Environ Geol (2008) 55:1797–1809
DOI 10.1007/s00254-007-1131-x
ORIGINAL ARTICLE
Potential environmental impact at São Domingos mining district
(Iberian Pyrite Belt, SW Iberian Peninsula): evidence
from a chemical and mineralogical characterization
A. M. Álvarez-Valero Æ R. Pérez-López Æ
J. Matos Æ M. A. Capitán Æ J. M. Nieto Æ
R. Sáez Æ J. Delgado Æ M. Caraballo
Received: 24 April 2007 / Accepted: 12 November 2007 / Published online: 28 November 2007
Ó Springer-Verlag 2007
Abstract São Domingos like other long-term activity
mines of the Iberian Pyrite Belt (IPB) dating back to pre-
Roman times, is supposed to produce considerable amounts
of mining wastes which cause significant downstream
negative environment impact related to the acid mine
drainage (AMD) production and high content of potentially
toxic metals and metalloids in Chanza and Guadiana
Rivers. The AMD production of a given mining waste
depends on the ratio of its acid production to neutralizing
phases. In this work, a chemical and mineralogical char-
acterization of the sulphide-rich wastes from São
Domingos has been developed to discriminate which resi-
dues are the main sources of AMD generation. A total of 47
representative samples of the different residue types were
collected to estimate their possible contamination hazards
through detailed studies of (1) for a mineralogical charac-
terization: reflected-light optical microscope, scanning
electron microscope (SEM) and XRD analysis; and (2) for
a chemical characterization: bulk-rock analysis. AMD
prediction by the standard acid-base accounting method
(ABA) was used in order to determine the acidification
potential of each residue type. This study also offers an
estimation of the contribution of toxic elements to the
A. M. Álvarez-Valero (&)
R. Pérez-López

M. A. Capitán
J. M. Nieto
R. Sáez
J. Delgado

M. Caraballo
Department of Geology, Faculty of Experimental Sciences,
University of Huelva, Campus El Carmen,
Avda. Fuerzas Armadas, s/n, 21071, Huelva, Spain
e-mail: antoniomiguel.alvarez@dgeo.uhu.es
J. Matos
INETI, R. Frei Amador Arrais 39 rc,
Ap. 104 7800.902, Beja, Portugal
environment, being thus, a base for future remediation
actions at São Domingos and other abandoned massive
sulphide mines within the IPB.
Keywords Iberian Pyrite Belt
Mining wastes

Acid mine drainage
São Domingos mine

Environmental impact
Introduction
The exploitation of mineral resources has been one of the
essential activities for the development of the humanity.
However, the human intrusion in the environment produces
adverse alterations that always finish getting into debt to
the man with the nature. A clear example of this is the
Iberian Pyrite Belt (IPB), located in the southwest part of
the Iberian Peninsula. It is one of the largest metallogenetic
provinces of massive sulphides in the world with original
reserves over 1,700 Mt (Sáez et al. 1999). The mining-
metallurgical wealth of the region was the economic sup-
port of numerous civilizations seated from prehistoric
times (Nocete et al. 2005). The intense mining activity
produced considerable amount of residues, which have
caused the environmental deterioration of the zone in all its
meanings: soil degradation, water resources pollution,
biodiversity decrease, and even, atmospheric pollution in
some moments of the history. The most important envi-
ronmental problem derives from the sulphide (mainly
pyrite) oxidation contained in the aforementioned residues.
This process produces an extremely acid leachate with high
contents of sulphate, metals and metalloids known as acid
mine drainage (AMD) (Lowson 1982; Parker and Robert-
son 1999; Younger et al. 2002). The AMD is the main
pollution source of natural watercourses in mining
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1798
environments of the IPB (Guadiana, Tinto and Odiel rivers)
(Olı́as et al. 2006; Nieto et al. 2007).
In particular, the São Domingos mine is one of the most
emblematic Portuguese massive sulphide deposits. The
mining district is located in the northern sector of the IPB,
about 5 km from the Spanish border (Fig. 1). Although
mining activity has ceased at present, the large-scale
exploitation of this deposit between 1857 and 1966 favoured
the production of enormous waste dumps, where oxidation
of pyrite and associated sulphides is resulting in the AMD
production. The final acid discharge with high contents of
metals from São Domingos reaches the Chanza river, main
effluent of Guadiana river, causing its partial pollution.
The field-bearing secondary minerals within waste
deposits indicate that these materials are reactive. Jarosite
and other secondary low crystalline minerals as oxides, ox-
hydroxides, iron hydroxy-sulphates are important for the
environment as they play a crucial role in the solubility of
the potentially toxic chemical elements. For this reason
the chemical and mineralogical detailed studies at the
intensively contaminated area of São Domingos are fun-
damental to know the processes that influence liberation,
transport, retention and likely later remobilization of free-
metals after sulphide-oxidation.
A variety of proposals for restoration have been sug-
gested to reduce the environmental impact associated with
the AMD generation on the river basins of the IPB (Serrano
et al. 1995). The different technologies applied were
basically the passive treatment of AMD by means of
anaerobic compost wetlands and anoxic limestone drains
(Viñas and López Fernández 1994). Nevertheless, the
Fig. 1 Geographic location of the Iberian Pyrite Belt and related
main mining districts
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Environ Geol (2008) 55:1797–1809
treatment of the acidic waters generated in the IPB is a
short-term solution to the problem. The extreme acidity
and high concentration of metals (mainly Fe) of these
drainages saturate rapidly the treatment systems.
Summarizing, the sulphide oxidation processes at São
Domingos inevitably produces AMD leachates rich in
sulphates, iron and other heavy metals and metalloids
which are an important source of pollution, and hence a
threat to the ecologic equilibrium. The SW Iberian Penin-
sula climate favours the AMD generation process at São
Domingos and adjacent mining districts within the IPB.
The main objective of this work is the chemical and
mineralogical characterization of all types of mining and
smelting wastes in the São Domingos mining district, as a
base for the assessment of their environmental impact. This
will be the foot to design future remediation actions in the
area. For instance, recent investigations have been focused
on direct treatment of the mine residues, as sources of this
type of drainages. The experiments in laboratory of Pérez-
López et al. (2007a, b) show how the addition of a strongly
alkaline substance as fly ash material to a pyrite-rich
mining residue, favours the acid neutralization, metal
retention in AMD, and therefore, the improvement of the
quality of the leachates produced. Only to carry out a
treatment of this type in the field, the preliminary step is to
characterize and identify which are the potentially acid
producing wastes.
A brief geological setting
The IPB is located in the Sud-Portuguese Zone (ZSP) of the
Hesperic Range (Fig. 1). It contains a complex stratigraphic
succession composed by volcanic and sedimentary rocks
ranging in age from Devonian to Carboniferous (Scher-
merhörn 1971). The middle series known as volcanic-
sedimentary complex (VSC) comprise essentially felsic
volcanic and subvolcanic rocks, with local basic flows and
sills, intercalated in a volcanoclastic sequence including
some marker horizons of purple slates and jasper. The VSC
host the massive sulphide deposits in the IPB. The São
Domingos pyrite orebody is located near the top of the VSC.
It is a single subvertical body of massive sulphides, which
main features can be summarised as follows: (1) lense
shaped 537 m long and 45–70 m thick; (2) mineral assem-
blage composed by pyrite, sphalerite, chalcopyrite, galena,
arsenopyrite and sulphosalts; (3) reserves 27 Mt at 1.25%
Cu, 1% Pb, 2% Zn and 45–48% S (Leistel et al. 1998); (4)
products as pyrite, roasted pyrite, sulphur and copper.
Although the São Domingos orebody was mined since
the Calcolithic age, the main activity began in Roman
times (Custódio 1996). Afterwards, the two more important
events of mining exploitation occurred in the last decades
Environ Geol (2008) 55:1797–1809
of the XIX century, and within the 1930s–1960s. Different
residue types were generated as a consequence of this
historical mining activity.
Methodology
Sampling and Mapping
Forty-seven samples (approx. 2 kg each) were collected in
the whole mining area, in the range of 3–7 samples of each
residue type, using a polypropylene shovel, and subse-
quently transferred to clean polypropylene bags in April
2006. The identification and sampling of the wastes in the
field were coeval to the cartographic activity.
The waste impact cartographic map at scale of 1:2,500
was compelled with two main objectives: (1) to make a
detailed map of the abandoned open pit, mainly of the
orebody hydrothermal system and its structural control; (2)
to possess a two dimensional overview of the mining
infrastructures and detailed distribution of the wastes
(Matos 2004). The mapping was also supported by aerial
photograph and multispectral remote sensing data (GIS-
ArcView 3.2Ó and CAD software) from INETI MINEO
project. A global understanding of the mining site was
always present during the mapping development, mainly
the location of the most important mine infrastructures (e.g.
open pit, tunnels, railway, ore mills, leaching and cemen-
tation tanks, sulphur plants, acid water dams and channels).
Additionally, a theoretical reconstruction of the volume
occupied by the different residue types was performed
considering the surface values, dump body shapes and
respective thickness (estimated from some old boreholes
drilled into the dumps; Table 1).
Mineralogy and chemistry
The chemical analyses and the mineralogical character-
ization were performed on the 47 samples of each residue
types. Samples were collected and immediately air-dried,
weakly rolled to break the aggregates and passed through a
2 mm sieve. The mineralogical characterization of all
samples was carried out by X-ray diffraction (XRD, pow-
der method) using a Bruker diffractometer (model D8
Advanced). Working conditions were slit fixed at 12 mm,
Cu Ka monochromatic radiation, 20 mA and 40 kV.
Samples were run at a speed of 0.3° 2h/min (5–60°). Semi-
quantitative mineralogical determination was estimated
with DIFFRACplus software. In order to complete the
mineralogical characterization, samples were also observed
by means of a scanning electron microscopy equipped with
an energy dispersive system (SEM-EDS) for the chemical
1799
microanalysis (JEOL JSM–5410), and in some occasions
with reflected and transmitted light optical microscope.
Bulk rock composition of the samples was analyzed by
Acme Analytical Laboratories Ltd (Vancouver, Canada),
accredited under ISO 9002, through its Italian affiliate (ERS
Srl, Napoli). The major (Si, Al, Fe, Mg, Ca, Na, K, Ti and P)
and minor (Ba, Co, Rb, Sn, Sr, Ta, Th, U, V, W and Zr)
elements were subjected to LiBO2 fusion/dilute nitric
digestion and analyzed by ICP-AES (inductively coupled
plasma-atomic emission spectroscopy) and ICP-MS
(inductively coupled plasma-mass spectrometry), respec-
tively. The heavy metals and metalloids (Mo, Cu, Pb, Zn,
Ni, As, Cd, Sb, Bi, Ag, Au, Hg, Tl and Se) were determined
by leaching of 0.5 g of each sample with aqua regia extracts
(3:1 HCl–HNO3) at 95°C for 1 h, follow by ICP-AES
analysis. Volatile phases were calculated by loss on ignition
(LOI, 550°C), and total carbon and sulphur by Leco.
A Sobek acid base accounting (ABA) test (Sobek et al.
1978) was also used to calculate the AMD generation
capacity (acidic potential or AP) and the AMD neutralizing
capacity (neutralization potential or NP) in all residues
through the modified ABA procedure proposed by Law-
rence and Wang (1997). AP was calculated following the
equation: AP = % total S 9 30.6 (expressed in kg H2SO4/t
equivalent) and the NP was determined by titration
methods (expressed in kg H2SO4/t equivalent). The
difference between the NP and AP values represent the
net neutralization potential (NNP) of the sample, i.e.
NP - AP = NNP. Thus, if the sample shows a NNP value
lower than -20 kg H2SO4/t, it is considered AMD gener-
ating, while a NNP value higher than +20 kg H2SO4/t
indicates that the sample is non-AMD generating. If NNP
values are between -20 and 20 kg H2SO4/t, the sample is
within an uncertainty zone (Lawrence and Wang 1997).
Results and discussion
Mapping
Figure 2 shows the cartographic map of the different resi-
due types in the São Domingos mining area. Two main
groups of mining residues can be recognized: (1) industrial
wastes derived from the ore processing operations, includ-
ing: Roman and modern slags, iron oxides, smelting ashes,
pyrite-rich waste dumps, leaching tanks refuses, and
industrial landfills; and (2) mine wastes heaped as dumps,
including gossan and sulphide disseminated country rocks
(host volcanic rocks and shales). Slags are the residues from
Cu ore (mainly chalcopyrite) smelted in furnaces (Fig. 3a,
b). Smelting ashes (Fig. 3c) derive from the cleaning of high
temperature condensers during the smelting process.
However, the preferred method for extracting copper was
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1800 Environ Geol (2008) 55:1797–1809

Table 1 Waste types and origin of the São Domingos mining area extracted from the geological and mining map of Fig. 2
Rock type Mining Surface (m2) Volume (m3) Predominant location Waste origin
waste
Roman XIX 1930s–
period century 1960s

Ore Modern slag – – 109,717 877,736 Open pit, Moitinha, Residues from Cu ore, smelted in
processing Achada furnaces
wastes Roman slag 28,173(a) – – 225,384 Open pit cleaning of HT condensers during
Smelting – – 27,968 27,968 Moitinha, Achada the smelting process
ashes products from Cu ore roasting
Pyrite-rich – – 8,035 64,280 Open pit, Moitinha, process
samples Achada remains of pyrite-rich wastes
Iron oxides – 3,606 – 3,606 Achada compacted and spread as
Leaching – 152,306 ? 1,218,448 Moitinha containment barriers
tanks adjacent material heaped as dumps
Industrial – 501,265 4,010,120 São Domingos valley
landfills

Ore extracting Gossan – 209,832 – 1,678,656 Open pit, Village,

wastes wastes Moitinha, Achada
Country – 334,214 – 2,673,712 Open pit
rocks

Surface covered by wastes [255,300 2,963,900 Total From open pit to

(b) (c) m3 = 10,779,910 Chumbeiro
25,753,600 (d)
Classification as a function of the ore origin. Surface data obtained by CAD geological and mining mapping. Volume values calculated after the
surface and thickness data observation. (a) Inferred surface; (b) total surface and volume affected by the mining activity including; (c) mining
wastes areas and volumes; (d) area under village houses and contaminated urban landfill (not considered for the study. See details in the text)

cementation, where low-grade Cu ores were roasted in piles
and washed with acidic water to extract the soluble Cu that
was later precipitated onto Fe sheets. Iron oxides are the
waste products from this Cu ore roasting process. The
pyrite-rich waste dumps (i.e. samples of brittle pyrite and
pyrite blocks) are the input material for this roasting pro-
cess, previously crushed in the case of brittle pyrite.
Leaching tank refuses (Fig. 3d) correspond to remains of
pyrite-rich wastes in which the leaching process is in such
an advanced state that pyrite is practically dissolved.
Finally, industrial landfills refer to those residues com-
pacted and spread in layers used as containment barriers.
From a chronological point of view, the three main
groups of wastes are: (1) Roman slags related to gossan and
supergene enrichment of exploitation zone; (2) gos-
san + host rocks + local reworked Roman slags + roasted
ore related to XIX century open pit/underground exploita-
tion; and (3) ore related to XX century mine exploitation as
modern slags + sulphide roasted ashes + brittle pyrite
ore + coarse blocks of pyrite + smelting ashes + dumps.
Figure 3e shows the gossan wastes field appearance.
The extremely final acid drainage after the residues
leaching (Fig. 3f) achieves the Chanza dam, main reservoir
supplying ‘‘potable’’ water to the Huelva province,
although the contamination is relatively attenuated.
The surface and volume of the waste dumps, and a rief
description of the wastes origin is presented in Table 1.
The total area affected by mining activities in São Do-
mingos is around 3,200,000 m2, where ca. 544,000 m2 is
occupied by waste material from the ore extraction and
around 831,000 m2 by residues from the ore processing
including industrial landfills and leaching tank refuses. The
rest of the affected area, ca. 1,610,000 m2, is occupied by
material under the village houses, never sampled including,
e.g. acid drainage related with evaporation process; acid
waters lagoons/dams; leached clay materials; and cemen-
tation tanks. Taking into account the different thickness of
each residue, a total of 25 Mm3 of mining wastes can be
estimated in the total area of the mine (Table 1). However,
around 14 Mm3 of this total is under the village houses
whereas the total of the ore extracting wastes and the ore
processing residue types are around 11 Mm3 (ca. 32 Mt of
mining wastes).
Mineralogical characterization of the wastes
The mineralogical composition of the wastes from São
Domingos is summarized in Table 2. The typical mineral
association of the wastes is as follows: quartz, goethite,

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Environ Geol (2008) 55:1797–1809 1801

Fig. 2 Geological and mining

map of the São Domingos area,
including the cartography of the
main type of wastes. Geology:
(1) Quaternary alluvium
sediments; (2) Palaeozoic
Basement (South Portuguese
Zone): Mértola Fm. (Upper
Viséan); Volcano Sedimentary
Complex (Late Famennian–Late
Viséan); Phyllite-Quartzite
Group (Frasnian–Late
Famennian); Represa Fm. (Late
Famennian); Barranco do
Homem Fm. (Famennian?);
Gafo Fm. (Lower Frasnian).
Mining wastes: Tailings: E1—
Modern slag; E2—Roman slag;
E3—Gossan; E4—
Volcanics + shales; E5—
Shales; E6—Brittle pyrite ore;
E7—Roasted pyrite ore (sulphur
factories ashes); E8—Iron
oxides (hematite roasted pyrite).
Landfills and infrastructures:
F— Leached materials in
seasonal flooded areas; L—
Mine landfill; U—Urban
contaminated landfills; (AMD)
unvegetated area affected by
extreme acid mine drainage;
(LF) Pyrite ore leaching plateau;
(3) Acid water dam/lagoon; (4)
Clean water dam; (5) Cu
cementation tank; (6) Orkla
sulphur factories; (7) Railway
station; (8) Power plant; (9)
Abandoned mine railway; (10)
Mine channel; (11) Stream

hematite, jarosite and mica. The sulphides presence/
absence within the wastes (Table 2) determines their main
subdivision from an AMD-origin point of view. The cli-
mate of the area is of a Mediterranean type, which
alternate long warm-dry periods and short but intense
rainy periods. The oxidation of pyrite and other minor
metallic sulphides in pyrite-bearing wastes (modern and
Roman slags, smelting ashes and pyrite-rich samples)
produce direct AMD generation during the entire year.
The large AMD production became a huge problem for
carrying out the labours during mining activity periods.
For this reason, most of pyrite-absence wastes (mainly the
most volumetric ones, i.e. leaching tanks and industrial
landfill) were strategically collocated for blocking the
acidic discharges, and later loose them by evaporation in
warm periods. This favours the precipitation of evaporitic
soluble salts in these residues, besides in direct AMD
producing residues.

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1802
Fig. 3 Field occurrence of: a modern and b Roman slags; c smelting ashes; d leaching tank refuses; e gossan wastes; and f final AMD discharge
São Domingos processing ore wastes
As mentioned in ‘‘Mapping’’, Fig. 2 and Table 1 show the
processing ore wastes: modern and Roman slags, smelting
ashes, iron oxides, pyrite-rich waste dumps (coarse blocks
and brittle pyrite), leaching tanks refuses and industrial
landfills. Both, Roman and modern slags typically show
quartz (20–35%), olivine-group minerals (mainly fayalite)
in the range of 15–25%, magnetite up to 40%, Fe oxides
(10–15% of hematite and goethite), glass, sulphides up to
15% (pyrite and chalcopyrite), and minor secondary phases
formed by sulphide weathering (e.g., jarosite). Two
immiscible glass types (quenched melt) also occur as evi-
dence of the base-metal smelting process: (1) the original
melt from the mixing of the processing material doped with
a flux; and (2) the metallic alloy segregated from the ori-
ginal melt (Fig. 3c). Fine grain-sized smelting ashes
mainly comprise of silicate minerals (quartz and feldspar),
relatively high contents of gypsum (around 20 wt%) and
graphite (5–10 wt%), and minor proportions of pyrite (1–5
wt%).
The pyrite-rich samples are mainly composed of quartz
(25–40%), pyrite (15–40%), and minor goethite, hematite,
jarosite and rare micas (Fig. 3d, e). Iron oxides from piles
of roasted pyrite ore are typically composed of hematite/
goethite (Fig. 3f). Leaching tanks refuses have a mineral
composition of quartz (around 80%) and minor gypsum
and sulphide oxidation phases, like hematite, goethite,
jarosite. Industrial landfill material show similar miner-
alogy to the leaching tanks refuses. Quartz is present up to
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Environ Geol (2008) 55:1797–1809
90%, hematite, goethite, jarosite also occur as minor
phases, and gypsum is absent. SEM images of Fig. 4
show the pyrite-bearing residues involving minor metallic
sulphide phases, not detectable by XRD owing to low
proportions, as galena, sphalerite and arsenopyrite. These
minerals are the original source for the metallic elements
as Pb, Zn, As, inherited by the residues. The percolation
of air and water into the pyrite-bearing dumps controls the
depth of pyrite oxidation. The residues are highly porous
media favouring thus the O2 diffusion (in water or air)
and hence the oxidation of pyrite and other minor sulp-
hides (Ritchie 1994; Lefebvre et al. 2001). In the pyrite-
bearing residues, the pyrite grains present features evi-
dencing the oxidation process, and hence, the AMD
production in time. Figure 4a, for instance, shows pyrite
grains rounded by secondary oxidation minerals as jaro-
site (image from pyrite-rich samples) and Fig. 4b presents
a pyrite grain totally corroded (image from smelting
ashes).
São Domingos extraction ore wastes
The residues of this group (see Table 2) are: gossan
wastes (gossan coarse blocks, gossan brittle, gossanized
volcanics), and country rocks (host volcanics with shales,
and shales). The mineralogy of the oxidized gossan
wastes is mainly characterized by quartz (70–85%),
minor micas and typical mineral assemblages of sulphide
oxidation covers (i.e. hematite and goethite, jarosite,
Environ Geol (2008) 55:1797–1809 1803

Jarosite
beudantite and Fe–Cu metals hydrated sulphates as co-

10–15
5–10

5–10
piapite and poitevinite). The country rocks waste group

1–5
1–5
1–5
1–5
Hematite presents a similar mineralogy to the gossan wastes. They
include quartz ranging from 75 to 85%, and minor micas
10–15
and K-feldspar (Fig. 3b). This group also contains sul-

5–10

5–10
1–5
1–5
1–5
95
phide oxidation minerals including hematite, goethite and
also jarosite.
Gypsum

Efflorescent salts can be observed in situ in both res-

1–5
20

idue types of São Domingos (Fig. 5). They are low-

Secondary minerals (wt%)

crystalline metallic hydrated sulphate minerals and hence

Goethite

not identified by XRD within the host residue. Figure 5

10–15

5–10
1–5

1–5
1–5
1–5
1–5
shows examples of copiapite (Fe2+Fe3+ 4 (SO4)6(OH)2

5

20(H2O)) and poitevinite (Cu,Fe2+,Zn)SO4(H2O)). Buckby

Beudantite

et al. (2003) and Sánchez-España et al. (2005) described

these salts within the IPB as epsomite, hexahydrite, co-
1–5

piapite, halotrichite, rozenite, coquimbite, among others.

Those from the processing residues occur after pyrite
Quartz

25–40

70–80
75–85

samples oxidation, whereas the salts related to the extrac-

20
30
60

80
90

tion process residues precipitated after water evaporation

during warm seasons. In fact, recent data from Smuda
Py + Cpy

et al. (2007) suggest that AMD formation is strongly

10–15

15–40
5–10
1–5

controlled by the local climate. During the normal warm-

hot season from May to October in the SW Iberian Pen-
Muscovite

insula, high evaporation of porous solutions outcrops and

subsequently precipitation of efflorescent salts may provide
5–10

5–10
1–5

a heavy metal-enrichment at the base of the waste rock

dumps (Fig. 5). The rain-waters (during rainy seasons) and
Magnetite

the acid waters from the mining (fluxes addressed by the

miner), may cause both the dissolution of most of efflo-
1–5
40

rescent salts, and remove the enrichment at the base of the

waste heap, leading to a washout of acid solutions rich in
K-feldspar

heavy metal elements. The dissolved elements are further

1–5

precipitated within the sulphate mineral during the water

15

evaporation. In fact, the residual dumps at São Domingos

Kaolinite
Table 2 Mineralogical composition of the São Domingos residues

are the contamination source of the adjacent areas, espe-

5–10

cially to the catchments area of the Chanza and Guadiana

1–5
1–5

Rivers, supplying acidic waters with high amounts of

metals in solution. These stream water samples, flowing
Halloysite

from the dumps, show pH values ranging from 2 to 2.8

10–15

1–5

1–5
1–5

(Delgado et al. 2006). Hence, even lower pH values

Primary minerals (wt%)

probably occur at those stream waters directly leachated

Graphite

from the dumps. In fact, recent works (e.g., Freitas et al.

5–10

2004; Gerhardt et al. 2005; Gadanho and Sampaio 2006)

evidence the AMD toxic effects on plants and diverse
water-soils kinds of life in the São Domingos mining
Fayalite

district.
15
20

Pyrite-rich samples

Industrial landfills

Geochemical characterization of the wastes

Leaching tanks
Smelting ashes

Gossan wastes
Country rocks
Mining waste

Modern slag
Roman slag

Iron oxides

Major elements composition of the different residue types

are presented in Table 3 and minor and trace element
compositions are graphically shown in Fig. 6.

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1804 Environ Geol (2008) 55:1797–1809

Fig. 4 SEM views of: a, b

corroded (oxidized) pyrite
crystals within the from pyrite-
rich samples and smelting ashes,
respectively. The jarosite
presence (secondary) evidences
the pyrite oxidation process,
whereas galena is a primary
phase as pyrite; c Roman slag
with fayalite crystals, quartz,
and both immiscible melt types:
one original melt from the
processing material, and another
from the metallic alloy
segregated from the original
melt; d iron-oxide residue

Fig. 5 Photos of efflorescent

salts precipitated during warm
periods: a copiapite and b
poitevinite. c XRD patterns of
these evaporitic salts. d SEM
view of the same copiapite

São Domingos processing ore wastes
Slags are hugely variable in Zn and As contents. Modern
slags show average values of Zn around 8,500 ppm and As
ca. 215 ppm, whereas Roman slags have Zn ca. 210 ppm
and As around 760 ppm. Modern slags have the highest
values of Ca, around 4.5 CaO wt%. ABA test calculations
indicate an average positive acid potential for both slag
types (90–170), and hence a negative NNP (Fig. 7). The
sequential extraction study of Piatak et al. (2004) in slags

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Environ Geol (2008) 55:1797–1809 1805

Table 3 Geochemical composition and NNP of the São Domingos wastes in major elements, LOI, and total content of C and S
Minning waste SiO2 Al2O3 Fe2O3 MgO CaO Na2 K2O TiO2 P2O5 LOI Total/C Total/S Sum

Modern slag Mean (wt%) 28.61 1.64 59.58 0.11 4.27 0.10 0.21 0.12 0.07 4.40 3.24 2.97 97.72
(NNPa = -170 ± 42) SD 3.43 0.73 4.01 0.03 1.29 0.04 0.08 0.02 0.01 5.88 5.23 0.06 0.25
Roman slag Mean (wt%) 36.27 6.87 51.15 0.34 1.03 0.29 1.46 0.47 0.18 2.44 0.29 1.09 98.74
(NNP = -90 ± 33) SD 11.83 4.02 20.51 0.17 0.40 0.13 0.73 0.17 0.06 5.23 0.26 0.31 0.83
Smelting ashes Mean (wt%) 54.89 10.27 11.11 0.16 0.07 1.37 1.71 0.70 0.09 17.95 0.44 6.39 98.30
(NNP = -35 ± 17) SD 18.20 2.98 7.05 0.16 0.02 1.03 0.80 0.25 0.05 14.50 0.05 7.64 1.83
Pyrite-rich samples Mean (wt%) 46.31 11.12 15.39 0.18 0.44 0.89 1.93 0.68 0.13 21.86 0.72 7.12 98.97
(NNP = -250 ± 26) SD 11.03 2.50 0.91 0.04 0.36 0.20 0.59 0.32 0.01 5.93 0.30 1.79 0.27
Iron oxides Mean (wt%) 3.38 0.35 88.70 0.01 0.02 0.07 0.13 0.02 0.02 5.75 0.07 1.12 98.43
(NNP = no value) SD 2.85 0.30 5.76 0.00 0.01 0.05 0.01 0.01 0.01 1.34 0.07 0.81 1.20
Leaching tanks Mean (wt%) 42.52 8.66 28.84 0.11 1.24 0.86 1.23 0.53 0.08 14.70 0.44 3.37 98.57
(NNP = 15 ± 12) SD 5.31 6.19 20.31 0.06 2.05 0.75 1.13 0.20 0.02 13.17 0.22 1.25 1.28
Industrial landfills Mean (wt%) 60.77 4.11 21.38 0.08 0.32 0.37 0.72 1.14 0.11 9.50 1.73 1.17 98.53
(NNP = no value) SD 4.22 2.25 2.88 0.06 0.37 0.38 0.57 0.35 0.02 4.38 1.46 0.87 0.54
Gossan wastes Mean (wt%) 58.24 7.96 22.16 0.16 0.14 0.28 1.20 1.07 0.13 7.24 0.40 0.78 98.62
(NNP = no value) SD 5.46 3.97 7.25 0.07 0.10 0.14 0.64 0.29 0.03 0.99 0.10 0.17 1.13
Country rocks Mean (wt%) 57.78 11.78 16.43 0.22 0.14 0.43 2.08 0.86 0.14 9.54 0.79 1.18 99.46
(NNP = no value) SD 11.26 3.10 6.71 0.05 0.04 0.15 0.59 0.31 0.03 2.26 0.48 0.45 0.08
‘‘no value’’ indicates that NP = 0 and AP = 0. However, AP cannot be estimated since pyrite is absent, and the AMD generating capacity
derives from dissolution of evaporitic soluble salts (which cannot be calculated)
a
Net neutralization potential (kg H2SO4/t)

shows the importance of the slags as source of toxic metals
in abandoned mine sites, and how the existence of jarosite,
which only occurs at pH \ 4.2, evidences the acidic con-
dition of leaching.
Smelting ashes are characterized by high contents of
numerous elements as Pb, As, Sn, Sb, Cd, Mo, Se and Cu
(ca. 5,900, 840, 485, 135, 1.5, 14, 55, 2,200 ppm, respec-
tively). The NNP typically gives values within the
uncertainty zone (Fig. 7). According to the studies from
Dudka et al. (1995) and Adamo et al. (1996), this residue
could emits and release large quantities of S, Zn and Pb
into the environment when their metallic sulphides hosts
are oxidized. Similar circumstances have been mentioned
in other mining wastes by e.g., Lefebvre and Gélinas
(1995) and Romero et al. (2006).
Pyrite-rich samples contain high contents of Pb (ca.
4,700 ppm) and As (ca. 1,700 ppm). They have the highest
acid potential values in the whole São Domingos mining
district (around 250 kg H2SO4/t), and therefore the highest
negative NNP (Fig. 7).
The iron oxides samples show high contents of Pb
(around 7,900 ppm) and Sb (ca. 290 ppm), and a NNP
within the uncertainty zone. They have been described as
intensely mine-impacted soils, when internal drainage
(endorheic drain) occurs (Velasco et al. 2005). The
potential pollution of this common residue at the IPB has
been shown by, e.g. Pauwels et al. (2002), Sáinz et al.
(2003), Romero et al. (2006), who describe how the spoils
of this treatment caused many environmental problems due
to the release of SO2 to the atmosphere, and further
replacement by a variant of the extraction process which
consisted on the extraction by irrigating with acidic water
in open-air for more than 2 years. Leaching tank refuses
are characterized by high concentrations of As, Pb, Se, and
Zn (ca. 1,750; 4,700; 55; 2,750 ppm, respectively). Their
NNP values are within the uncertainty zone (Fig. 7). The
industrial landfill material shows high Pb (around
8,400 ppm), As (ca. 3,700 ppm) and Se (ca. 75 ppm)
concentrations, and the NNP are within the uncertainty
zone.
São Domingos extraction ore wastes
The gossan wastes and country rocks typically contain high
amounts of Pb (ca. 5,700 and 2,700 ppm, respectively) and
As (around 3,550 and 1,250, respectively), and do not
present acid potential due to the absence of pyrite or any
other sulphide phase. Hence, the potential toxicity of gos-
san wastes and country rocks is based on the dissolution of
their secondary soluble sulphates, e.g. beudantite and
jarosite (precipitated during warm seasons) and soluble
salts, which release their important amounts of heavy
metals (e.g., As and Pb) to the environment.

123
1806
Fig. 6 Selected hazardous minor and trace elements composition of the nine different residue types
Fig. 7 Values of the neutralization, acidification and net neutralizing
potentials (NP, AP, NNP) from the ABA test calculations. AP
calculated base on S content within sulphide minerals; note that a no
AP value can produce acidity on dissolving sulphates as jarosite. Note
that the absent wastes have NP and AP values equal to zero. The
Concluding remarks
The interpretation of the results presented in the previous
section lead to the following main conclusions:
123
Environ Geol (2008) 55:1797–1809
AMD generation from the sulphide-absent residues is from the
soluble salts precipitation. (I) Acidification zone, (II) Uncertainty
zone, (III) Neutralization zone. (LT: leaching tank refuses; PS: pyrite
samples; SA: smelting ashes; RS: Roman slags; MS: modern slags)
1. In São Domingos, the potential pollution and contam-
ination dynamics of the residues are continuous since
the dissolution process of the heavy-metal fraction
during the rainy period is cyclical. The presence of
Environ Geol (2008) 55:1797–1809 1807

Table 4 Amount (tons) of metals contained in the mining wastes calculated base on mass/volume ratio estimation, and total acidity in tons of
H2SO4
Mining waste Volume Mass Elements (t)
(m3) (Mt)
Acidity As Cd Cu Fe Ni Pb Sb Sn V Zn
(in H2SO4)

Modern slag 1,097,170 4.68 -795,018 999 6 15,777 1,948,813 138 14,418 166 561 181 39,696
Roman slag 84,519 0.27 -23,896 201 0.0 658 94,989 4 1,151 60 391 22 55
Smelting ashes 55,936 0.14 -4,795 115 0.2 295 10,645 1.1 804 18 66 15 129
Pyrite-rich 88,196 0.27 -68,294 463 0.4 282 29,405 3 1,277 24 67 36 195
samples
Iron oxides 7,212 0.04 – 80 0.009 15 22,528 0.5 286 11 16 0.4 2.5
Leaching tanks 1,523,060 3.56 53,349 6,218 2 6,475 717,416 48 16,693 208 1,168 276 9,756
Industrial landfills 5,012,650 11.46 – 41,944 3 3,813 1,713,750 192 95,951 1,457 4,212 699 4,389
Gossan wastes 1,783,572 4.34 – 15,344 0.7 780 672,556 44 24,579 372 3,496 489 447
Country rocks 2,840,819 6.83 – 8,574 1.5 1,564 785,286 82 18,342 125 388 895 623
Total impact 12,493,134 32 -838,654 73,938 15 29,659 5,995,387 513 173,501 2,441 10,366 2613 55,295

sulphides (mainly pyrite) within numerous waste types
(Table 2) favours AMD production during the whole
year. In warm periods, one part of the AMD-pollutants
is retained by precipitation of evaporitic salts (Fig. 6)
that is further re-dissolved in rainy periods. Hence, as
the São Domingos environment presents pyrite, this
process is repeated every year and the pollution is
assured. Although iron oxides, leaching tank refuses,
industrial landfill, gossan wastes and country rocks are
pyrite-absent residues, the circulation of AMD through
them favour the precipitation of these soluble metallic
salts, activating thus their pollution potential.
2. In order to have an idea of the polluting potential of all
residues it is important to consider: (1) the amount of
contaminants (Table 3; Fig. 6) and (2) the residue
mass/volume rate, e.g. industrial landfill is one of the
residues with the lowest total metals content but the
most volumetric one. As a result, the maximum
amount of contaminants present in each waste can be
estimated taking both factors into account (Table 4).
Thus, if the absolute quantity of metals is summed, the
hazard order of residues is: modern slag [ industrial
landfills [ country rocks [ leaching tank refuses [
gossan wastes [ Roman slag [ pyrite-rich samples [
iron oxides [ smelting ashes. The total quantity of
metals at São Domingos is under-valuated as there are
very significant residue volumes beneath the village
houses that cannot be considered.
3. The AP calculations for the São Domingos waste
dumps indicate that the main sources of AMD are
the slags, smelting ashes and pyrite-rich samples in
spite of their reduced volume which represent ca.
20% of the total volume of residues. The huge heavy
metal content and highest acid potential of these
residues (Fig. 7; Table 4) is mainly due to: (1) their
richness in sulphides (mainly pyrite) and other
secondary sulphate phases as jarosite after pyrite
oxidation; (2) the absence of neutralizing minerals as
carbonates, and (3) their wide exposed distribution
(Figs. 2, 3).
4. Despite São Domingos is considered as a relatively
medium-sized mine (approximately 32 Mt of exposed
residues), the average thick of their dumps/landfills
assure a significant waste exposition volume (around
25 Mm3, see Table 1), and the large total acidification
potential is nowadays an alert concerning the impor-
tance of pollution environmental impact.
5. The AMD process at São Domingos, as confirm the
studied textures of the pyrite oxidation and dissolution
(Figs. 4, 5), is still active.
6. The main intention and recommendation of this work
is the application of the São Domingos characteriza-
tion methodology and database for future restoration
plans on this abandoned mine and other mines of the
IPB, like Caveira, Lousal and Aljustrel in Portugal
(e.g., Oliveira 1997; Oliveira et al. 2002; Matos and
Martins 2006), and Rio Tinto, Tharsis, La Zarza, Peña
del Hierro in Spain (e.g., Braungardt et al. 2003;
Sánchez-España et al. 2005; Romero et al. 2006),
where similar mining wastes are present with large
amounts of residues and may be as São Domingos
being still active from the contamination point of view.
A next interesting study to continue the contamination
assessment at São Domingos is to know the amount of
bio-available contaminants that would be contained in
each residue.

123
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Acknowledgments This work has been financed by Spanish Min-
istry of Education and Science through project REN2003-09590–
C04-03, and by the EU through project e-EcoRisk.
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