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Mineralogical and geochemical study of element mobility at the sulfide-rich

Excelsior waste rock dump from the polymetallic Zn-Pb-(Ag-Bi-Cu) deposit,
Cerro de Pasco, Peru

Article  in  Journal of Geochemical Exploration · February 2007

DOI: 10.1016/j.gexplo.2006.08.001

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 Journal of Geochemical Exploration 92 (2007) 97 – 110
www.elsevier.com/locate/jgeoexp

Mineralogical and geochemical study of element mobility at the

sulfide-rich Excelsior waste rock dump from the polymetallic
Zn–Pb–(Ag–Bi–Cu) deposit, Cerro de Pasco, Peru
Jochen Smuda a,d,⁎, Bernhard Dold a,1 , Kurt Friese b,2 ,
Peter Morgenstern c,3 , Walter Glaesser d,4
a
Centre d'Analyse Minérale, Anthropole, University of Lausanne, 1015 Lausanne, Switzerland
b
UFZ-Umweltforschungszentrum, Department Lake Research, Brueckstr. 3a, D-39114 Magdeburg, Germany
c
UFZ-Umweltforschungszentrum, Department Chemical Analytic, Permoserstraβe 15, D-04303 Leipzig, Germany
d
University of Leipzig, Institute of Geophysics and Geology, Talstr. 35, D-04211 Leipzig, Germany
Accepted 8 August 2006
Available online 2 October 2006

Abstract

We present a mineralogical and geochemical study of the sulfide-rich waste rock dump Excelsior (size: 94 ha) originating from the
Cerro de Pasco mine (altitude: 4300 m a.s.l.), Central Andes, Peru. The aims of this study were: to characterise (1) the secondary
mineral assemblage and (2) the acid mine drainage (AMD) from this waste rock dump. (3) This information was used to create a model
of the element transport in and out of the waste rock dump under the highly variable mountain climate with high precipitation during
the wet season and high evaporation during the dry season. The main ore minerals found in the polymetallic Pb–Zn–(Ag–Bi–Cu)
deposit are pyrite, sphalerite, galena and enargite with minor finds of tennantite, covellite and cerrusite. Gangue was dominantly
quartz ± hematite ± siderite ± muscovite. The waste rocks had a high potential of acid generation with low neutralization potential
(estimated N 60 wt.% pyrite, b 5 wt.% calcite/dolomite) with an already acidic environment (average paste – pH 2.8). Gypsum,
different types of jarosite and a variety of Fe-sulfates (e.g. melanterite (Fe(SO4)·7H2O) and rozenite (Fe(SO4)·4H2O)) were the
dominant secondary minerals. Less frequent secondary minerals were: Fe(III)-hydroxides (schwertmannite (Fe16O16(OH)12(SO4)2),
fibroferrite (Fe(SO4)(OH)·5H2O)), and Mg-, Mn- and Zn-sulfates (e.g. starkeyite (Mg(SO4)·4H2O), mallardite (Mn(SO4)·7H2O),
goslarite (Zn(SO4)·7H2O), respectively).
For the primary mineral assemblage, X-ray fluorescence analyses displayed average concentrations of the heavy metals: Cu 0.1
wt.%, Zn 1.1 wt.%, Pb 1.2 wt.% and Cd 40 mg/kg and of the metalloid As 0.15 wt.%. In secondary minerals an average enrichment
of Cu: 0.8 wt.%, Zn: 2.9 wt.%, As: 0.27 wt.% and Cd: 71 mg/kg was observed. Effects of rain events on the waste rocks were simulated
by water-leach tests of (1) solid samples from the top, representing waste rocks leached by infiltrating rainwater and (2) solid samples
around the base, representing waste rocks affected by outcropping AMD generated in the waste rock dump. The leachates showed
stored acidity (pH 1.2–5.6 of the leachates) and high solubility of secondary minerals (average electrical conductivity: 9.7 mS/cm and
average concentrations for Fe: 928 mg/L, Zn: 315 mg/L, Cu: 7.5 mg/L, As: 4.1 mg/L, Cd: 1.59 mg/L, and Pb: 0.31 mg/L). The AMD

⁎ Corresponding author. Centre d'Analyse Minérale, Anthropole, University of Lausanne, 1015 Lausanne, Switzerland. Fax: +41 21 692 4315.
E-mail addresses: Jochen.Smuda@unil.ch (J. Smuda), Bernhard.Dold@unil.ch (B. Dold), Kurt.Friese@ufz.de (K. Friese),
Peter.Morgenstern@ufz.de (P. Morgenstern), Walter.Glaesser@ufz.de (W. Glaesser).
1
Tel./fax: +41 21 692 4324.
2
Tel./fax: +49 391 8109 150.
3
Tel./fax: +49 341 235 2625.
4
Tel./fax: +49 341 973 2809.

0375-6742/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.gexplo.2006.08.001
98 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110

output at springs at the base of the waste rock dump is chemically similar to the leachates (acidic pH (2.78–5.10), oxidizing Eh (319–
684 mV)), but higher charged with maximum concentrations for Fe: 5640 mg/L, Zn: 3000 mg/L, Cu: 161 mg/L, As: 8.0 mg/L, Cd:
6.6 mg/L, and with higher electrical conductivity (19–26 mS/cm).
The data suggest that AMD formation is strongly controlled by the local climate. During the dry winter season, high evaporation of
outcropping pore solutions and subsequently precipitation of efflorescent salts resulted in a heavy metal-enrichment at the base of the
Excelsior waste rock dump. During the wet summer season, rain events caused the dissolution of most efflorescent salts, removed the
enrichment at the base and resulted in a washout of acid solutions rich in Fe, Mn, Zn, Cu, Cd, As and S.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Acid mine drainage; Waste rock dump; Climate; Efflorescent salts; Heavy metal-sulfates; Leach test

1. Introduction loaded solutions. In this study, we focused on differ-

Sulfidic mine waste dumps are an important source of
metal contamination in the mining environment. While
acid mine drainage (AMD) in mine tailings has been
studied extensively (e.g. Jambor, 1994; Dold and
Fontboté, 2001), there are still few works on the subject
of AMD formation in sulphidic waste rock dumps.
Sracek et al., 2004, studied AMD and secondary min-
erals from a waste rock dump with a low pyrite content.
They pointed out that physical and geochemical pro-
cesses within a waste rock dump are interconnected and
depend strongly on climate, waste rock texture and sta-
bility. Recently, the importance of climate for the AMD
generation due to formation and dissolution of water-
soluble secondary minerals at mining sites has been
recognised. Gierè et al. (2003) studied the role of
secondary mineralogy in the control of the migration of
heavy metals and As at a relatively small sulfide-rich
waste rock dump in Russia. Beside a characterisation of
the secondary mineral assemblage of sulfidic waste
dumps, their analyses of climatic influences on the sec-
ondary minerals suggested that AMD output is strongly
controlled by rain events. Frau (2000) reported that
highly water-soluble secondary melanterite from pyrite
alteration can store acidity and heavy metals during dry
seasons which are then released due to the dissolution of
this mineral during wet seasons. We studied a sulfide-rich
waste rock dump at the elevated plain of the Central
Andes of Peru to characterise these secondary minerals,
their water-solubility and the element outflow from this
waste rock dump under the high precipitation–high evap-
oration mountain climate.
Water-leach tests are useful to simulate rain events
and evaluate the solubility of secondary minerals and
the element/acid liberation. Hammarstrom et al. (2005)
showed with this type of leach tests that efflorescent
salts from different mining waste locations in the eastern
US dissolve easily in water, producing acidic, metal-
ences between solid samples and leachates from sam-
ples from the upper terraces of the waste rock dump and
from samples from its base. The geochemical and min-
eralogical differences between these samples were used
to evaluate water pathways and effects of the climate on
element transport and fixation. Geochemical data from
the outcropping AMD displayed the subsequent transport
of elements out of the waste rock dump system.
2. Description of the studied waste rock dump
The open pit and underground mine of Cerro de
Pasco (Volcan Corporation S.A.A.) is located in the
Sierra Central of Peru at an altitude of 4300 m above sea
terrace (Fig. 1A). Since the 16th century, Cu and Ag
have been exploited from the Cerro de Pasco ore body. In
1963, the exploitation moved to Pb–Zn–Ag. The studied
Excelsior waste rock dump operated from 1943 until
2000 initially as a dump for rocks with non-economic
Cu – and later for non-economic Zn and Pb concentra-
tions. The waste rock dump is located in the SW of the
mine in the bottom of a valley and occupies an area of
94 ha, containing 26,400,000 m3 of broken rocks. It
partly overlies the downstream Quiulacocha tailings
impoundment (ca. 60 ha covered, 114 ha not covered).
The bedrock of the deposition zone consists of Devonian
phyllites and shales with low hydraulic conductivity.
2.1. Ore and regional geology
The polymetallic Zn–Pb–(Ag–Bi–Cu) Cerro de
Pasco deposit represents an economically vital poly-
metallic source with an estimated total amount of
100 Mt at about 7 wt.% Zn, 2 wt.% Pb and 3 oz/t Ag
(Baumgartner et al., 2003). Hydrothermal solutions
associated with volcanic activity formed as the first
stage of sulfide deposition an extensive replacement
body of quartz–pyrite in Triassic–Jurassic limestone/
 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110
Fig. 1. (A) Location and geological setting of the Cerro de Pasco mine area, Peru. (B) Topographical map of the Excelsior waste rock dump with the
sampling points.
dolomite which represents 90 vol.% of the entire ore
body (Einaudi, 1977). At the contact zone between the
host rock and the quartz–pyrite body, carbonates of the
host rock formation were altered to ankerite and siderite.
Tertiary volcanic rocks (quartz monzonite/tuff) which
partially overlaid the host rock formation were altered in
contact with this quartz–pyrite body to muscovite–
quartz–pyrite. The second stage of sulfide deposition
formed the main Zn–Pb ore in the form of pipes with
dominantly sphalerite–galena and minor tennantite,
marmantite and chalcopyrite. Veins rich in enargite,
luzonite, galena and minor tennantite represent a third
stage of sulfide deposition. The final hydrothermal
activity resulted in local leaching and formation of a
mineral assemblage of pyrite–hematite–realgar associ-
ated with a high Ag-mineralization. The oxidation of the
top of the sulfide body formed a gossan which contains
quartz and hematite/goetite as major phases (Petersen,
1965).
99
2.2. Mining and deposition processes
The waste rocks deposited at the Excelsior waste
rock dump had an average size of 10 cm and are up to
2.5 m in diameter; the fraction of grains smaller than
2 mm were estimated as about 10 vol.%. The waste rock
impoundment consisted of three terraces constructed by
the downpour of fractured rocks at the slopes of the
different terraces with an uncontrolled mixing of
different rock types. As result, cross-bedding of the
waste rocks and a gradation of rocks with big boulders at
the base and fine grain material at the top were observed
(Fig. 2A). The deposition commenced in the northern
part with waste rocks from the Cu-ore and advanced
with the later deposition of waste rocks from the Zn–Pb
ore successively to the south and from the 1st terrace to
the 3rd terrace, respectively. The northern part and lower
terraces were therefore exposed to alteration for a longer
period than the southern parts and the top terrace. The
100 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110

Fig. 2. Schematic cross-section of the Excelsior waste rock dump: (A) structure; (B) main water pathways.

surfaces of the terraces were mainly floored with a 10 to
30 cm thick cover of rugged pyrite-rich waste rocks to
prevent heavy mine equipment from getting stuck. The
maximum height of the dump is 55 m; the slope
inclination is mainly between 33° and 36°.
2.3. Climate and hydrology
Based on data from the local meteorological stations
(Cerro de Pasco and Upamayo), the climate at Excelsior
waste rock dump is characterised by an average precip-
itation of 1025 mm/year (mainly in the summer period),
an average evaporation of 988 mm/year and an average
annual temperature of 4.2 °C.
The hydrological system of the Excelsior waste rock
dump received water mainly from rain. Two water path-
ways were observed in the waste dump (Fig. 2B): (1)
Surface run-off at the waste dump slopes after rain
events; and (2) water infiltration into the dump. In the
waste rock dump, the main direction of water infiltration
was suggested to be vertical. At different positions of the
waste rock dump, base material was removed which
formed overhangs. It was observed that the precipitation
of efflorescent salts at these outcrops was favoured at
discrete cross-bedding layers (Fig. 3). This observation
suggested a certain influence on the water infiltration by
the cross-bedding. A broad spring zone existed at the
south-western limit of the Excelsior waste rock dump

Fig. 3. Outcrop at the south-western base of the Excelsior waste rock dump (sampling point CPE-30, Fig. 1B) with efflorescent salts (melanterite; ES
sample) and oxidizing primary rocks (pyrite, volcanic rocks; AR sample). The preferential formation of ES stalactites at grain-size boundaries
suggested the control of solution flow by the cross-bedding in the waste rock dump.
 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110
(water sampling points CPE-W1-3, Fig. 1B). These
water outcrops were explained by the difference of
hydraulic permeability between the coarse waste rock
dump material (high water permeability, not water
saturated) and the underlying sandy/silty tailings mate-
rial (low water permeability, water saturated). Similar to
an aquitard, the underlying tailings impoundment
seemed to retard infiltration through its fine material.
This led to a horizontal water transport with spring-like
outcrops at the southern base of the dump. The AMD
from the springs was channelled and conducted to a
lagoon on the southern part of the Quiulacocha tailings
impoundment.
3. Methods
3.1. Sampling and field methods
The field campaign was carried out during the dry
season 2003 (May to July). Water and solid sampling
was undertaken focussing on the element output of the
waste rock dump. A total of 68 mineral and rock
samples at 53 sampling points and 4 water samples at
4 sampling points were taken from the surface of the
Excelsior waste rock dump (Fig. 1B). The mainly ver-
tical water pathway suggested an element transport from
the top to the base. Therefore, solid samples were clas-
sified as: (1) altered rock samples from the surface of the
top terraces (altered primary minerals with a lower
amount of mainly in situ-formed secondary mineral),
termed “AR top” samples in this study; (2) altered rock
samples from the base of the Excelsior waste rock
dump, termed “AR base” samples (Fig. 3); (3) precip-
itated secondary mineral samples (efflorescent salts)
from the surface of the top terraces, termed “ES top”
samples and (4) precipitated secondary mineral samples
(efflorescent salts) from the base, termed “ES base”
samples (Fig. 3, centre).
3.1.1. Water sampling
At water sampling points, temperature, pH (WTW®
pH meter), Eh (WTW® Eh meter) and electrical conduc-
tivity were measured immediately on-site. The samples
were filtered through a 0.2 μm cellulose membrane filter
and split into two sub-samples. One was acidified to
pH b 2 with HNO3 for cation analysis. The second un-
treated sample was stored b 4 °C for anion analysis.
3.1.2. Solid sampling
Solid sampling points were described in the field by
rock type, alteration degree and, if possible, a description
and identification of mineral content. The paste pH of the
101
sample was taken according to MEND (1991) with a
WTW® pH meter. Samples were air-dried (b 35 °C) and
homogenised by crushing/grounding with an agate mill.
Humid ES samples were sealed in PET-sampling bottles
directly on-site to prevent the alteration of minerals.
3.2. Geochemical methods
3.2.1. X-ray fluorescence spectroscopy
For trace element analysis of solids, aliquots (4 g) of
78 samples were dried at 105 °C, ground with an agate
ball mill (Retsch®), mixed with Hoechst® wax, pressed
to pellets and analysed using energy-dispersive X-ray
fluorescence (EDXRF). The measurements were per-
formed with the XRF-spectrometer XLAB 2000®
(SPECTRO® Instruments) running the software pack-
age X-LAB Pro 2.2. The calibration of the spectrometer
was based on certified and measured data of about
50 reference materials including iron-rich soils, river
and lake sediments and geological materials. In cases in
which the analysed samples were strongly enriched with
heavy metals (e.g. Fe, Cu, Zn and Pb), the sample
material was diluted with SiO2 powder (Riedel-de-
Haen®) to adjust the metal concentration to within the
working ranges of the available calibration.
For major element analysis, a further part of the
sample powder was diluted with (Li2B4O7) (1 g sample +
7 g (Li2B4O7)) to prepare glass discs produced by fusion.
The measurements were performed using the wave-
length dispersive X-ray fluorescence (WDXRF) spec-
trometer S4 Pioneer® (Bruker-axs®), equipped with a
4 kW Rhodium X-ray tube. The spectrometer was
operated in vacuum conditions and the 34 mm collimator
mask was utilised in conjunction with the analysing
crystals OVO55, Ge, LIF100 and LIF110. The calibra-
tions of the WDXRF spectrometer for the major
elements were adjusted by certified reference materials,
CANMET-LKSD1-LKSD4 (lake sediments), CAN-
MET-STSD1-STSD4 and GBW07309-11 (stream sedi-
ments), NIST-SRM2689 and NIST-SRM2691 (coal fly
ashes) using the software package SPECTRAplus®.
3.2.2. Leach tests and water analysis
The German standard method DIN38414 (1984) was
used to analyse the solubility of waste rock minerals in
water. The chemical properties of the leachates and the
water-soluble fraction from solid samples from the
upper terraces and the base of the Excelsior waste rock
dump were compared to analyse enrichment and fixa-
tion of elements.
From the base of Excelsior waste rock dump, 9 AR
samples with similar distances between the sampling
102 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110

points were chosen. From the top of the Excelsior waste The milled samples were treated in the first step with
rock dump, 10 AR samples were chosen. From each distilled water for 1 h and in the second step in darkness
sample, pre-dried (b 35 °C) and milled aliquots of 10 g with 0.2 M ammonium oxalate at pH 3, for 15 min (after
were mixed with 100 ml of deionised water (pH 7, Eh of Dold, 2003). Scans were done before and after each
0.45 V, not buffered) and shaken for 24 h at 100 rpm. treatment step. Scans from the ammonium oxalate-
The leachates were filtered through 0.2 μm cellulose– treated samples were intensity-corrected and then sub-
nitrate filters. The conductivity and pH of the leachates tracted from the scans of the water-treated samples. The
were measured immediately. The leached solid samples leachates from the sequential extraction were filtered
were dried (b35 °C) and weighed to calculate the per- (0.2 μm) and analysed for element concentrations as
centage of soluble phases. described in Leach tests and water analysis (3.2.2).
Major elements of leachates and water samples from
the Excelsior waste rock dump were analysed using ion 4. Results
chromatography (Dionex® DX-120). Trace elements
were analysed using ICP–MS (Hewlett-Packard® 4500, 4.1. Mineralogy
Institute F.-A. Forel, University of Geneva, Switzerland)
and ICP–AES (Spectro® Spectroflame® P/M, UFZ At the Excelsior waste rock dump, three different
Umweltforschungszentrum, Leipzig, Germany). Leach types of waste rocks were found (Table 1): (1) sulfide-
tests for 9 ES samples (5 samples from the upper terrace, rich rocks from the quartz–pyrite ore body and its Fe
4 samples from the base of the Excelsior waste rock (III)-oxide-rich oxidation products near the surface, (2)
dump) were performed to confirm the high water-solu- sericitised monzonites/tuff and (3) dolomitic rocks from
bility of pure efflorescent salt samples (water soluble the host rock formation. These rocks were characterised
fraction between 89.2 and 94.4 wt.%). Due to their high by their different contents of acid-producing/acid-con-
water-solubility, XRF data of ES samples were used suming minerals and their different degree of alteration.
instead of leach test data for the above mentioned anal-
ysis of element enrichment and fixation. 4.1.1. Quartz–pyrite rocks
The main waste rock at the Excelsior waste rock
3.3. Mineralogical methods dump belonged to the quartz–pyrite body. Quartz and
pyrite as major phases dominated the mineral
3.3.1. Optical microscopy
Polished sections and polished thin sections of selec-
ted bulk samples were prepared using epoxy resin to Table 1
embed the loose-packed samples and analysed using AMD-relevant characteristics of rock types at the Excelsior waste rock
dump
transmitted light and reflected light microscopy.
Rock type Quartz–pyrite Volcanic Carbonatic
rocks rocks rocks
3.3.2. X-ray diffraction analysis
All samples were analysed as bulk samples with the Volume share 70–80% 15–20% ca. 5%
AMD-neutral Quartz, Quartz, Quartz
aid of X-ray diffraction (XRD), using a Siemens
primary minerals hematite muscovite
D5000® diffractometer equipped with monochromated Acid-producing Pyrite Pyrite Not present
CuKα (λ = 1.54056 Å) X-radiation. Conserved humid primary minerals
ES samples were grounded with an agate mortar and Alteration degree Low (b10%) Very high High
analysed immediately to prevent the alteration of min- (estimated in field) (N90%) (N50%)
Acid-consuming Not present Albite Dolomite
erals, e.g. by the loss of crystal water. Scan settings were
primary minerals
0.05° 2θ step size and 2 s counting time per step. Peak Liberated elements Fe, Zn, Cu, Mn, S Fe, S Ca, Mg
interpretation was performed using the program suite (major fraction)
DIFFRAC AT®. Liberated elements Pb, As, Cd K, Ca
(minor fraction)
Secondary minerals Gypsum, Hydronium Gypsum, Mg
3.3.3. Differential X-ray diffraction analyses
jarosite, jarosite, sulfates
The poorly crystalline Fe(III) hydroxide schwertman- plumbojarosite, jarosite,
nite was detected in a two-step sequential extraction hydronium kaolinite,
procedure and differential X-ray diffraction (DXRD) as jarosite, metal Fe sulfates,
described by Dold (2003). The diffractometer settings sulfates, Fe(III) Fe(III)
hydroxides hydroxides
were 0.05° 2θ step size and 20 s counting time per step.
 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110
assemblage in AR samples. The ore minerals sphalerite,
tennantite, cerussite, galena and coronadite were iden-
tified as minor and trace phases and anglesite as a
primary and possibly secondary trace mineral in the
Excelsior waste rock dump. A different alteration
intensity of small pyrite grains (up to 2 mm) was
observed in thin sections. Intact, idiomorphic pyrite
crystals were found in close proximity to strongly altered
pyrite. Pyrite grains greater than 2 mm showed alteration
rims of varying thickness (up to 1.5 mm) consisting of
microcrystalline Fe(III) hydroxides. Massive pyrite
rocks in the field showed superficial alteration with
alteration rims of less than 1 mm. Due to the observed
oxidation grades, a long-term AMD potential by the
pyrite content must be assumed. A minor fraction of
waste rocks from the quartz–pyrite body belonged to
the oxidized top of the quartz–pyrite body in situ at
the deposit. Rocks from this gossan contain quartz and
hematite/goetite as major phases.
4.1.2. Volcanic rocks
Volcanic rocks (quartz monzonite/tuff) in contact
with the ore body could originally contain up to 15 vol.%
pyrite in disseminated distribution due to the sericitic
alteration during the sulfide deposition (personal com-
munication, Volcan geologists). This contributed a fur-
ther important quantity of pyrite to the system in
addition to the pyrite from the ore body. Pyrite crystals
in volcanic rocks are small in size (b 1 mm), the rock
matrix has a high porosity. At the Excelsior waste
rock dump volcanic rocks were observed to be already
strongly altered. Boulders of volcanic rocks of up to
1 m in diameter had already completely decomposed
into white, loose material with grain sizes of several
mm and a strongly acidic paste pH (1.31–2.58, n = 6).
Microscopic and XRD studies showed that the main
primary mineral fractions of these rocks were quartz
(∼20 vol.%) and altered relicts of albite (NaAlSi3O8)
(∼ 5 vol.%). Agglomerates of secondary minerals (mi-
crocrystalline Fe(III) hydroxides, muscovite, kaolinite
and gypsum) made up the major fraction (N 70 vol.%).
From the original pyrite content, only relicts remained,
contributing less than 1 vol.% of the total volcanic
rock mineral assemblage. These observations pointed to
the interpretation that due to the small crystal size and
the high rock porosity, pyrite in the volcanic rocks
oxidized much faster than massive pyrite from the
quartz–pyrite body. This resulted locally in strongly
acidic environment where volcanic rocks were depos-
ited. AMD from these areas was suggested to accelerate
the further alteration of other waste rocks in the waste
rock dump.
103
4.1.3. Carbonatic host rocks
Less than 5 wt.% of the waste rocks belonged to the
host rock formation and contained quartz, dolomite and
siderite as major mineral phases. While dolomite can
neutralize protons, siderite may additionally produce
protons through the hydrolysis of liberated Fe(III),
which can oxidize pyrite. This fact reduces the neutral-
ization capacity of this type of carbonatic waste rocks.
At the surface of the Excelsior waste rock dump,
dolomite was still present at some sites. This suggested
that rain infiltrated rapidly into the Excelsior waste rock
dump and that acid solution could not migrate
horizontally on the surface. Inside the Excelsior waste
rock dump, carbonates were assumed to be mostly
dissolved due to acid pore water. The generally low
proportion of carbonatic rocks on the waste rock as-
semblage and the mix of acid-consuming and acid-
producing carbonates in this rock type indicated that the
Excelsior waste rock dump has an extremely low acid
neutralization capacity. This led to an acidic environ-
ment with an average paste pH of 2.8. The pH depended
strongly on the presence of dolomite; values varied
between pH 0.8 and 4.7 for waste rock areas without
dolomite (48 sampling points) and between pH 5.1 and
7.3 for areas with dolomite (6 sampling points).
4.1.4. Low soluble secondary minerals
Solid solutions of secondary hydronium jarosite
((H3O)Fe3(SO4)2(OH)6) and K-jarosite (KFe3(SO4)2
(OH)6) were observed in most AR samples. The X-ray
patterns of solid solutions of alkali jarosites as pointed
out by Dutrizac and Jambor (2000) are very similar to
the X-ray pattern of hydronium jarosite ((H3O)Fe(SO4)2
(OH)6). However, the small amounts of feldspars and
other alkali-bearing minerals in the Excelsior waste rock
dump resulted in a low availability, especially of Na, and
were likely to favour the formation of hydronium
jarosite instead of the thermodynamically more
favoured solid solution of alkali jarosites. The XRD
identification of hydronium jarosite also in samples with
Na concentrations below detection limit supported this
interpretation. In samples rich in Pb, the XRD inter-
pretations suggested the presence of solid solutions
between jarosite, hydronium jarosite and plumbojarosite
(PbFe6(SO4)4(OH)12), possibly associated with beudan-
tite (PbFe3(AsO4)(SO4)(OH)6).
Goethite as a minor phase was found in samples with
the typical altered rock–mineral association pyrite–
(hydronium/plumbo–) jarosite–gypsum.
Some AR samples were collected at superficial water
pathways. These samples were characterised by small
grain sizes (b 1 mm), quartz as the major primary
104 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110

Table 2 marginal intergrowth with microcrystalline Fe(III)

Major secondary Fe-, Mg-, Zn- and Pb-sulfates of the Excelsior waste hydroxides, and (2) very small idiomorphic crystals at
rock dump
the boundary to submicroscopical size, possibly result-
Fe-sulfates Mg-sulfates Zn-sulfates Pb- ing from fresh precipitation from pore water and/or as
sulfates
result of precipitation during the drying process after
Melanterite Epsomite Goslarite Anglesite sampling.
(FeSO4·7H2O) (MgSO4·7H2O) (ZnSO4·7H2O) (PbSO4)
Siderolite Starkeyite Gunningite
(FeSO4·5H2O) (MgSO4·4H2O) (ZnSO4·2H2O) 4.2. Geochemical results
Fibroferrit (Fe(SO4) Kieserite Changoite
(OH)·5H2O) (MgSO4·H2O) (Na2Zn 4.2.1. Solid sample analyses
(SO4)2·4H2O)
Rozenite
4.2.1.1. Major elements. Si, Fe and S from the quartz–
(FeSO4·4H2O)
Szomolnokite pyrite body dominated the element composition of
(FeSO4·H2O) the AR samples average concentrations (Table 3) with
Romerite (Fe3 average concentrations of 28.2 ± 10.5 wt.% SiO2 in AR
(SO4)4·14H2O) top samples/32.5 ± 15.0 wt.% SiO2 in AR base sam-
Copiapite (FeFe4
ples, 27.0 ± 9.5 wt.% Fe2O3 in AR top samples/22.4 ±
(SO4)6(OH)2·20H2O)
12.1 wt.% Fe2O3 in AR base samples, 7.44 ± 2.81 wt.% S
in AR top samples/6.83 ± 4.48 wt.% S in AR base sam-
mineral fraction and a high content of secondary Fe(III) ples. The volcanic rocks also contribute to these elements.
hydroxides (up to 60 vol.%). Fe(III) hydroxides Fe and S are the major elements in the ES samples
appeared as light yellow to dark brownish agglomerates. (average concentrations: 21.5 ± 5.9 wt.% Fe2O3 in top
A clear identification for these samples by XRD was not samples/18.8 ± 12.4 wt.% Fe2O3 in base samples, 12.0 ±
possible. One sample from the top of the waste rock 1.3 wt.% S in top samples/11.4 ± 2.6 wt.% S in base
dump (CPE-61(AR), Fig. 1B) and one from the base of samples). Fe and S concentrations were slightly higher
the waste rock dump (CPE-32(AR)), both with a high in top samples than in base samples, while Si concentra-
content of ‘poorly crystalline Fe(III) hydroxides’, were tions showed an opposite trend. These trends resulted
selected for DXRD analyses. In both samples, schwert- probably from the flooring of the top terraces with pyrite-
mannite (Fe16O16(OH)12(SO4)2) was identified as main rich rocks. Aluminium in AR samples had its origin
secondary Fe-mineral. mainly in muscovite from altered volcanic rocks. A sig-
nificant Al concentration in ES samples is only found in
4.1.5. Water-soluble secondary minerals impure samples with high primary mineral content. This
Gypsum, Mg-sulfates and heavy metal sulfates were
the major phases in ES samples. This mineral group Table 3
represented the water-soluble efflorescent salts precipi- XRF data from AR and ES samples from the upper terraces (top) and
tated from oversaturated pore solutions. The most from the base (base) of the Excelsior waste rock dump: average
frequent metal sulfates (Table 2) were Fe-sulfates concentrations ± standard deviation of selected major and trace
elements
(melanterite, rozenite, less frequently romerite, sidero-
lite, copiapite, szomolnokite and fibroferrite) followed Element AR (top) AR (base) ES (top) ES (base)
(n = 17) (n = 32) (n = 5) (n = 12)
by Mg-sulfates (epsomite, starkeyite and kieserite). In
addition to these minerals, Zn-sulfates (goslarite, Na2O (wt.%) 0.15 ± 0.15 0.30 ± 0.32 0.49 ± 0.28 0.62 ± 0.46
K2O (wt.%) 1.41 ± 0.78 1.40 ± 1.92 0.18 ± 0.40 0.27 ± 0.38
gunningite, changoite) and Mn-sulfates (mallardite,
CaO (wt.%) 1.94 ± 4.23 4.86 ± 4.62 0.35 ± 0.41 3.69 ± 5.98
MnSO4·7H2O) could be found at some sites. Al2O3 (wt.%) 6.23 ± 2.60 5.93 ± 4.44 1.09 ± 1.53 0.92 ± 0.84
Cu concentrations reached up to 10 wt.% in ES SiO2 (wt.%) 28.16 ± 10.45 32.51 ± 15.00 2.81 ± 4.53 3.77 ± 4.23
samples. An identification of Cu-minerals by means of MgO (wt.%) 0.67 ± 0.34 1.53 ± 1.96 2.02 ± 1.33 2.57 ± 1.98
XRD or optical microscopy was not possible. This Mn (wt.%) 0.23 ± 0.23 0.65 ± 0.74 1.14 ± 0.59 2.73 ± 3.05
Fe2O3 (wt.%) 26.95 ± 9.47 22.38 ± 12.09 21.48 ± 5.92 18.79 ± 12.44
suggested that Cu was not precipitated as a Cu-mineral
S (wt.%) 7.44 ± 2.81 6.83 ± 4.48 11.99 ± 1.25 11.38 ± 2.45
but substituted metals in other sulfates (mainly melan- Cu (wt.%) 0.11 ± 0.21 0.08 ± 0.20 1.27 ± 2.36 0.81 ± 2.79
terite) as also described from other sites (Jambor et al., Zn (wt.%) 0.87 ± 0.57 1.19 ± 1.13 2.94 ± 1.31 3.40 ± 2.90
2000). Pb (wt.%) 1.10 ± 0.82 1.14 ± 2.28 0.10 ± 0.22 0.13 ± 0.18
Two different types of gypsum appeared: (1) crystals Cd (mg/kg) 23 ± 15 48 ± 83 77 ± 62 80 ± 88
As (mg/kg) 2030 ± 1433 1205 ± 1052 896 ± 561 2043 ± 3694
of between 0.05 and 0.4 mm with irregular shapes and
 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110 105

suggested that high Al contents were mainly related to
primary silicates. The concentrations for Na and K in
AR samples were low due to the low content of primary
Na and K-minerals in the primary mineral assemblage
(average concentrations: 0.15 ± 0.15 wt.% Na2O for AR
top samples/0.30 ± 0.32 wt.% Na2O for AR base
samples; 1.41 ± 0.78 wt.% K2O for AR top samples/
1.40 ± 1.42 wt.% K2O for AR base samples). While Na
was enriched in ES samples (0.49 ± 0.28 wt.% Na2O for
ES top samples/0.62 ± 0.46 wt.% Na2O for ES base
samples), K showed a contrary trend (0.18 ± 0.40 wt.%
K2O for ES top samples/0.27 ± 0.38 wt.% K2O for
ES base samples). This suggested that K was stronger
fixed in the system, probably due to the formation of
K-jarosite.
Ca and Mg from the dolomitic ore host rock had
lower average concentrations in AR samples from the
upper terraces (1.94 ± 4.23 wt.% CaO in top samples/
4.86 ± 4.62 wt.% CaO in base samples, 0.67 ± 0.34 wt.%
MgO in top samples/1.53 ± 1.96 wt.% in base samples).
The reason for this observation was also the flooring of
the top terraces with pyrite-rich, Ca-/Mg-mineral-poor
rocks. Ca is not enriched in ES samples while Mg
showed enrichment (average concentrations: 0.35 ±
0.41 wt.% CaO in top samples/3.69 ± 5.98 wt.% CaO
in base samples, 2.02 ± 1.33 wt.% MgO in top samples/
2.57 ± 1.98 wt.% MgO in base samples).
with ∼10 wt.% tennantite ((Cu,Fe)12As4S13), 381 mg/kg
Cd). The average Cd concentrations in the ES samples
showed enrichment (77 ± 62 mg/kg Cd for top samples/
80 ± 88 mg/kg Cd for base samples) in comparison to
the AR samples (averages: 48 ± 83 mg/kg Cd in top
samples/23 ± 15 mg/kg Cd in base samples). Cadmium
was suggested to be incorporated into or coprecipitated
with metal sulfates (e.g. in the sample CPE-30b(ES)
with rozenite, starkeyite and 300 mg/kg Cd; sample
CPE-52(ES) with szomolnokite and 192 mg/kg Cd), as
described from other sites (Alpers et al., 1994).
4.2.2.2. Lead. The sulfide ore mineral galena PbS and
its alteration product anglesite (PbSO4) (as primary
mineral and also as freshly formed secondary mineral)
represented the lead content in the Excelsior waste rock
dump (average of 1.10 ± 0.82 wt.% Pb for AR top
samples/1.14 ± 2.28 wt.% Pb for AR base samples). In
the zones where secondary efflorescent salts particularly
precipitated (mainly at the base of the waste rock dump),
the average Pb concentration was nearly one tenth of
that in the AR samples (average of 0.10 ± 0.22 wt.% Pb
for ES top samples/0.13 ± 0.18 wt.% Pb for ES base
samples). The low concentration of Pb in the ES
samples pointed to the low solubility of the mineral
anglesite and the low mobility of Pb in the sulfate-rich
Excelsior waste rock dump environment.

4.2.2. Heavy metals and arsenic 4.2.3. Arsenic

Sources for arsenic at the Excelsior waste rock dump
4.2.2.1. Copper, zinc and cadmium. AR samples were mainly the arsenic-rich pyrite, arsenopyrite
contained a higher average Cu concentration in top sam- (FeAsS) and enargite (Cu3AsS4)/luzonite (Cu3AsS4)
ples (0.11 ± 0.21 wt.% Cu) than in base samples (0.08 ± from the ore body, but also realgar (As4S4) and orpiment
0.20 wt.% Cu) due to enargite–tennantite veins in the (As2S3), which were part of the supergene mineral
quartz–pyrite body (Einaudi, 1977) and the flooring of the assemblage of the Cerro de Pasco mine (Einaudi, 1977).
terraces with pyrite-rich rocks. Cu is enriched in ES
samples (average concentrations of 1.27 ± 2.36 wt.% in
Table 4
top samples/0.81 ± 2.79 wt.% in base samples). Heavy metal and arsenic concentrations (ICP–MS) of sequential
The primary mineral assemblage of the waste dump extractions for the Fe(III) hydroxides
displayed a high average concentration of Zn (0.87 ±
Type As Cd Cu Fe Mn Pb Zn
0.57 wt.% for AR top samples/1.19 ± 1.13 wt.% for AR sample (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
base samples), due to the main Zn minerals sphalerite
Water leach
(ZnS) and marmatite ((Zn,Fe)S) from the ore body. In ES CPE-32 0.26 0.02 0.31 84.5 45.72 0.003 32.52
samples, Zn was enriched in the form of efflorescent salts (AR)
(averages: 2.94 ± 1.31 wt.% Zn in top samples/3.40 ± CPE-61 b0.06 0.02 0.02 2.6 11.21 0.009 8.20
2.90 wt.% Zn in base samples). Especially at overhangs (AR)
which formed a protection against rain at the base of
NH4-ox. AC leach
Excelsior waste rock dump, maximum Zn concentrations CPE-32 73.74 b0.01 0.12 803 0.26 0.044 0.73
(up to 8.5 wt.% Zn, sample CPE-31(ES)) were found. (AR)
Cadmium occurred as a substitute in sulfide miner- CPE-61 b0.06 b0.01 0.02 922 0.22 0.005 0.45
als of the ore body (e.g. in sample CPE-2(AR) with (AR)
∼ 15 wt.% sphalerite, 295 mg/kg Cd; and CPE-12(AR) Sampling locations: see in Fig. 1B.
106 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110

AR samples displayed higher average concentrations in
top samples (2030 ± 1433 mg/kg As) than in base sam-
ples (1205 ± 1052 mg/kg As) due to the flooring of top
terraces with pyrite-rich rocks. Sequential extraction of
an Fe(III) hydroxide-rich AR sample from the base of the
Excelsior waste rock dump (CPE-32(AR)) showed a
high concentration for As (up to 73.7 mg/L) in the Fe(III)
hydroxide leach step (Table 4). This confirmed the
known sorption capacity of Fe(III) hydroxides for As
(Dold and Fontboté, 2001; Fukushi et al., 2003; Lebrun
et al., 2004). In a second AR sample (CPE-61(AR)) from
the top terrace of the Excelsior waste rock dump,
schwertmannite was also identified. In contrast to the
first mentioned sample, this sample contained a low
concentration of As in the Fe(III) hydroxide leach step
(b0.06 mg/L). The low As concentration most probably
resulted from As-poor sulfides in this sampled area.
ES samples displayed a high average concentration of
arsenic and enrichment at the base of the Excelsior waste
rock dump (averages: 896 ± 561 mg/kg As for ES top
samples/2043 ± 3694 mg/kg As for ES base samples),
suggesting that mobile arsenic can be fixed when metal
sulfates precipitate, as observed at other waste rock dumps
(Gierè et al., 2003).
4.2.4. Water leach tests
After 24 h of stirring, all leachates possessed acidic pH
values varying between 1.2 and 5.6 for the AR samples
(Table 5). The water-soluble fraction of the leached AR
samples represented between 2.6 and 39.6 wt.% and led in

Table 5
Water analyses of leachates from AR sample and AMD water samples: pH, Eh, electrical conductivity (EC), pH, ICP–MS data and soluble fraction
(SF)/total dissolved solids (TDS) of selected elements; average and standard deviation of the different sample categories
Type/ pH Eh EC As Ca Cd Cu Fe K Mg Mn Na Pb S Zn SF
Sample (mV) (mS/cm) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (wt.%)
Leachates
AR (top)
CPE-44 2.43 n.m. 4.0 0.92 105 0.47 0.50 452 2.64 70 75.6 7.24 0.06 917 167 6.3
CPE-48 1.20 n.m. 5.4 3.30 60 0.26 0.00 677 4.86 69 91.1 6.90 1.85 1110 103 9.8
CPE-49 2.56 n.m. 4.6 0.74 539 0.57 4.80 541 4.49 91 90.4 8.15 0.03 1620 152 5.9
CPE-50 2.32 n.m. 5.2 14.81 66 0.38 10.92 1225 4.14 88 145.2 6.98 0.02 1650 127 21.3
CPE-54 2.33 n.m. 3.5 0.02 83 0.25 0.00 157 6.60 74 71.8 8.61 0.05 540 86 5.9
CPE-55 2.17 n.m. 5.0 4.63 259 0.47 22.45 872 7.57 6 69.1 6.28 0.16 1250 130 8.4
CPE-56 2.74 n.m. 4.0 0.08 501 0.50 0.00 49 7.64 104 186.9 7.80 0.11 720 146 7.4
CPE-57 2.32 n.m. 6.3 11.99 219 0.31 0.00 1968 7.32 7 29.3 11.58 0.28 1890 116 14.1
CPE-59 2.33 n.m. 14.5 33.27 360 4.49 35.76 7400 7.38 145 85.3 5.43 0.08 10660 1389 39.6
CPE-62 2.32 n.m. 7.0 7.07 164 0.89 13.86 1720 6.76 116 226.1 8.36 0.03 2468 290 13.2
Average 2.27 6.0 7.68 236 0.86 8.83 1506 5.94 77 107.1 7.73 0.27 2283 271 13.2
S.D. 0.41 3.2 10.35 178 1.29 12.19 2164 1.76 44 60.3 1.67 0.56 3000 397 10.5
AR (base)
CPE-2 4.02 n.m. 3.6 0.08 567 14.81 15.55 76 0.4 95 n.m. 1.2 2.27 1024 447 27.4
CPE-7 5.60 n.m. 2.4 bdl 635 0.46 bdl 0.8 2.1 29 n.m. 0.8 0.35 535 107 2.6
CPE-11 3.79 n.m. 8.7 bdl 517 1.76 1.51 251 bdl 657 n.m. 0.9 0.07 2110 708 12.7
CPE-15 2.82 n.m. 5.2 0.10 566 0.92 4.67 263 bdl 52 n.m. bdl 0.14 1085 322 5.4
CPE-18 5.47 n.m. 3.2 bdl 564 0.34 bdl 0.1 3.6 263 n.m. 3.1 bdl 820 68 4.6
CPE-24 2.88 n.m. 9.7 bdl 504 0.58 3.53 141 bdl 987 n.m. 0.5 0.06 2074 491 13
CPE-28 2.91 n.m. 3.0 0.14 523 1.26 16.67 1452 bdl 178 n.m. bdl 0.22 1928 611 3.3
CPE-30 2.77 n.m. 8.3 0.12 608 0.04 0.71 44.9 13.0 31 n.m. 0.8 0.06 634 18 11.8
CPE-35 3.20 n.m. 5.1 0.26 382 1.40 11.78 350 bdl 194 n.m. bdl bdl 1139 521 6.4
Average 3.72 5.5 0.08 541 2.40 6.05 286 2.1 276 0.8 0.35 1261 366 9.7
S.D. 1.12 2.8 0.09 73 4.69 6.77 454 4.3 330 1.0 0.73 616 250 7.8
All leachates
Average 2.96 5.7 4.08 541 1.59 7.51 928 2.1 276 107 0.8 0.31 1261 315 11.5
S.D. 1.09 8.3 8.29 73 3.35 9.84 1681 4.3 330 70 1.0 0.63 617 330 9.2
AMD water TDS
CPE-W1 4.86 359 21.2 2.81 411 0.92 1.08 3685 19.2 3158 2258 73.8 1.17 8100 1845 4.7
CPE-W2 4.94 336 19.0 2.09 559 0.57 1.13 3152 25.0 3549 1752 121 0.55 6820 1218 5.6
CPE-W3 5.10 319 23.3 1.98 694 3.58 1.28 5640 27.7 4716 2467 8.2 1.28 9730 2302 5.2
CPE-W4 2.78 684 26.0 7.99 614 6.60 161.1 1632 3.1 7792 2625 bdl 0.14 9800 3000 7.5
Abbreviations: top: samples from the surface of the upper terraces of the Excelsior waste rock dump; base: samples from the base of the Excelsior
waste rock dump; S.D.: standard deviation; n.m.: not measured; bdl: below detection limit. Sampling locations: see Fig. 1B.
 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110
high electrical conductivity in the leachates (between 2.4
and 14.5 mS/cm). All leachates showed high concentra-
tions of heavy metals and also of Ca (average: 236 ±
178 mg/L for AR top samples/541 ± 73 mg/L for AR base
samples), Mg (average: 77 ± 44 mg/L for AR top samples/
276 ± 330 mg/L for AR base samples), As (average: 7.7±
10.4 mg/L for AR top samples/0.08 ± 0.09 mg/L for AR
base samples) and S (average: 2283 ± 3000 mg/L for AR
top samples/1261 ± 616 mg/L for AR base samples). The
high concentrations of Ca and Mg represented the content
of water-soluble secondary gypsum and Mg-sulfates (e.g.
starkeyite, MgSO4·4H2O).
The dissolution of Fe sulfates generated high Fe
concentrations (average: 1506 ± 2164 mg/L for AR top
samples/286 ± 454 mg/L for AR base samples) in the
leachates. The liberated Fe(II) can be oxidized to form
Fe(III) which is an effective sulfide oxidizer (Singer and
Stumm, 1970). This process is supposed to enhance the
sulfide oxidation at the Excelsior waste rock dump.
The average concentrations of Cu and Zn in leachates
were 8.8 ± 12.2 mg/L for AR top samples/6.1 ± 6.8 mg/L
for AR base samples and 271 ± 397 mg/L for AR top
samples/366 ± 250 mg/L for AR base samples, respec-
tively. The high concentrations displayed clearly that
Zn- and Cu-containing secondary sulfates dissolve
rapidly in contact with water and liberate these metals.
Pb showed low concentrations in the leachates
(average 0.27 ± 0.56 mg/L for AR top samples/0.35 ±
0.73 mg/L for AR base samples) due to the already
discussed low solubility of anglesite.
The concentrations of arsenic in the leachates varied
greatly between samples from different locations and
showed lower concentration in base sample leachates
(average: 7.7 ± 10.4 mg/L for AR top samples/0.08 ±
0.09 mg/L for AR base samples). Fixation of As on Fe(III)
hydroxides lowered possibly the concentration of As in
pore solutions at the base of the waste dump. At the top
local low As concentrations seemed to result from low
concentrations of As in the surrounding primary minerals,
as shown by the Fe(III) hydroxide leach test. Samples with
high arsenic concentrations in the leachates (up to 33.3 mg/
L, sample CPE-59(AR)) had a very low paste pH (1.1–1.7)
in the field, suggesting a high pyrite oxidation in these
zones. This oxidation process liberated As which was fixed
in the sulfides and resulted in the observed high
concentration of As in the leachates.
The leachates had an average Cd concentration of 0.9 ±
1.3 mg/L for AR top samples/2.4 ± 4.7 mg/L for AR base
samples. This observation confirmed the suggestion that
Cd was enriched at the base of the Excelsior waste rock
dump in water-soluble secondary minerals, as discussed
with the XRF data from solid samples.
107
Element concentrations varied widely, demonstrating
the different content and composition of water-soluble
secondary minerals in the samples.
4.2.4.1. AMD from the Excelsior waste rock dump.
AMD samples originated from the broad spring zone at the
south-western base of the Excelsior waste rock dump
(CPE-W1 to 3, Fig. 1B) and from a small water outcrop at
the north-western base (CPE-W4). CPE-W1 to 3 were
linked together as a broad spring zone at the most recent,
southern part of the Excelsior waste rock dump base. AMD
from this zone was characterized by an acid pH (range:
4.86–5.10), high electrical conductivity (range: 19.0–
23.3 mS/cm), a slightly oxidizing environment (range Eh:
319–359 mV) and a high charge of metals (Table 5). The
total flow rate of this spring zone is estimated to be around
10 L/s.
CPE-W4 is an isolated, small water outcrop at the
north-western, oldest area of the Excelsior waste rock
dump. The more acid pH (2.78), higher Eh (684 mV)
and higher electrical conductivity (26.0 mS/cm) in
comparison with the broad spring zone in the SW
seemed to result from the longer exposition of the waste
rocks in this area and the therefore more advanced
oxidation of sulfides. The high concentration of Cu in
the water sample CPE-W4 (161.1 mg/L) possibly
resulted from the source rocks in this area: the oldest
waste rocks from the historically first mined Cu-rich and
surface-near ore of the Cerro de Pasco deposit.
The trends of mineral solubility and element mobility
from the leach tests were confirmed by the heavy metal
concentrations in the AMD waters: Cu 1.1–1.3 mg/L at
CPE-W1 to 3, 161.1 mg/L at W4, Zn 1218–2302 mg/L
at W1 to 3, 3000 mg/L at W4, Fe 3685–5640 mg/L at
W1 to 3, 1623 mg/L at W4, Cd 0.9–3.6 mg/L at W1 to
3, 6.6 mg/L at W4. The metal concentrations were
higher in comparison with the average concentration of
the AR leaching tests. This observation was explained
by the high interaction of pore water with altered waste
rocks during the slow infiltration.
The AMD effluents also contained high concentra-
tions of As (CPE-W1 to 3: 2.0–2.1 mg/L As, CPE-W4:
8.0 mg/L As). Arsenic appeared to be not completely
retained by Fe(III) hydroxides during the flow path in
the Excelsior waste rock dump, probably due to its high
concentration.
Manganese showed high concentrations in leachates
(data only available for AR top sample leachates: aver-
age 107 ± 60 mg/L Mn). The sequential extraction data
of the water extraction step (Table 4, 11.2–45.7 mg/L
Mn) and the water data (Table 5, 1752–2625 mg/L Mn)
also displayed high concentrations of Mn. Source of
108 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110
Mn seemed to be the dissolution of Mn-sulfates (e.g.
mallardite, Mn(SO4)·7H2O).
5. Discussion
The comparison of the XRF, XRD, leach test and
AMD data was used to identify source rocks of AMD
and trace back the transport of acids and heavy metals
and their retention at the Excelsior waste rock dump in
form of freshly precipitated secondary minerals at the
Excelsior waste rock dump.
The heavy metals Zn, Cd, Mn as well as the alkaline
earth metals Ca and Mg showed higher concentrations
in AR samples from the base of the Excelsior waste
rock dump than from its top terraces. The leach tests
and XRF data from ES samples confirmed that these
metals were enriched in ES samples, especially at the
base of the waste rock dump. This enrichment was
explained by the transport of AMD from the top to the
base of the waste rock dump, leaching of heavy metals
inside of the waste rock dump by the acidic solutions
and the subsequent precipitation of metal sulfides due
to evaporation of outcropping AMD during the dry
season.
Cu concentrations were lower in AR samples and
their leachates from the base of the Excelsior waste rock
dump than from the top. In ES samples, Cu is enriched
in comparison to AR samples. This suggested that in the
dry season, secondary Cu-bearing sulfates precipitated
close to sites with high Cu concentration in altering
pyrite-rich primary rocks.
Water-soluble Fe-sulfates were the most abundant
heavy metal sulfates at the waste rock dump. AMD and
all leachates had high Fe and S concentrations indicating
high water-solubility of Fe-sulfates and mobility for iron
and sulfate, when water as solvent and transport medium
was available, e.g. during the rainy season. AR samples
from the top had higher concentrations of Fe and S due
to flooring with pyrite-rich waste rocks. Leachates from
AR samples and ES samples from the top terraces also
had higher concentrations of leachable Fe and S in
comparison with base samples and their leachates. This
suggested that water-soluble Fe-sulfates precipitated in
the dry season near to the oxidizing Fe-sulfides and
depended in their concentration on the local concentra-
tion of Fe-sulfides. A possible explication for the lower
Fe concentrations in leachates from samples from the
base of the waste rock dump was the precipitation of not
water-soluble secondary minerals like schwertmannite
and jarosite in this zone.
The heavy metal Pb showed no trends of enrichment.
Pb had in samples from the top and from the base similar
concentrations, most probably due to the low solubility
of primary and secondary anglesite.
Potassium concentrations in AR samples from top and
base samples were nearly the same, while AR samples
from the base had higher sodium concentrations than AR
samples from the top. The higher content of albite-rich
volcanic rocks at the base was suggested to be the source
of the higher concentrations of Na. Altering volcanic
rocks were most probably also the reason of Na
enrichment in ES samples at the base of the Excelsior
waste rock dump. High concentrations in AMD samples
displayed that both alkali metals were mobile after the
alteration of its source rocks. Na and K concentrations in
leachates from AR base samples were much lower than in
leachates from AR top samples. This observation
suggested that at the base of the waste rock dump K and
Na were at least partially fixed in freshly precipitated,
water-insoluble secondary minerals, e.g. jarosites.
The high arsenic concentration in AR samples from
the top resulted from the flooring of top terraces with
pyrite-rich, arsenic-containing waste rocks. The arsenic
enrichment in ES samples from the base suggested
transport of dissolved arsenic, while the lower concen-
trations in leachates from base samples contradicted the
mobility of As. These observations and the high As
concentrations in AMD waters at the base suggested that
As was mobile and transported to the base after
liberation by the oxidation of As-containing sulfides.
During the evaporation of pore water at the base of the
waste rock dump arsenic appeared to be fixed in
minerals with low water-solubility, e.g. due to adsorp-
tion on freshly precipitated Fe(III) hydroxides.
6. Conclusion
At the Excelsior waste rock dump, pyrite from two
different sources (ore body/volcanic rocks) was present
as an acid producer in a high concentration (estimated
N60 wt.% of the total mineral assemblage). Ore sulfides
(Zn, Pb) were found in local concentrations up to 10 wt.%.
Minerals with a capacity of neutralising AMD were
only minor or trace fractions (b5 wt.% carbonates).
Sulfide oxidation took place producing a strongly acidic
environment (average paste pH 2.8). Pyrite from the
Cerro de Pasco quartz–pyrite body (N 60 wt.% of the
total mineral assemblage) oxidized slowly, producing a
long-term risk of AMD. Pyrite from volcanic waste
rocks represented ca. 1 wt.% of the total mineral as-
semblage of the Excelsior waste rock dump. This pyrite
has due to small crystal size and high rock porosity a
high oxidation rate and liberated acids and Fe(III)
which could accelerate further pyrite oxidation. The
 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110
Fig. 4. Model of climatic effects on the formation and dissolution of efflorescent salts and the transport and mobility of acid, metal-rich solutions at the
Excelsior waste rock dump: (A) dry season; (B) rainy season.
current study allowed the development of a schematic
model of the seasonal variation in secondary mineral
formation and dissolution and subsequent element
outflow from the Excelsior waste rock dump (Fig. 4).
(A) High evaporation during dry seasons concentrated
the acidic, metal-rich pore solutions near to the surface
of the Excelsior waste rock dump up to supersaturation
and caused the successive precipitation of efflorescent
metal salts. The formation of secondary gypsum, Fe
(III)-hydroxides, Fe-sulfates (partly Cu-bearing) and
minor quantities of Mg-, Zn- and Mn-sulfates was
observed. At the base of the Excelsior waste rock dump
a major precipitation zone of efflorescent salts was
found during the dry season as result of outcropping,
evaporating pore solutions. (B) Rainwater dissolved
during the wet season water-soluble secondary minerals
precipitated during the dry period, infiltrated and trans-
ported acids and mobile elements into the waste rock
dump where they react with primary minerals and leach
heavy metals (Zn, Cu, Cd) out of primary sulfides. The
heavy metals Fe, Mn, Zn, Cu, Cd (as cations), Ca
and Mg (as cations) and the anion SO42− were mobile
in the Excelsior waste rock dump system. Arsenic was
only partly retarded in the system by adsorption on Fe
(III) hydroxides, AMD waters still contained up to
7.99 mg/L As. The mobility of Pb was limited by the
low solubility of the Pb mineral anglesite. Most of the
heavy metal sulfides precipitated during the dry season
seemed to be dissolved during the wet season and left
the Excelsior waste rock dump as AMD. As result, the
formation of an enrichment of heavy metal as efflo-
rescent salts at the base of the Excelsior waste rock
dump was limited to the dry season.
Two main pathways were assumed for the outcropping
highly mineralized acid solutions: (1) outcrop at a broad
109
spring zone at the base of the waste rock dump where the
AMD was channelled and conducted to a lagoon on the
Quiulacocha tailings impoundment, and (2) infiltration
from the waste rock dump into the underlying parts of the
Quiulacocha tailings impoundment.
Due to the high quantity of sulfides (N 60 wt.%) in
and the low neutralization potential of the waste rocks
(b5 wt.% carbonates) as well as the slow oxidation of
the pyrite content, a long-term AMD potential for the
Excelsior waste rock dump must be assumed.
Acknowledgements
We thank A. Cornejo and J. Rosa del Castillo (Cen-
tromin Peru) for their permission, access to their
properties and also their interest and support. Special
thanks are due to the management and geologists and all
staff involved in this project from VOLCAN S.A.A. for
their interest, the access to the properties, their logistic
support and their collaboration, especially V. Gobitz,
F. Grimaldo, L. Osorio and W. Hevedia. We thank
P. Schreiter, P. Schreck, W. Schmitz and G. Kommichau,
University of Leipzig, Germany, as well as H.-R. Pfeifer
and L. Dufresne, University of Lausanne, Switzerland, for
analytical support and helpful discussions. For the ICP–
MS analyses, we give many thanks to P.-Y. Favarger from
the Institute F.-A. Forel, Geneva, Switzerland. We thank
R. Wennrich (UFZ Leipzig-Halle, Germany) for his
analytical support. For their support in Peru in the field
work, sample preparation and analytical approaches,
we also would like to thank R. Mucho and R. Paredes
(INGEMMET Peru) and J. Torrejón (GEPASAC Peru).
The project was supported by the German National
Academic Foundation and the Swiss National Science
Foundation.
110 J. Smuda et al. / Journal of Geochemical Exploration 92 (2007) 97–110
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