77.19 78.13
100.10 99.48 100.10 99.52
<10 15 51 20
35 39 25 35
186 n.a. 41 n.a.
3940 2612 3765 3222
96 n.a. 21 n.a.
7 <2 1 <2
4 n.a. 4 n.a.
1 n.a. 1 n.a.
7312 7869 6513 6509
1343
100 90
r Inc
80
Ferrous AMD
ing idis Ox ing ons eas nditi co
70 Fe 2+ /Fe total (%) 60

>95% Fe2+ => Eh~570 mV
30 20 10 0 400 500
Eh~640 mV
40
>95% Fe3+ => Eh~720 mV
50
Ferric AMD
(r=-0.92, 5%-95% range)
600 Eh (mV)
700
800
900
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 reported for Iron Mountain (with negative pH values and Fe, Al, Zn and Cu contents of tens of grams per litre; Nordstrom and Alpers, 1999a) show clearly more extreme conditions than the IPB acid drainage. Chemical composition of the studied AMD always shows high contents of Zn and Cu (and to a lesser degree, As, Pb, Cd, Co and Ni), which is a common feature of mine waters draining massive sulphide deposits (Ball and Nordstrom, 1989; Goldfarb et al., 1996; Plumlee et al., 1999; Nordstrom and Alpers, 1999a). However, the most remarkable observation that can be made on the AMD chemistry is its dependence on the deposit geology and mineralogy, so that a strong geologic control on AMD composition is suggested. Thus, the increasing contents of Zn, Cu, Mn, As, Cd, Co, Ni or Pb with increasing SO4 content (Fig. 13) indicate a progressive dissolution of pyritic and polymetallic (complex) ores (containing abundant sphalerite, chalcopyrite, galena, arsenopyrite and tetrahedrite-tenantite) at the mine sites. The observed Al, Mg, Na, K and Ca concentrations are indicative of dissolution of the accompanying gangue minerals (mainly chlorite, sericite and feldspars). Also, a good correlation of r = 0.96 (p < 0.05; n = 9) has been obtained between the Zn/Cu ratio of acid mine waters and that of the drained mineralization (only taking into account the cases of mine adits with AMD discharges for which both chemical data for water and metal grades for mineralization are available). In fact, the average Zn/Cu ratio of AMD in the IPB is 2.7, similar
to the average ratio of the IPB ore mineralization (Zn/ Cu = 2.3; see Leistel et al., 1998). Another interesting feature of the AMD chemical composition is the high U and Th contents. The good correlations found between U and elements such as: (1) Al (r = 0.92), Mg (r = 0.90), Mn (r = 0.91) and (2) Zn (r = 0.90), Cd (r = 0.82) together with SO4 (r = 0.89), suggest that U could be derived from the dissolution of: (1) some aluminosilicates such as Mg-chlorite and/or K-feldspars (present in the acid volcanic and vocanoclastic lithologies such as rhyolite and dacite) and/or (2) other phases related with sphalerite-rich complex ores. Uranium concentrations ranging from 1 to 9 and from 0.3 to 2.3 ppm have been measured in rhyolites and polymetallic to complex ores from the IPB, respectively (Marcoux, 1998). The Th contents of the IPB volcanic and sedimentary rocks (225 ppm on average; Sanchez Espana, 2000) suggest that these lithologies are the most probable sources of this element. 5.1.6. Metal speciation Geochemical calculations performed with the PHREEQC code reveal dierent dissolved metal species in the acid solutions (Table 9). The geochemical predictions indicate that the dissolved metals in the acid mine waters are likely present in the form of either individual free ions (Cu2+, Zn2+, Mn2+) or as a number of dierent sulphate ionic species e:g:; FeSO ; FeSO4 ; 2 4 2 FeHSO4 . Additionally, other ionic species in the form of hydroxide (e.g., Fe(OH)2+) and/or chloride (e.g., CdCl+) complexes, could be locally present, although they would be quantitatively very minor.
1344
850
A
800 750
Ehcalculated (mV)
700 650 600 550 500 300
R2=0.82
400
500
600
700
800
900
Ehmeasured (mV)
0.6
B
Ehmeasured -Eh calculated (Volts)
0.4 0.2 0 -0.2 -0.4 -8 -6 -4 -2 Log Total Dissolved Iron, molality 0
Fe2+ <5% Fet Fe2+ >95% Fet
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 trivalent cations (Fe3+, Al3+) would be essentially present as Al- and Fe-sulphate ionic species AlSO ; 4 AlSO4 ; FeSO ; FeSO4 , bivalent cations would 4 2 2 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, dissolved O2, and Fe, Al, SO4, Na and K concentrations, along with available solubility products of Fe- and Albearing 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 crystalline (goethite, hematite) are always supersaturated (SI > 0) in the acid solutions, therefore tending to precipitate (Table 9). On the other hand, ferrihydrite and the amorphous to poorly crystalline Al-phases (basaluminite, jurbanite, alunite, gibbsite) are mostly undersaturated (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).

10,000
1345
Acidity (pH=3.7)
1,000
R2=0.91
100
10 10 100 1,000 10,000
Fe3+ (mg/L)
10,000
Acidity (pH 3.7-5.0)
1,000
R2=0.95
100
10 10 100 1,000 10,000
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.
3+
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 solubility 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) constant 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 separation 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, ferrihydrite 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

2000 A Sample 938-51 1800 1600 17% 1400 Fe2+ hydrolysis 1200 15% 1000 Al3+ hydrolysis 800 600 400 3+ 200 26% Fe hydrolysis 0 2 3 4 5 6 7 8 pH 7000 B Sample 937-16 6000 5000 4000 3000 2000 1000 0 2 6000 3 4 5 pH 6 7 8 9 35% Fe3+ hydrolysis 26% Al3+ hydrolysis 9000 8000 D 7000 6000 5000 4000 52% 3000 2000 1000 11% 0 2 3 12000 Acidity (mg/L CaCO3) 10000 8000 6000 4000 2000 22% 0 2 3 4 5 pH 3000 Acidity (mg/L CaCO3) Fe2+
O2 n H 2 itio d ad
Acidity (mg /L CaCO3 )
Acidity (mg/L CaCO3)
Sample 938-4
Al3+ hydrolysis Fe3+ hydrolysis 4 5 pH 6 7 8 9
Sample 959-16
35%
Al3+ hydrolysis
Fe3+ hydrolysis 6 7 8 9
Sample 937-108
5000 4000 3000 2000 1000 0 2 3 4 5 pH 6 7 8 Fe3+
Sample 938-127
2500 2000
O2 n H 2 itio d ad
1500 1000 500 0 2 3 4 5 Fe3+
Fe2+
6 pH
10
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 should be best considered as a product of mineralogical transformation of metastable Fe(III) phases (schwertmannite, ferrihydrite, jarosite) than a mineral directly precipitated from the AMD solutions. In fact, both goethite and hematite show much slower growth kinetics than schwertmannite, ferrihydrite and jarosite (Nordstrom and Alpers, 1999a). Therefore, although the geochemical calculations predict the precipitation of goethite and hematite (Table 9; Fig. 15), they seem to require more stable conditions and a longer time to form. Although the Al-phases have not been identied by XRD, basaluminite is the mineral that best explains the Al behaviour of acid solutions, and is the authors preferred option to account for the control of Al concentration at the critical pH range of 45. Alunogen be-
comes stable only at negative pH values, and gibbsite is usually unstable at pH < 5.5 (depending on sulphate activity), being rare in acid-sulphate environments (Nordstrom, 1982; Nordstrom et al., 1984; Nordstrom and Alpers, 1999a). Jurbanite is the most stable mineral and thermodynamically favoured to precipitate at pH below 4, although it rarely appears as an AMD precipitate. On the other hand, basaluminite is the more widespread mineral phase known to precipitate from AMD solutions at pH values of 5 or above (Nordstrom et al., 1984; Nordstrom and Alpers, 1999a). In summary, and in agreement with previous works in other mine districts (e.g., Bigham et al., 1996; Lee et al., 2002), a good correlation has been found between pH and mineralogy of the MDM at the watershed scale, with ferrihydrite precipitating at pH values above 6, amorphous Al-oxyhydroxysulphate (probably

3,000 2,500
1347
A
Al Zn Cu
Al 0) 0.9 (r=
mg/L
2,000 1,500 1,000 500 0 0 10,000 9,000 8,000 7,000 6,000 5,000 4,000 3,000 2,000 1,000 0 0
Table 9 Theoretical metal speciation in a typical AMD solution from the IPB (exemplied by sample 938-112, see Tables 35 for a detailed chemical composition), and calculations of the saturation indices (SI) of selected Fe and Al mineral phases with respect to this AMD uid Element Al
3+
) =0.87 Zn (r
Species AlSO4 2 AlSO 4 3+ Al
Molality 6.72E 02 4.04E 02 2.09E 02 5.86E 03 2.23E 03 1.49E 03 5.35E 04 1.08E 04 7.23E 05 1.61E 05 3.60E 02 2.11E 02 1.46E 02 2.23E 04 9.92E 02 4.93E 02 5.00E 02 4.93E 03 2.90E 03 1.99E 03 3.79E 05 7.33E 03 3.27E 03 4.02E 03 2.61E 03 1.18E 03 1.43E 03 2.02E 05 7.25E 06 5.86E 06 5.16E 06 1.86E 06 6.94E 03 3.04E 03 2.53E 03 1.34E 03
mol% 60 31 9 67 24 5 3 1 59 40 1 50 50 59 40 1 45 55
Cu (r=0.70)
10
20 30 SO4= (g/L)
40
50
Fe3+ FeSO 4 FeSO4 2 3+ Fe Fe(OH)2+ FeHSO2 4 Fe2+ Fe2+ FeSO4 FeHSO 4 Mg2+ MgSO4 Mg2+ Mn2+ Mn2+ MnSO4 MnCl+ Ca2+ CaSO4 Ca2+ Cu2+ CuSO4 Cu2+ Cd2+ CdSO4 Cd2+ CdSO4 2 2 CdCl+ Zn2+ Zn2+ ZnSO4 ZnSO4 2 2 Saturation indices Phase Formula Dissolving minerals Al(OH)3 Al(OH)3(a) Alunite KAl3(SO4)2(OH)6 Basaluminite Al4(OH)10SO4 Gibbsite Al(OH)3 Jurbanite AlOHSO4 Fe(OH)3 Fe(OH)3(a) Ferrihydrite Fe5HO8 4H2O Gypsum CaSO4 2H2O
B
As
As 0 0.2 (r= )
Mn Cd
g/L
0 Cd (r=
.76)
Mn (mg/L; r=0.83)
10
20 30 SO4= (g/L)
40
50
Fig. 13. Binary plots with regresion lines and correlation (Pearson-Product moment) values of SO2 with dierent 4 dissolved metals: (A) Al, Zn, Cu and (B) As, Mn, Cd.
basaluminite) at pH > 4, and a mineralogical assemblage of schwertmannitejarositegoethite found in AMD with pH between 2 and 4. 5.2.2. Iron precipitates and eorescent sulphates as trace metal sorbents Iron colloidal precipitates such as schwertmannite or ferrihydrite have been found to act as sorbents for trace metal removal in AMD systems, with a high pH-dependence of metal sorption (e.g., Smith, 1999). Sorption of the less soluble elements like As or Pb on these mineral phases can occur at pH around 4.55, whereas 100% sorption of other cations like Cu, Zn or Cd only occurs in circumneutral conditions (e.g., Smith, 1999; Lee et al., 2002). The analyzed mineral samples collected from AMD sites showing a schwertmannitejarositegoethite mineral paragenesis always have As, Cu, Pb and Zn concentrations in the range of tens to a few thousand ppm (Table 7). These values are higher than those observed for the samples dominated by quartz and aluminosilicates (chlorite, feldspar, mica; Table 6), and suggest that the high specic surface area of the Fe precipitates would have favoured metal sorption. Titration experiments conducted in AMD samples from the area (unpublished data) have shown virtually total As removal from solution during schwertmannite
45 55
36 29 26 9
44 36 19
log K
SI
11.06 5.90 1.34 0.61 22.70 9.41 8.34 3.17 3.23 0.76 4.89 1.68 5.00 1.79 4.58 0.16 (continued on next page)
1348 Table 9 (continued) Phase Formula
log K 3.70 0.64 14.49 10.84 18.00
SI 10.12 2.56 6.66 5.16 11.30
Precipitating minerals Hematite Fe2O3 Goethite FeOOH K-Jarosite KFe3(SO4)2(OH)6 Na-Jarosite NaFe3(SO4)2(OH)6 Schwertmannite Fe8O8(SO4)(OH)6
Relative abundances of the dierent ionic species in molal percentage. The log K values used for the SI calculation are indicated for each mineral phase.
precipitation at pH 3.5. This is in agreement with the high As contents found in the naturally occurring schwertmannite (1700 ppm As on average; Table 7). Additional mass-balance calculations performed in the Odiel river (unpublished data) suggest a considerable retention of Zn and a practically complete removal of Pb and Cu at pH $ 8. This trace metal retention would have resulted from adsorption by the abundant Fe and Al colloidal phases produced after the mixing of the Odiel river with several AMD discharges. These results are in agreement with available data of metal sorption on hydrous Fe(III) oxide in AMD systems (e.g., Webster et al., 1998; Smith, 1999; Lee et al., 2002; Fukushi et al., 2003), and indicate that trace metal retention by sorption onto Fe and Al colloidal precipitates can be an eective mechanism for natural attenuation of dissolved metal loads. With regard to the chemistry of the salts, chemical analyses of SO4 eorescences show that these phases can contain very high Zn and Cu concentrations (Table 8). These metals are sorbed and/or co-precipitated dur-
ing the evaporative processes taking place in extremely concentrated AMD pools. However, these sulphates are only temporal sinks and can release high quantities of acidity, SO4 and metals again to the water courses during rainfall, causing a rapid pH decrease and a high increase in dissolved solids, as described in other mine districts (e.g., Alpers et al., 1994; Kimball, 1999; Nordstrom, 1999). This process was observed during a eld visit performed on 1st October 2003, when the rst rainfall discharge after the dry season dissolved in a few hours around 5090% (varying among the mine sites) of the salts formed during the summer. This salt dissolution provoked signicant pH decreases and conductivity increases in the studied streams. 5.3. Environmental implications 5.3.1. Eects on water quality and calculation of metal loads It has been estimated that 29% (390 of 1360 km) of the total length of streams and water courses in the Odiel river watershed are aected to a variable degree by AMD pollution (Fig. 16). This mine-related contamination, which aects about 85% of the Odiel river main course (104 of 122 km), is evident in the Odiel river mouth, where pH values of 3.0 0.5, and average (median) metallic contents of 16 mg/L Fe, 12 mg/L Mn, 7 mg/ L Cu, 20 mg/L Zn and 66 lg/L Cd, are usually measured (data from the period 19902001; COCA network; Con federacion Hidrograca del Guadiana, unpublished report). Based on measured chemical compositions and water ow of the AMD discharges, SO4 and metal loads have 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.

20 15 10 5
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Iron phases Aluminium phases
pH=2.7
Schw Hem K-Jar Na-Jar Goet Ferr Gib Basal
SI
0 -5 -10 -15 -20 0 10 2 4 6 8 10 12
Distance (km)
B
5 0
Basal
SI
-5 -10 -15 -20 0 2 4
mixing
Jur Gib
pH=4.5
pH=2.7
Alun
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 estimations have been performed considering two dierent scenarios (winter and summer), as yearly average values for chemical composition and ow rate are highly unrealistic, 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 received 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
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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 uxes. Thus, during the winter months of 2003, an average of around 4 t of Al, 9 t of Mg, 0.9 t of Mn, 1.4 t of Zn, 0.6 t of Cu, 0.2 t of Fe, 9 kg of Cd, 6 kg of Pb and
0.5 kg of As, would have been daily transferred as dissolved load to the estuarine system. If added to the summer loads, these data imply a total yearly load of about 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 (Tn/day) Upper Odiel Angostura Concepcion Corta Atalaya (Rio Tinto) El Soldado Esperanza La Poderosa San Miguel San Platon Winter Summer Winter Summer Winter Summer Winter Summer* Winter Summer Winter Summer Winter Summer Winter Summer 0.4 0.2 12 4 350 50 2.5 0.9 2 0.6 8 2 11 0.8 2 0.2 184 0.2 0.1 1.1 0.8 172 61.2 0.2 0.1 0.7 0.2 3.6 1.1 5.2 0.1 1.0 0.1 41 Winter Summer Winter* Summer Winter Summer Winter* Summer Winter Summer Winter Summer Winter Summer Winter Summer 1 2 0.7 4 0.2 0.3 0.1 1 125 20 2 0.3 5 3 38 3 0.3 0.05 1 0.5 3 Winter Summer Winter Summer Winter Summer Winter 3 3.5 1.6 2 0.5 1.1 0.4 1.4 0.1 0.2 0.5 0.2 0.6 0.02 0.02 0.01 0.05 0.2 Fe (kg/day) 9759 4 2 160 93 6760 3240 33 14 159 64 960 295 1420 42 263 35 1821 67 190 79 267 6 5 2 2 1040 43 20 4 230 45 670 52 208 71 410 114 38 17 55 13 26 11 21 0.5 1 0.4 1 230 10 4 0.7 17 5 105 12 47 25 25 19 350 14 30 6 44 25 88 16 5 3 8 4 Al (kg/day) 10,731 2 1 57 48 10,200 3167 7 3 29 10 138 45 255 6 43 4 305 5 10 4 33 1 1 0.4 3 43 2 5 1 14 8 15 2 4 0.4 5 1 Mg (kg/day) 14,711 3 2 18 21 14,370 1776 7 3 19 14 36 16 243 3 15 2 479 8 2 1 31 0.7 0.2 0.05 0.8 32 1 0.5 0.1 7 4 13 4 132 17 8 2.5 Mn (kg/day) 1845 0.1 0.1 1.3 3 1820 825 0.2 0.1 0.6 0.3 0.7 1 21 0.8 1 0.2 98 2 10 4 3 0.1 2 0.7 0.2 90 4 0.5 0.1 27 15 156 16 Cu (kg/day) 2022 0.7 0.4 5 3 1872 570 1.1 0.5 7 2 104 28 20 0.2 12 0.5 55 1 14 6 9 0.3 0.1 0.03 0.6 Zn (kg/day) 3213 0.2 0.1 3 48 3100 1110 2 0.9 5 1 52 17 12 6 39 4 147 5 As (g/day) 7723 0.1 0.1 16 10 6020 280 7 3 3 20 600 630 870 13 207 19 2556 976 n.a. n.a. 600 21 2 0.7 13 n.a. n.a. 15 3 950 398 397 73 n.d. n.d. 324 103 260 n.d. 29 7 n.a. n.a. 22 0.5 0.2 0.07 1 n.a. n.a. 1 0.2 41 17 349 60 Cd (g/day) 23,425 1.6 1 21 10 23,000 3730 9 4 9 4 330 70 0.7 1 54 7 69 4 Pb (g/day) 4274 1 0.6 10 7 4200 40 19 8 12 2 2 3 27 0.7 3 0.2 12 2 n.a. n.a. 6 0.2 0.1 0.03 3 n.a. n.a. 1 0.2 1 0.1 4001 43 3950 n.d. 8 1
Lower-middle Odiel Campanario Castillo-Buitron Descamisada Gloria La Torerera Sotiel-Almagrera Tincheron Tinto-Sta Rosa
Olivargas Aguas Tenidas Cueva de la Mora La Zarza Monte Romero
Line missing
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Summer Table 10 (continued) Mine district
(continued on next page) J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356
Season Q (L/s) Sulphate and metal loads SO4 (Tn/day) Oraque Confesionarios El Carpio El Perrunal Lomero-Poyatos San Telmo Tharsis Winter Summer* Winter Summer Winter Summer Winter Summer Winter Summer Winter Summer 15 3 1.6 1 0.3 6 2.5 363 3 50 10 64 5.2 1.3 0.3 0.16 0.23 3.0 0.9 12.1 1.0 433 13 12 Winter Summer Winter Summer Winter Summer Winter Summer 25 2 671 106 2700a 450a 12.01 1 303 85 96 24 68 72 1.1 1 360 115 1966 32 6523 1960 1973 1973 392 25,064 7157 224 77 99 99 Fe (kg/day) 10,842 1950 507 41 5.3 1.5 52 17 385 31 2117 631 275 275 127 14,218 4210 4043 1080 72 74 Al (kg/day) 2802 233 61 10 14 6 323 109 820 118 4169 1225 540 540 235 21,399 3687 8986 2565 58 30 Mg (kg/day) 5582 242 63 14 4 1 7 2 120 11 417 125 63 63 21 2584 1014 900 350 65 65 Mn (kg/day) 563 14 4 1 0.3 0.1 4 1 76 5 307 89 50 50 15 2535 726 642 156 75 79 Cu (kg/day) 395 2 0.5 5 0.7 0.2 12 3 263 22 1024 306 97 97 53 4922 1618 1350 430 73 73 Zn (kg/day) 1310 6 2 3 4 0.5 200 50 650 3 36,440 11,032 5550 5550 1700 54289 14,466 450 156 99 99 As (g/day) 38,063 700 180 69 1 0.4 20 8 1000 40 2061 610 1779 1779 122 28,956 4694 9435 2020 67 57 Cd (g/day) 3334 240 62 12 1 0.5 400 140 200 13 337 93 6463 6463 19 15,700 331 5616 64 Pb (g/day) 950 10 3 2
Meca Tharsis Total AMD 20032004 Odiel outlet at Gibraleon (pH 4.2) 20032004 (pH 3.3) Dissolved metal loads retained in Basin (%) 20032004
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
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5.3.2. Duration and future evolution of the acid mine drainage Some of the studied acid emissions have been emanating 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 considerable thickness (1050 cm) which record hydrologic episodes (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 improvement of stream water quality at the basin-scale. Unfortunately, there is no historical record of water quality data for the cited mine discharges with which to compare 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 regional scale. In this sense, several studies have reported little chemical change of acid euents emanating for hundreds of years, whereas others state that poor drainage 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 climatic, hydrogeological, geological, and mineralogical factors. This variability in the AMD hydrogeochemistry allows recognition of very dierent conditions of pH, Eh, DO, oxidation rate of Fe(II) and metal content among the studied acid euents. This fact has strong implications as it introduces additional diculties 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-
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 concentration of H+, but also by the content of Fe(III) and Al, whose hydrolysis (around 2.7 and 4.5, respectively) releases important amounts of additional acidity and provokes 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 schwertmannite, 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) precipitates 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 precipitate at circumneutral pH in the stream courses. Among the solid phases forming in the AMD systems, schwertmannite plays a major role: (1) in the control of Fe solubility 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 substantially remain in solid form within the Odiel basin. However, the remaining dissolved loadings that reach the Huelva estuary still imply impressive metal amounts of several thousand tonnes (specially the most soluble metals 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-Edwards and an anonimous reviewer are thanked for their helpful comments on an earlier version of this manuscript. 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 dedicate this work to the loving memory of the 192 people killed by the terrorist bombings in Madrid on 11March 2004.
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J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 Demchak, J., Skousen, J., McDonald, L.M., 2004. Longevity of acid discharges from underground mines located above the regional water table. J. Environ. Qual. 33, 656668. Dold, B., 2003. Dissolution kinetics of schwertmannite and ferrihydrite in oxidized mine samples and their detection by dierential X-ray diraction (DXRD). Appl. Geochem. 18, 15311540. Elbaz-Poulichet, F., Morley, N.H., Cruzado, A., Velasquez, Z., Achterberg, E.P., Braungardt, C.B., 1999. Trace metal and nutrient distribution in an extremely low pH(2.5) riverestuarine system, the Ria of Huelva (South-West Spain). Sci. Total Environ. 227, 7383. Elbaz-Poulichet, F., Braungardt, C., Achterberg, E., Morley, N., Cossa, D., Beckers, J.M., Nomerange, P., Cruzado, A., Leblanc, M., 2001. Metal biogeochemistry in the TintoOdiel rivers (Southern Spain) and in the Gulf of Cadiz: a synthesis of the results of TOROS project. Continental Shelf Res. 21, 19611973. Fukushi, K., Sasaki, M., Sato, T., Yanese, N., Amano, H., Ikeda, H., 2003. A natural attenuation of arsenic in drainage from an abandoned arsenic mine dump. Appl. Geochem. 18, 12671278. Goldfarb, R.J., Nelson, S.W., Taylor, C.D., dAngelo, W.M., Meier, A.M., 1996. Acid mine drainage associated with volcanogenic massive sulphide deposits, Prince William Sound, Alaska. In: Dumoulin, J.A., Gray, J.E. (Eds.), Geologic Studies in Alaska by the U.S. Geological Survey 1995: U.S. Geol. Surv. Prof. Pap. 1574, pp. 318. Gonzalez-Toril, E., Llobet-Brossa, E., Casamayor, E.O., Amann, R., Ails, R., 2003. Microbial ecology of an extreme acidic environment, the Tinto River. Appl. Environ. Microbiol. 6, 48534865. Hudson-Edwards, K., Schell, C., Macklin, M.G., 1999. Mineralogy and geochemistry of alluvium contaminated by metal mining in the Ro Tinto area, southwest Spain. Appl. Geochem. 14, 10151030. IGME 1998. Inventario Nacional de Balsas y Escombreras. Unpublished database (in Spanish). Kawano, M., Tomita, K., 2001. Geochemical modeling of bacterially induced mineralization of schwertmannite and jarosite in sulfuric acid spring water. Am. Mineral. 86, 11561165. Kimball, B.A., 1999. Seasonal variation in metal concentrations in a stream aected by acid mine drainage, St. Kevin Gulch, Colorado. In: Filipek, L.H., Plumlee, G.S. (Eds.), The Environmental Geochemistry of Mineral Deposits, Part B. Case Studies and Research Topics: Society of Economic Geologists, Rev. Econ. Geol. 6B, pp. 467477. Kirby, C.S., Elder Brady, J.A.E., 1998. Field determination of Fe(II) oxidation rates in acid mine drainage using a continuously stirred tank reactor. Appl. Geochem. 13 (4), 509520. Kirby, C.S., Thomas, H.M., Southam, G., Donald, R., 1999. Relative contributions of abiotic and biological factors in Fe(II) oxidation in mine drainage. Appl. Geochem. 14, 511 530. Lee, G., Bigham, J.M., Faure, G., 2002. Removal of trace metals by coprecipitation with Fe, Al and Mn from natural waters contaminated with acid mine drainage in the Ducktown Mining District, Tennessee. Appl. Geochem. 17, 569581.
References
Achterberg, E.P., Herzl, V.M.C., Braungardt, C.B., Millward, G.E., 2003. Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter. Environ. Poll. 121, 283292. Ahonen, L., Tuovinen, O.H., 1989. Microbiological oxidation of ferrous iron at low temperatures. App. Environ. Microbiol. 55 (2), 312316. Alpers, C.N., Nordstrom, D.K., Thompson, J.M., 1994. Seasonal variations of Zn/Cu ratios in acid mine water from Iron Mountain, California. In: Alpers, C.N., Blowes, D.W. (Eds.) Environemntal geochemistry of sulphide oxidation, Am. Chem. Soc. Symp. Ser. 550, pp. 324344. Amaral Zettler, L.A., Messerli, M.A., Laatsch, A.D., Smith, P.J.S., Sogin, M.L., 2003. From genes to genomes: beyond biodiversity in Spains Rio Tinto. Biol. Bull. 204, 205209. AYESA, 1996. Estudio de correccion de euentes acidos en la cuenca del ro Odiel (Technical report with works descrip tion). Junta de Andaluca, unpublished report. Ball, J.W., Nordstrom, D.K., 1989. Final revised analyses of major and trace elements from acid mine waters in the Leviathan mine drainage basin, California and Nevada October 1981 to October 1982. U.S. Geol. Surv. WaterResour. Investig. Rep. 89-4138. Ball, J.W., Nordstrom, D.K., 1991. Users manual for WATEQ4F with revised thermodynsmic data base and test cases for calculating speciation of major, trace, and redox elements in natural waters. U.S. Geol. Surv. Open-File Rep. 91-183. Banwart, S.A., Malmstrom, M.E., 2001. Hydrochemical mod elling for preliminary assessment of minewater pollution. J. Geochem. Explor. 74, 7397. Bigham, J.M., Carlson, L., Murad, E., 1994. Schwertmannite, a new iron oxyhydroxysulphate from Pyhasalmi, Finland, and other localities. Mineral. Mag. 58, 641648. Bigham, J.M., Schwertmann, U., Carlson, L., Murad, E., 1990. A poorly crystallized oxyhydroxyulfate of iron formed by bacterial oxidation of Fe(II) in acid mine waters. Geochim. Cosmochim. Acta 54, 27432758. Bigham, J.M., Schwertmann, U., Traina, S.J., Winland, R.L., Wolf, M., 1996. Schwertmannite and the chemical modeling of iron in acid sulfate waters. Geochim. Cosmochim. Acta 60, 21112121. Braungardt, C.B., Achterberg, E.P., Elbaz-Poulichet, F., Morley, N.H., 2003. Metal geochemistry in a minepolluted estuarine system in Spain. Appl. Geochem. 18, 17571771. Buckby, T., Black, S., Coleman, M.L., Hodson, M.E., 2003. Fe-sulphate-rich evaporative mineral precipitates from the Ro Tinto, southwest Spain. Mineral. Mag. 67, 263278. Carlson, L., Schwertmann, U., 1981. Natural ferrihydrites in surface deposits from Finland and their association with silica. Geochim. Cosmochim. Acta 45, 421429. Cossa, D., Elbaz-Poulichet, F., Nieto, J.M., 2001. Mercury in the Tinto-Odiel Estuarine System (Gulf of Cadiz, Spain): sources and dispersion. Aquat. Geochem. 7, 112. Davis Jr., R.A., Welty, A.T., Borrego, J., Morales, J.A., Pendon, J.G., Ryan, J.G., 2000. Rio Tinto estuary (Spain): 5000 years of pollution. Environ. Geol. 39, 11071116.
J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 Leistel, J.M., Marcoux, E., Thieblemont, D., Quesada, C., Sanchez, A., Almodovar, G.R., Pascual, E., Saez, R., 1998. The volcanic-hosted massive sulphide deposits of the Iberian Pyrite Belt. Review and preface to the Thematic Issue. Mineral. Deposita 33, 230. Lopez-Archilla, A.I., Amils, R., 1999. A comparative ecological study of two acidic rivers in southwestern Spain. Microbial Ecol. 38, 146156. Lopez-Archilla, A.I., Marn, I., Amils, R., 2001. Microbial community composition and ecology of an acidic aquatic environment: the Tinto river, Spain. Microbial Ecol. 41 (1), 2035. Majzlan, J., Navrotsky, A., Schwertmann, U., 2004. Thermodynamics of iron oxides: Part III. Enthalpies of formation and stability of ferrihydrite (Fe(OH)3), schwertmannite (FeO(OH)3/4(SO4)1/8), and e-Fe2O3. Geochim. Cosmochim. Acta 68 (5), 10491059. Marcoux, E., 1998. Lead isotope systematics of the giant massive sulphide deposits in the Iberian Pyrite Belt. Mineral. Deposita 33, 4558. Murad, E., Schwertmann, U., Bigham, J.M., Carlson, L., 1994. Mineralogical characteristics of poorly crystallized precipitates formed by oxidation of Fe(II) in acid sulphate waters. In: Alpers, C.N., Blowes, D.W. (Eds.), Environmental Geochemistry of Sulphide Oxidation. Am. Chem. Soc. Symp. Series 550, pp. 190200. Nelson, C.H., Lamothe, P.J., 1993. Heavy metal anomalies in the Tinto and Odiel River and Estuary system, Spain. Estuaries 16, 496511. Nordstrom, D.K., 1977. Thermochemical redox equilibria of ZoBells solution. Geochim. Cosmochim. Acta 41, 1835 1841. Nordstrom, D.K., 1982. The eect of sulphate on aluminum concentrations in natural waters: some stability relations in the system Al2O3SO3H2O at 298 K. Geochim. Cosmochim. Acta 46, 681692. Nordstrom, D.K., 1985. The rate of ferrous iron oxidation in a stream recieving acid mine euent. Selected papers in the hydrologic sciences. U.S. Geol. Surv. Water Supply Pap., 113119. Nordstrom, D.K., 1999. Eorescent salts and their eects on water quality and mine plugging. In: Fernandez Rubio (Ed.) IMWA Internat. Congress, September 1317, 1999, Sevilla, Mine, Water and the Environment 2, pp. 543546. Nordstrom, D.K., 2000. Aqueous redox chemistry and the behavior of iron in acid mine waters. In: Wilkin, R.T., Ludwig, R.D., Ford, R.G. (Eds.), Proceedings of the workshop on monitoring oxidation-reduction processes for ground-water restoration, Dallas, Texas, April 2527, 2000, US Environmental Protection Agency, EPA/600/R-02/002, pp. 4347. Nordstrom, D.K., Alpers, C.N., 1999a. Geochemistry of acid mine waters. In: Plumlee, G.S., Logsdon, M.J. (Eds.), The Environmental Geochemistry of Mineral Deposits, Part A. Processes, Techniques, and Health Issues: Society of Economic Geologists, Rev. Econ. Geol. 6A, pp. 133156. Nordstrom, D.K., Alpers, C.N., 1999b. Negative pH, eorescent mineralogy, and consequences for environmental restoration at the Iron Mountain Superfund site, California. Proc. Natl. Acad. Sci. USA 96, 34553462.
1355
Nordstrom, D.K., Ball, J.W., Robertson, C.E., Hanshaw, B.B., 1984. The eect of sulphate on aluminum concentrations in natural waters: II. Field occurrences and identication of aluminum hydroxysulphate precipitates. Geol. Soc. Am. Program Abstr. 16 (6), 611. Parkhurst, D.L., Appelo, C.A.J., 1999. Users guide to PHREEQC (Version 2) A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. US Geol. Surv. Water-Resour. Investig. Rep. 99-4259, Denver-Colorado. Plumlee, G.S., Smith, K.S., Montour, M.R., Ficklin, W.H., Mosier, E.L., 1999. Geologic controls on the composition of natural waters and mine waters draining diverse mineraldeposit types. In: Filipek, L.H., Plumlee, G.S. (Eds.), The Environmental Geochemistry of Mineral Deposits, Part B. Case Studies and Research Topics: Society of Economic Geologists, Rev. Econ. Geol. 6B, pp. 373432. Pinedo Vara, I., 1963. Piritas de Huelva (su historia, minera y aprovechamiento). Madrid, Ed. Summa. Regenspurg, S., Brand, A., Peier, S., 2004. Formation and stability of schwertmannite in acidic mining lakes. Geochim. Cosmochim. Acta 68, 11851197. Sanchez Espana, F.J., 2000. Mineralogy and geochemistry of the massive sulphide deposits of the Northern area of the Iberian Pyrite Belt (San Telmo-San Miguel-Pena del Hierro), Huelva, Spain. Ph.D. Thesis, University of Pas Vasco, Bilbao. Serrano, J., Vinas, L., Lopez Fernandez, A.J., 1995. Proyecto de regeneracion de los ros Tinto y Odiel (Huelva). Tecnoambiente 53, 5356. Singer, P.C., Stumm, W., 1970. Acidic mine drainage: the ratedetermining step. Science 167, 11211123. Smith, K.S., 1999. Metal sorption on mineral surfaces: an overview with examples relating to mineral deposits. In: Plumlee, G.S., Losdon, M.J. (Eds.), The Environmental Geochemistry of Mineral Deposits, Part A. Processes, Techniques, and Health Issues: Society of Economic Geologists, Rev. Econ. Geol. 6A, pp. 161182. Stumm, W., Lee, G.F., 1961. Oxygenation of ferrous iron. Indus. Eng. Chem. 53, 143146. Stumm, W., Morgan, J.J., 1981. Aquatic Chemistry, second ed. Wiley, New York. Van Geen, A., Boyle, E.A., Moore, W.S., 1991. Trace metal enrichments in waters of the Gulf of Cadiz, Spain. Geochim. Cosmochim. Acta 55, 21732191. Van Geen, A., Adkins, J.F., Boyle, E.A., Nelson, C.H., Palanques, A., 1997. A 120 yr record of widespread contamination from mining of the Iberian pyrite belt. Geology 25 (4), 291294. Velasco, F., Sanchez-Espana, F.J., Boyce, A., Fallick, A., Saez, R., Almodovar, G.R., 1998. A new sulphur isotopic study of some IPB deposits: evidence of a textural control on the sulphur isotope composition. Mineral. Deposita 33 (8), 418. Vinas, L., Lopez Fernandez, A., 1994. Correccion medioambi ental de impactos de origen minero en la Cuenca del Odiel. Residuos 3, 6771. Waddell, R.K., 1978. Evaluation of a surcial application of limestone and ue dust in the abatement of acidic drainage: Jonathan Run Drainage Basin at Interstate 80, Centre County, Pennsylvania. Ph.D. dissertation, Pennsylvania State University.
1356
J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 Williamson, M.A., Kirby, C.S., Rimstidt, J.D., 1992. The kinetics of iron oxidation in acid mine drainage. Programs and Abstracts, V.M. Goldschmidt Conference. Yu, J., Heo, B., Choi, I., Chang, H., 1999. Apparent solubilities of schwertmannite and ferrihydrite in natural stream waters polluted by mine drainage. Geochim. Cosmochim. Acta 63, 34073416.
Webster, J.G., Swedlund, P.J., Webster, K.S., 1998. Trace metal adsorption onto acid mine drainage Fe(III) oxyhydroxysulphate. Environ. Sci. Technol. 32, 13611368. Williams, D.J., Bigham, J.M., Cravotta, C.A., Traina, S.J., Anderson, J.E., Lyon, J.G., 2002. Assessing mine drainage pH from the color and spectral reectance of chemical precipitates. Appl. Geochem. 17, 12731286.

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Applied Geochemistry

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

1. Introduction and scopes

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

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

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

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

Rainfall discharge (mm/day)

Diary rainfall discharge Odiel waterheads 2003

Jan Feb Mar Apr May Jun

Aug Sep Oct

Flow rate (Hm /year)

Daily Water Flow (m 3/s)

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

VSC rocks Undifferentiated rocks

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El Soldado Esperanza Gloria La Poderosa La Poderosa La Poderosa

938-119 938-122 960-103 938-103 938-113 938-114

La Poderosa La Torerera La Zarza-Perrunal

Waste-rock pile leachate Waste-rock pile leachate Mine adit

938-118 959-100 937-108

Monte Romero Rio Tinto

Waste-rock pile leachate Ore dump leachate

Ore dump leachate Water reservoir outow Mine adit

938-117 938-48 938-102

Rio Tinto (Corta Atalaya)

Waste-rock pile leachate

Rio Tinto (Corta Atalaya) Rio Tinto (Corta Atalaya)

Waste-rock pile leachate Waste-rock pile leachate

Rio Tinto (Corta Atalaya)

Waste-rock pile leachate

Rio Tinto (Corta Atalaya)

Waste-rock pile leachate

Rio Rio Rio San

938-127 938-128 938-129 938-108 938-121

San Platon San Platon San Telmo

ALD outow Mine adit Waste-rock pile leachate

938-106 938-123 937-104

Waste-rock pile leachate

Pit lake outow

Waste-rock pile leachates

Waste-rock pile leachate

Ore dump leachate Ore dump leachate

92 99 102 57 91 60 6 11 10 0 4 12 97 60 0 7 48 0 0 46 95 0 93 41 85 3 6 0 5 25 47 100 4 5 26 5 4 5 11 1 101 100 92 92 93 88 99 90 89 80 70 79 40

J. Sanchez Espana et al. / Applied Geochemistry 20 (2005) 13201356 1329

959-107 959-108 959-110 960-100 960-101 960-102 960-104

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

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

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

262 167 35 100 65 14.7 15 35 51

1142 696 3.2 0.3 Mar-04 960-104

Average IPB AMD

Tinto-Sta Rosa Trincheron

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

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

IPB Iron Mountain

10,000 1,000 100 10 1 -3.0

100,000 10,000 1,000 100 10 1 0 10 100 1,000 10,000 100,000 1,000,000

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