Applied Geochemistry 18 (2003) 13471359

www.elsevier.com/locate/apgeochem

The role of secondary minerals in controlling the

migration of arsenic and metals from high-sulde
wastes (Berikul gold mine, Siberia)
R. Gierea,*, N.V. Sidenkob, E.V. Lazarevab
a

Department of Earth and Atmospheric Sciences, Purdue University, West Lafayette, IN 47907-1397, USA
The United Institute of Geology, Geophysics and Mineralogy, pr. Koptyuga 3, Novosibirsk 630090, Russia

Abstract
The role of secondary minerals in controlling the migration of As, Cu, Zn, Pb and Cd has been investigated in piles
of high-sulde waste at the Berikul Au mine, Kemerovo region, Russia. These wastes contain 4045 wt.% suldes and
have been stored for approximately 50 a near the Mokry Berikul river. Sulde oxidation generates acid pore solutions
(pH=1.7) with high concentrations of SO2

4 (190 g/l), Fe (57 g/l), As (22 g/l), Zn (2 g/l), Cu (0.4 g/l), Pb (0.04 g/l), and
Cd (0.03 g/l). From these solutions, As is precipitated as amorphous non-stoichiometric Fe-sulfoarsenates in the lower
horizons of the waste piles. During precipitation of the Fe-sulfoarsenates, the concentration of Fe in these phases
decreases from 34 to 21 wt.%, that of As increases from 11 to 22 wt.%, while the S content remains approximately
constant (5.45.8 wt.%). Arsenic is also accumulated in jarosite-beudantite solid solutions (up to 8.4 wt.% As), which
occur as inclusions in the amorphous Fe-sulfoarsenates. In eorescent crusts on the surface of the waste pile, As coprecipitates with the Fe(III) sulfates copiapite (0.27 wt.% As) and rhomboclase (0.87 wt.% As). Zinc and Cu are
incorporated primarily into Fe(II) sulfates, i.e. melanterite in the interior of the waste pile, and rozenite in the eorescent crust. The Zn mineral dietrichite is also formed at the surface of the waste pile as a result of evaporation of pore
solutions, and is the only Fe(II) sulfate containing detectable amounts of As (0.64 wt.%). Lead is mainly co-precipitated with minerals of the jarosite group, where the Pb content may reach 4.3 wt.%. Co-precipitation of toxic elements with sulfates and sulfoarsenates of Fe is shown to be a signicant mechanism in controlling the concentration of
heavy metals in pore solutions of high-sulde mine wastes. Precipitation of secondary phases causes the formation of a
hardpan layer with low permeability at a depth of 11.5 m below the surface of the waste pile. Rainwater accumulates
above the hardpan horizons and slowly drains along these aquicludes to the bottom of the pile. Most of the rainwater
evaporates during inltration. This leads to formation of the described eorescent sulfate crusts. Dissolution of these
crusts during the next rain storm produces highly acidic surface waters (pH=1.1) rich in SO2

4 (30 g/l), Fe (18 g/l), As
(0.24 g/l), Zn (0.12 g/l), Cu (0.04 g/l), Pb and Cd (0.002 g/l). During the warm (t> 0  C) period of the year, which lasts
about 7 months, these surface waters transport a total of a few tens of kilograms of As and Zn, several kilograms of
Cu, and a few hundred grams of Pb and Cd from the waste pile into the Mokry Berikul river. As a result, the concentrations of these metals in the river water increase by an order of magnitude, thus reaching levels close to, or
exceeding the maximum values permissible for drinking water.
# 2003 Elsevier Science Ltd. All rights reserved.

* Corresponding author.
E-mail address: giere@purdue.edu (R. Giere).
0883-2927/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0883-2927(03)00055-6

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

1348

1. Introduction
Abandoned mine wastes containing high sulde concentrations are among the most serious sources of
environmental pollution. Understanding the geochemical processes which control precipitation and dissolution of secondary minerals in abandoned sulde mines is
crucial for the formulation of models that predict the
environmental impact of such sites. Moreover, a better
knowledge of these mechanisms will allow remediation
of existing problem sites and/or a reduction of the
extent of future pollution. Pore waters in and drainage
solutions from high-sulde waste are characterized by
low pH values and high concentrations of various heavy
metals (Blowes et al., 1991; Nordstrom, 1991). The
concentration of heavy metals in the pore solutions is
mainly controlled by their precipitation together with Fe
hydroxides and/or sulfates (Blowes and Jambor, 1990).
Precipitation and dissolution cycles of some secondary
minerals are strongly inuenced by seasonal wetting and
drying cycles (Frau, 2000), and thus it is important to
include meteorological parameters in models that simulate environmental impacts. Although mobilization of
As from mine waste is discussed in the literature, most
reports focus on low-sulde wastes only (e.g., Al et al.,
1994; Leblanc et al., 1996; Roussel et al., 1998; Langmuir et al., 1999; Shuvaeva et al., 2000; Ardau et al.,
2001; Gaskova and Bortnikova, 2001).
The goal of the present study is to understand the
processes controlling the migration and sequestration of
Cu, Zn, and Pb and, in particular, the mobility of As in
high-sulde waste piles. To achieve this goal, the authors
investigated high-sulde mine wastes at the Berikul Au
mine in Siberia. A specic objective of the present paper
is to combine detailed mineralogical investigations of
the secondary phases occurring in the waste with both
meteorological observations and studies of the water

chemistry of samples collected in various parts of the

waste pile and in the nearby river.

2. Description of the waste site

The Berikul Au mine is situated in the northern part
of the Kemerovo region, Western Siberia, about 450 km
NE of Novosibirsk (Fig. 1). The deposit, an Au-suldequartz vein with a Au content of 15 g/t, was mined
exclusively for Au. The mine was in operation between
1942 and 1991, but no other production data were
available to the authors. Gold occurred as ne-grained
intergrowths with sulde minerals, mainly pyrite and
arsenopyrite. From these suldes, Au was extracted at
the Berikul mill by using the cyanide technique. After
removal of the Au-bearing cyanide solutions, the sulde
otation residues were neutralized by adding Ca(ClO)2
before being dumped on waste piles. The waste studied
here has been in a pile since 1952, while waste from
other piles was used for road construction when new
tailings impoundments were built in 1972.
The discarded material contains 4045 wt.% negrained suldes, including pyrite (3540 wt.%), arsenopyrite (25 wt.%), and minor amounts of pyrrhotite,
sphalerite, chalcopyrite, and galena. Among the gangue
minerals found in the wastes, the predominant phases
are quartz (3035 wt.%), albite (510 wt.%), chlorite
(510 wt.%), muscovite (about 5 wt.%), and calcite (35
wt.%). The studied high-sulde wastes have been
deposited on alluvial material, consisting of carbonate
boulders, and were stored for about 50 a on the left
bank of the Mokry Berikul river. The waste pile has a
length of approximately 250 m, a width of 50 m at its
base, and a height of 3 m (Fig. 2). The alluvial material
around the waste pile is dry, and no springs have been
detected near the river bank, suggesting that the river

Fig. 1. Map showing the location of the Berikul Au mine in the Kemerovo region of Southwestern Siberia.

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

1349

Fig. 2. Schematic map of the studied waste pile and the surrounding area at the Berikul site showing sample localities, hydrological
stations, and excavation pits.

represents the local ground water table. The only

springs found are drainage water emanations at the
base of the waste piles (Plate IA, Fig. 2).
The Berikul site is located at an altitude of 850 m
above sea level. The average yearly temperature is

1.5  C, and the total precipitation averages 600 mm of
rain and snow annually. There is, however, a distinct
warm period during which the temperature is above
freezing. This warm period lasts from May to October,
and most of the precipitation (approximately 400 mm)
falls during this time.

3. Methods of investigation
Solid samples were collected from both surface outcrops and excavation pits, which were dug with a
mechanical excavator in dierent parts of the waste pile
(see Fig. 2). The pits were excavated in order to gain an
insight into the stratication of the waste pile, to compare vertical and lateral zoning, and to collect samples
from the interior of the pile. The solids were then put

into hermetically sealed polyethylene bags and frozen

immediately to preserve the initial characteristics of
pore waters. The solid waste material was studied by
reected light microscopy and scanning electron microscopy (Jeol JSM-36). X-ray powder diraction (XRD)
analyses were performed with a DRON-UM diffractometer (Burevestnik, made in Russia) using ltered
Cu-Ka radiation. Thermogravimetric analysis (TGA)
was carried out with a MOM device (made in Hungary),
using a 120 mg sample, which was heated from room
temperature to 1000  C, at 12  C/min.
The compositions of the secondary phases were
determined with a CAMECA-SX50 electron microprobe at the Department of Earth and Atmospheric Sciences of Purdue University. The instrument is equipped
with 4 wavelength dispersive spectrometers, and was
operated for quantitative analysis at an acceleration
potential of 20 kV and a beam current of 80 nA measured on a Faraday cup. Samples and standards were
coated with 20 nm of C. Well-characterized minerals
and synthetic oxides were used as standards. Data collection time was 20 s for most major elements, and

1350

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

Plate I. (A) Drainage water emanates from the waste pile and forms reddish-brown streamlets which eventually enter the Mokry
Berikul river. This photograph shows where drainage water sample B-3 was collected (see Fig. 2). (B) Photomicrograph displaying
sequence of alteration zones around leaching cavities within the hardpan layer (horizon 2 in Fig. 3). The leaching cavities appear as
open space (white) in the upper part of the gure. Zone 1: suldes + gypsum. Note large euhedral secondary gypsum crystals; Zone 2:
hydronium jarosite + gypsum +suldes; Zone 3: amorphous Fe-sulfoarsenates (reddish-yellow, see arrow). Note that these Fe-sulfoarsenates encrust the walls of the leaching cavity. Plane-polarized light. (C). Photomicrographs showing the dierent morphologies
of jarosite. Left: spherical aggregates of hydronium jarosite (arrows) in horizon 4 (see Fig. 3); Right: oolites of jarosite in a crack in
horizon 4 (see Fig. 3). Both pictures taken in plane-polarized light. (D). Backscattered electron image (BSE1) and element distributions maps (for As, Fe, Al, K and Pb) showing matrix and inclusions in the amorphous Fe-sulfoarsenates of horizon 4 (see Fig. 3).
Color coding: elemental concentrations increase from blue to green, to yellow, to red.

3060 s for minor elements. Data collection on background positions on either side of each peak was half
the time of data collection on the corresponding peak
position. The raw data were corrected on-line by the
PAP correction procedure (Pouchou and Pichoir, 1984).
Detection limits for dierent components varied from
0.01 to 0.05 wt.%, and analytical precision was
approximately 2% for most major elements, and better
than 10% for most of the trace elements. Element distribution maps were generated at 20 kV and 100 nA,
and the data were collected for 100 ms/pixel in wavelength dispersive mode.
In water-soluble phases, the concentrations of As, Cu,
Zn, and Pb were determined by X-ray uorescence
(XRF) analysis. For this purpose, less than 1 mg of
single-crystal particles and monomineralic aggregates
(about 100 mm across) were selected, identied by XRD,
and then mounted on polyethylene lm, which was
inserted into a Russian-made IRIS-3 spectrometer. The

sample was analyzed using the method described by

Kolmogorov and Trounova (2002). Detection limits of
the XRF analysis were 0.05 wt.% for As, and 0.01 wt.%
for Cu, Zn, and Pb, and the analytical precision was
within 20%.
Water samples from the surface of the waste pile were
collected during rain events using special catchers,
resembling gutters and connected to a tank, to estimate
the volume of water owing down the slopes of the
waste pile during each rain event. The amount of rain
was measured with a pluviometer. Samples of drainage
solutions were collected from streamlets that emanate at
the bottom of the waste pile (Plate IA, Fig. 2). Water
samples of the Mokry Berikul river were collected at 3
sites: upstream (200 m away from the waste pile),
downstream (200 m away), and near the bank, where
the waste is stored (see Fig. 2). Pore solutions were
extracted from the moist silt material by uid expulsion
at a pressure of 100 Pa after the samples had been

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

thawed in the laboratory. With the exception of the pore

solutions, the Eh and the pH of all water samples were
measured in the eld immediately after sampling by
using an INFRASPAK potentiometer (made in Russia),
whereby the precision of a single measurement was 10
mV for Eh, and  0.08 for pH. The Eh and pH measurements for the pore solutions were carried out only
after the samples had been thawed and the solutions
extracted in the laboratory. Approximately 100 ml of
solution were collected by a syringe through a lter
(0.45 mm) into glassware, and were subsequently divided
into two aliquots. One of the aliquots was then acidied
with HNO3 to preserve the metal concentration,
whereas the other aliquot was preserved in its initial
state. All water samples were stored about 1 month at a
temperature 46  C in a refrigerator. The concentrations
in the acidied solutions of As, Ca, Cd, Cu, Fe, K, Mg,
Na, Pb, and Zn were determined by ame atomicabsorption spectrometry (AAS; Perkin-Elmer equipment, model 3030E equipped with an HGA-600
graphite furnace) and by thermal-electric AAS (PueUnikam equipment, model SP-9). The contents of




2





NH+
were deter4 , Cl , F , NO3 , HCO3 , and SO4
mined in the second aliquot by ion chromatography
using a Russian-made MILIXROM chromatograph.

1351

4. Results and discussion

4.1. The waste pile in cross-section
During the fty 50 a of storage in the pile, the waste
was subjected to supergene alteration, which led to a
characteristic layering. In cross-section, 5 main horizons can be distinguished in the waste pile (Fig. 3).
These are distinct in terms of mineral content, color,
porosity and hardness, and comprise, from bottom to
top:
4.1.1. Horizon 1
This zone consists of friable, only slightly altered sulde wastes of gray-green color. It contains 35 wt.%
calcite, and is approximately 11.5 m thick.
4.1.2. Horizon 2
Overlying horizon 1, this layer consists of lithied
waste containing gypsum as binding material. It is a
hardpan layer with a thickness of approximately 1 m.
Leaching cavities are observed in this zone (shown in
black in Fig. 3), and these are often lled by jarosite and
amorphous Fe-sulfoarsenates (Plate IB). As a rule, such
hardpan layers are characterized by low permeability,
which prevents penetration of solutions and gases into
the deeper horizons of waste piles (Blowes et al., 1991).
At the studied site, the hardpan layer contains trace
amounts of calcite, i.e. approximately 1 wt.%, but all
overlying horizons are devoid of calcite.
4.1.3. Horizon 3
Overlying the hardpan layer is a tobacco-colored,
0.51 m thick horizon, which consists of very moist and
ne-grained wastes of silt size. This zone, referred to as
the melanterite zone, contains leached relics of hardpan
material (Fig. 3), which are overgrown by melanterite
aggregates (up to 10 cm across). The presence of such
relics of lithied material in horizons above the actual
hardpan layer documents that the lithied waste is dissolving as a result of decreasing pH in the pore solutions
during sulde weathering. The hardpan material,
however, decomposes only slowly, because of its low
permeability.
4.1.4. Horizon 4
This thin intermediate zone has a gray color, and is
composed of quartz, jarosite and suldes. It separates
the melanterite zone from the overlying horizon 5.

Fig. 3. Supergene weathering prole through the waste pile at

the Berikul site. This prole displays the situation encountered
in excavation pit B-2/99 in the eastern part of the waste pile (see
Fig. 2), but it is representative of the entire site. The numbered
horizons are described in the text.

4.1.5. Horizon 5
The uppermost horizon is distinctly yellow, is up to
0.5 m thick, and contains some strongly oxidized relics
of hardpan material. The predominant phase is jarosite;
hence, this horizon is referred to below as the jarosite
zone.

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

1352

The second jarosite variety, jarosite sensu stricto,

occurs as oolites of about 5 mm in diameter along cracks
(Plate IC) in horizon 4 (see Fig. 3). It also forms rims
around hydronium jarosite, showing clearly that it precipitated after hydronium jarosite. Jarosite is considerably richer in Cu and Zn than hydronium jarosite
(Table 1). Moreover, jarosite is characterized by signicantly higher contents of both As (1.7 wt.%) and Pb
(4.3 wt.%). Joint incorporation of As and Pb into jarosite is consistent with the possible occurrence of a solid
solution between jarosite [KFe3+
3 (SO4)2(OH)6] and
beudantite [PbFe3+
(AsO
,SO
)(OH)
3
4
4
6; see also Jambor
and Dutrizac, 1983; Rattray et al., 1996].

4.2. Secondary minerals

4.2.1. Gypsum (CaSO42H2O)
Gypsum is the earliest secondary mineral found, and
it occurs even in the slightly altered sulde wastes of
zone 1. In the hardpan layer, gypsum crystals are up to
2 mm across and form a framework that binds the negrained sulde phases (Plate IB). The concentrations of
As, Cu, Zn, and Pb in gypsum are all below detection
limits.
4.2.2. Jarosite solid solutions
Two main varieties of jarosite-group phases were
detected, and these can be distinguished on the basis of
the predominance of alkali-site ions (Table 1). The rst
variety is hydronium jarosite (H3O,K,Na)Fe3+
3 (SO4)2(OH)6. The second variety is jarosite sensu stricto,
(K,H3O,Na)Fe3+
3 (SO4)2(OH)6, with K concentrations
that are considerably higher (3.1 wt.%) than in hydronium jarosite. Average Na concentrations are low in
both varieties, namely 0.3 and 0.5 wt.% in hydronium
jarosite and jarosite, respectively. Hydronium jarosite
forms spherical aggregates up to 20 mm in size, which
were observed in all horizons (Plate IC). Extensive precipitation of hydronium jarosite must have started after
formation of gypsum in the hardpan layers, as documented by the mineralogical zoning observed around
leaching cavities in the hardpan (typical zoning shown
in Plate IB).
The zones more distant from the open cavity are less
altered and contain the earliest secondary phase, i.e.
gypsum (Zone 1 in Plate IB). In the more weathered
material, which forms the walls of cavities (Zone 2 in
Plate IB), hydronium jarosite begins to appear. Sulfoarsenates are observed closest to and as incrustations
of the cavities (Zone 3 in Plate IB). From these observations, it is concluded that during the weathering of the
waste material, the secondary minerals crystallized in
the following sequence: gypsum ! hydronium jarosite
! sulfoarsenates.

4.2.3. Amorphous iron sulfoarsenates (AISA)

Sulfoarsenates of Fe are precipitated in the leaching
cavities observed in the hardpan layer (Plate IB), as well
as in the lithied hardpan relics in the waste of the
overlying horizons 3 and 5 (Fig. 3). These phases are Xray amorphous, and exhibit a reddish-brown to reddishorange color. As outlined below, there are 3 varieties of
AISA, which can be distinguished on the basis of their
chemical composition. Since the authors were unable to
select enough material of a specic type of AISA based
on its physical appearance, a sample of non-distinct
AISA had to be used for infrared (IR) spectroscopy,
TGA and XRD. The IR spectrum of this material is
similar to that of sarmientite, Fe3+
2 (AsO4)(SO4)OH5H2O, and thus qualitatively points to a similar composition (Fig. 4a). The thermal properties of
these two phases are also similar, as documented by the
weight loss curves shown in Fig. 4b. The weight loss
between 100 and 685  C, representing water content, is
30.2% for the amorphous phase, and 23.0% for sarmientite. The weight losses between 685 and 980  C,
representing the SO3 content, are 4.8 and 16.4% for the
amorphous phase and sarmientite, respectively. To
explore which phases would crystallize from the amorphous substance if it were heated, the AISA sample was
heated to 220  C and kept at that temperature for 6 h.

Table 1
Average elemental concentrations (with standard deviations) in sulfoarsenates and sulfates of Fe (wt.%), as determined by electron
probe microanalysis

Hydronium jarosite from horizon 4

Hydronium jarosite from horizon 5
Jarosite from horizon 4
AISA, matrix of group I
AISA, matrix of group II
AISA, group III
Inclusions in matrix of group I
Inclusions in matrix of group II

Al

As

Cu

Fe

Pb

7
24
7
12
33
82
6
16

0.11 0.07
0.12 0.08
0.06 0.02
0.30 0.11
1.2 0.3
1.9 0.4
0.20 0.10
2.9 0.9

0.73 0.10
0.35 0.13
1.7 0.2
11.0 1.0
14.0 1.3
21.6 1.4
8.1 2.3
8.4 2.5

0.010.01
0.030.02
0.240.08
0.040.03
0.030.03
0.090.04
0.040.03
0.030.03

28.81.3
27.22.3
29.90.6
34.31.4
28.81.0
20.91.7
32.01.1
25.22.6

0.970.26
1.60.3
3.10.4
0.070.08
0.020.03
0.030.10
1.00.5
1.81.5

0.310.08 11.8 0.3 0.01 0.02

0.360.24 10.8 0.7 0.02 0.02
4.30.8 12.5 0.3 0.17 0.09
0.070.03 5.4 0.7 0.08 0.05
0.090.05 5.9 0.4 0.26 0.10
0.890.35 5.5 1.0 0.29 0.07
0.340.26 7.8 1.4 0.06 0.04
1.71.1
8.0 1.2 0.24 0.10

n=Number of analyses; AISA is amorphous Fe-sulfoarsenates.

Zn

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

1353

Fig. 4. Properties of an amorphous Fe-sulfoarsenate sample. (a) Infrared (IR) absorption spectra showing the absorption bands corresponding to molecules of water, sulfate and arsenate. Solid line=spectrum for amorphous Fe-sulfoarsenate (this study); dotted
line=spectrum for sarmientite (from Abeledo and Benyacar, 1968.); (b) thermogravimetric data for amorphous Fe sulfoarsenate
(solid line) and sarmientite (dotted line); (c) powder XRD pattern obtained after heating the amorphous Fe-sulfoarsenate material.
The pattern reveals a mixture of beudantite (Bd), jarosite (Jr) and goethite (Gt).

Following heat treatment, an XRD pattern was generated, revealing peaks that correspond to the d-spacings
of the strongest lines of jarosite, beudantite, and goethite (Fig. 4c). The crystalline equivalent of the studied
AISA sample, thus, is a phase mixture, which displays
an overall similarity in IR and thermal properties to the
Fe-sulfoarsenate sarmientite. This crystalline phase
mixture, however, does not correspond exactly to the
amorphous starting material, because the heat treatment
must also have changed the water content (see Fig. 4b).

Among the amorphous Fe-sulfoarsenates, up to 3

types may be distinguished by chemical composition
and microstructure. The two earliest varieties, adjoining
the walls of the cavities, are reddish-brown in color and
consist of a matrix containing microscopic spherical
inclusions (Plate ID), which will be discussed below.
Farthest away from the cavity walls, a third zone occurs
which is reddish-orange in color, and does not contain
any inclusions. The As content in the matrix increases
from the earliest variety (AISA, group I, Table 1) to the

1354

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

Fig. 5. Ternary diagram (in mol%) for the system As2O5SO3Fe2O3H2O, showing the ideal composition (star symbols) of selected
minerals in the system, and the analyzed compositions of jarosites and amorphous Fe-sulfoarsenates (AISA) from the Berikul site.

latest one (group III) from 11 to 22 wt.%, while the Fe

content decreases in the same order, from 34 to 21
wt.%. The heavy metal contents increase to a lesser
extent, namely Zn from 0.08 to 0.29 wt.%, Cu from 0.04
to 0.09 wt.%, and Pb from 0.07 to 0.9 wt.%. This chemical evolution from group I to group III takes place at
nearly constant S contents (Table 1). In the ternary diagram shown in Fig. 5, the matrix of group II plots close
to the ideal composition of beudantite (PbFe3+
3 (AsO4,SO4)(OH)6), i.e., it is signicantly richer in Fe than
stoichiometric
bukovskyite
(Fe3+
2 (AsO4)(SO4)OH7H2O) and sarmientite. Bukovskyite and beudantite have been identied at the Carnoules Pb-(Zn)
mine, Gard, France where they are associated with
scorodite
(Fe3+AsO42H2O)
and
angelellite
(Fe3+
As
O
),
2 11 which were precipitated from acidic mine
4
waters (Leblanc et al., 1996). Group-III AISA plot near
the ideal composition of zykaite (Fe3+
4 (AsO4)3(SO4)OH15H2O) in Fig. 5, but they are richer in SO3.
As displayed in Fig. 5, the studied amorphous sulfoarsenates exhibit a wide compositional variation, and their
average compositions do not correspond to the stochiometry of the discussed minerals. The inclusions in group
I and II contain more Al, K, Pb and less As in comparison to the matrix (Plate ID, Table 1). On the ternary
As2O5SO3Fe2O3 diagram, the compositions of these

inclusions form distinct trends between jarosite and

beudantite, suggesting that they represent solid solutions between these two phases.
In summary, the chemical analyses and the X-ray
powder pattern of the heated amorphous substance
indicate that the inclusions may represent poorly crystallized
jarosite
(KFe3+
3 (SO4)2(OH)6)beudantite
(PbFe3+
(AsO
,SO
)(OH)
3
4
4
6) solid solutions. The average
contents of SO3 and As2O5 in jarositebeudantite are
similar in both group I and group II inclusions, but the
group I inclusions are richer in Fe (Table 1, Fig. 5).
Additionally, the second group is characterized by
higher concentrations of Al and Zn. The latter is substituting for Fe in the jarosite structure. The overall
sequential increase in Al, As, Zn and Pb observed for
both the matrix and the jarosite - beudantite inclusions
from earliest to latest varieties suggests that the concentrations of these elements in the pore solution
increased during formation of these phases. Such an
increase in concentration in solutions with simultaneous
deposition of solids is possible only if water evaporates.
4.2.4. Melanterite (Fe2+SO47H2O)
Melanterite occurs as green crystals (up to 2 cm
across) in the interior parts of the waste pile. This is in
contrast to other soluble Fe-sulfates, which have been

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

1355

Table 2
Average elemental concentrations (with standard deviations) of As, Zn, Cu and Pb in the soluble sulfate phases (wt.%)

Melanterite, Fe2+SO47H2O
Rozenite, Fe2+SO44H2O
Copiapite, Fe2+Fe3+
4 (SO4)6(OH)220H2O
Rhomboclase, HFe3+(SO4)24H2O
Dietrichite, (Zn,Fe2+)Al2(SO4)422H2O

As

Zn

Cu

Pb

3
1
3
3
3

< 0.05
< 0.05
0.27 0.04
0.87 0.36
0.64 0.27

0.340.28
0.5n.a.
0.130.09
0.080.03
3.251.73

0.240.2
0.16n.a.
0.180.17
0.120.04
0.080.01

< 0.01
0.05 n.a.
< 0.01
0.05 0.05
< 0.01

n=Number of analyses; n.a.=not enough analyses to calculate standard deviation.

found only on the surface of the waste pile. Melanterite

is observed to overgrow hardpan relics, which contain
jarosite solid solutions and amorphous Fe-sulfoarsenates, and therefore is clearly younger than both the
jarosite solid solutions and the amorphous Fe-sulfoarsenates. In the uppermost portions of the waste pile,
however, melanterite gives way to jarosite (horizons 4
and 5, Fig. 3), probably as a result of the more oxidizing conditions near the surface of the waste pile. Thus,
sulfates and sulfoarsenates of Fe3+ are precipitated
during the earliest and last stages of weathering,
whereas sulfates of Fe2+ (i.e. melanterite) are formed
during the intermediate stage. This unusual development of the weathering process, is at present not
understood.
Melanterite contains considerable amounts of Zn and
Cu (Table 2). Pisanites, i.e. CuZn varieties of melanterite, are common in wastes of sulde ore deposits in
the Ural region (Emlin, 1991), and Zn-bearing melanterite has been reported from Iron Mountain, California, USA (Alpers et al., 1994). Recently, melanterite
has also been described as an environmentally important secondary phase formed as a result of pyrite oxidation at an abandoned mine in Sardinia, Italy (Frau,
2000).
4.2.5. Iron sulfates in eorescent crust
On the slopes of the waste pile, eorescent crusts
consisting of Fe-sulfates were observed. In these crusts,
formed through evaporation of pore solutions, the following Fe-sulfates were identied: rozenite (Fe2+
SO44H2O), copiapite (Fe2+Fe3+
4 (SO4)6(OH)220H2O),
and rhomboclase (HFe3+(SO4)24H2O). The eorescent crusts further contain the Zn mineral dietrichite,
(Zn,Fe2+)Al2(SO4)422H2O, which was also identied
by powder XRD and which contains equal amounts of
Zn and Fe (3.3 wt.%). The Fe2+/Fe3+ ratio decreases
from rozenite to copiapite, to rhomboclase (see the formulae above), in parallel to the decrease in the contents
of Zn and Cu (Table 2). At the Berikul site, thus, Fe2+sulfates seem to be richer in Cu and Zn than Fe3+-sulfates. On the other hand, the highest As content is
observed in rhomboclase, suggesting that As is captured
when Fe(III) sulfates precipitate.

4.3. Water characteristics

During this study, 4 types of water were distinguished on
the basis of their occurrence: pore waters, drainage (inltrating) waters, surface waters, and water of the Mokry
Berikul river. Each type of water is a link in the pathway of
element migration into the environment (Fig. 6).
The pore solutions are generated through interaction
of suldes, rainwater and atmospheric O2. They are
accumulated above the low-permeable hardpan layer,
mainly in the melanterite zone (horizon 3, Fig. 3). It is
assumed that only a small part of the solutions could
penetrate through the hardpan layer, because the
slightly altered wastes in horizon 1 remained dry even

Table 3
Average chemical compositions (with standard deviations) of
the dierent types of water at the Berikul site. Concentrations
are in mg/l
Pore waters
x s

Drainage waters Surface waters

n x s

pH
1.70.1
6
2.3 0.1
Eh (mV)
62129
6
649 n.a.
As
22,25014,549 6
976 544
Ca
32145
6
218 n.a.
Cd
2719
6
11 14
780n.a. 1
184 156
Cl

CN

n.d.
n.d.
Cu
410183
6
74 51
F

200n.a. 1
93 53
Fe
57,33320,166 6 18,0949154
HCO2

<0.05
1 <0.05
3
K
15.57.5
6
5.4 2.8
Mg
63171294 6
519 n.a.
Na
6969
6
8.9 5.9
NO

<0.1
6 <0.1
3
O2 dissolv. n.d.
0.30 n.a.
Pb
369
6 17.1526.06
SO2

187,50020,065 6 19,7521256
4
Zn
19371314 6
616 804

n x s
8
2
7
2
8
3

8
3
8
8
6
2
5
1
2
8
3
8

1.1n.a. 2
635 6
4
235 64 4
247 n.a. 1
1.71.1 4
88n.a. 1
0.5n.a. 1
3913 4
65n.a. 1
17,8064297 4
<0.05
1
37n.a. 1
245 n.a. 1
17n.a. 1
<0.1
1
0.30 0.28 3
1.70.1 4
30,240n.a. 1
119 73 4

x=Average; s=standard deviations; n=number of analyses;

n.d.=no data; n.a.=not enough data to calculate standard
deviation.

1356

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

Fig. 6. Schematic diagram showing the sampling locations for the various water types: 1pore water; 2drainage water; 3surface
water; 4river water. Arrows represent the pathway of elemental migration from the Berikul waste pile to the river, whereby the
width of the arrows corresponds to the quantity of elements. Note that the waste pile rests on alluvial material made of carbonate
boulders.

after abundant rain fall (2 mm/3 h), whereas the silty

melanterite zone (horizon 3) was wet. Therefore, it was
possible to extract pore solutions only from horizons
35, i.e. from waste lying above the hardpan layer.
These pore solutions are characterized by a pH of 1.7,
an Eh of 621 mV, and a high salinity, with total salt
contents of about 270 g/l (Table 3). Major components
of the pore waters are SO2

4 (188 g/l), Fe (57 g/l), As (22
g/l) and Mg (6.3 g/l). Such extraordinary high As concentrations in low-temperature drainage solutions have
not been reported previously; the highest As concentration described so far in the literature is 340 mg/l,
determined for acid waters (pH=
1.0) draining from
sulde waste at Iron Mountain, California, USA
(Nordstrom, 1991). The studied pore solutions also
contain relatively high concentrations of Zn (1.9 g/l)
and Cl
(0.8 g/l). Among the dierent water types
occurring at the Berikul site, the highest contents of
heavy metals are detected in these pore waters (Table 3).
The pore water is evaporated during the inltration
process, as indicated by the presence of extensive eorescent crusts on the surface of the waste pile.
The drainage waters slowly move along the hardpan
layers to the bottom of the pile, from where they emanate to form puddles and streamlets with a reddishbrown color (Plate IA). The drainage waters almost
certainly do not contain a groundwater component,
since the alluvial material around the waste pile is dry,
and no springs occur on the river bank. The salinity of
the studied drainage water samples is about 40 g/l. The
solutions are acid (pH=2.3) and have an Eh of 649 mV.
Major components of these drainage solutions are SO2

4
(20 g/l) and Fe (18 g/l). Relative to the pore solutions
described above, the drainage waters have signicantly
lower heavy metal contents (by 26 times). Moreover, the
As concentration is 20 times lower than in the pore solutions. These observations suggest that the metal content

of the drainage waters has decreased relative to that of

the pore solutions, most likely due to precipitation of
secondary phases in the interior parts of the waste pile,
as well as outside the waste, where the drainage waters
have been in contact with atmospheric O2 before being
sampled. It is of note that the Ca/Mg ratio increases
from about 1:20 in the pore waters to about 1:2 in the
drainage waters (Table 3), suggesting that a Mg-rich
solid has perhaps been precipitated from the solutions.
No Mg-phase was observed, however, even though the
preliminary
thermodynamic
calculations
[using
WATEQ4F (Ball et al., 1987) and the data shown in
Table 3] indicate that the pore water is supersaturated
with respect to epsomite (MgSO47H2O) at 20  C
(Sidenko, 2001). Chlorite, which accounts for 510
wt.% of the waste, might contain signicant amounts of
Mg, but this element was not analyzed in any phase
since the study was focused on other metals.
The surface waters form as a result of dissolution of
the eorescent crusts by rainwater. The surface solutions, sampled during rain storms, are characterized by
the lowest pH values (1.1), an Eh of 635 mV, and by a
total salinity of 50 g/l (Table 3). Major components of
these solutions are SO2

4 (30 g/l) and Fe (18 g/l ). The
average contents of As, Cu, Zn, Pb and Cd are several
times lower than those in the drainage solutions
(Table 3). The quantity of As, Cu, Zn, Pb and Cd
removed from the waste pile by these surface waters was
estimated on the basis of meteorological, chemical and
hydrological measurements taken during two consecutive rain storms, which lasted about 3 h each. The
data in Table 4 document that both precipitation and
discharge during the second rain storm were similar to
those measured during the rst storm. Most of the metal
concentrations in the surface waters, however, were
considerably lower in the second event, which took
place only two days after the rst one. This indicates

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

1357

Table 4
Results of individual meteorological, chemical and hydrological measurements during two consecutive rainstorms in August 2000:
precipitation, elemental concentrations in surface waters (in mg/l), and volume of surface water (in l) discharged into the river for each
measuring station (see Fig. 2)
Precipitation

Sampling station

Zn

Cd

Pb

Cu

As

Volume

1.93 mm (20.08.2000)

ST-1/1
ST-1/2
ST-2/1
ST-2/2

200
160
55
60

2.6
2.6
0.7
0.8

1.9
1.6
1.7
1.7

52
47
26
30

300
280
170
190

446
500
423
551

1.96 mm (22.08.2000)

The data shown in Table 3 for the surface waters represent the average of all 4 measurements listed here.

that dissolution of surface minerals was much more

pronounced during the rst rain storm, probably
because the intermittent dry period between the storms
was too short to build up a signicant amount of secondary surface minerals in the eorescent crusts. Taking the average metal concentrations in the surface
waters (listed in Table 3) and the average discharge
volume for these two events (480 l), it was calculated
that each storm removed, on average, approximately
113 g As, 57 g Zn, 19 g Cu, 0.8 g Pb, and 0.8 g Cd from
the slope of the waste pile facing the Mokry Berikul
river, and discharged the metals into the river.
According to these measurements, and based on average meteorological data (400 mm of rain during the
warm season), it has been calculated that during the
warm season, a few tens of kilograms of As and Zn, sev-

eral kilograms of Cu, and a few hundred grams of Pb and

Cd might be transported into the Mokry Berikul river.
Some of the dissolved metals will be transformed into
suspended solid precipitates as soon as the acid surface
streams mix with the nearly neutral river water. The
above calculation assumes that the rainstorms which
were sampled are typical of other rainstorms during the
warm season, and thus the authors are unable to anticipate the eects of much heavier or much lighter rains.
The river water exhibits a pH that ranges from 7.6
(upstream, sample B-4) to 6.5 (downstream, sample
B-11), reecting the input of acid water from the waste
pile (Table 5). The river water samples have an average
Eh of +370 mV, and their total salt content is approximately 120 mg/l (Table 5). This water is a SO24-enriched
(12.5 mg/l on average) HCO2

3 Ca type, with average

Table 5
Water analyses of samples collected from the Mokry Berikul River (see Fig. 2). B-4: upstream; B-10: near waste pile; B-11: downstream
Sample #

B-4

B-10

B-11

MCL (US)

MCL (Russia)

pH
Eh (mV)
As
Ca
Cd
Cl

CN

Cu
F

Fe
HCO2

3
K
Mg
Na
NO

3
O2 dissolv.
Pb
SO2

4
Zn

7.6
389
<0.05
18.5
0.0001
0.16
n.d.
0.001
<0.05
<0.03
83.42
1.0
3.3
1.7
<0.1
6.8
0.004
11.9
0.038

7.1
359
0.3
17.8
0.0044
0.21
n.d.
0.005
<0.05
<0.03
81.48
1.3
3.1
1.5
<0.1
11
0.004
13.5
0.560

6.5
346
0.05
17.9
0.0119
0.37
n.d.
0.010
<0.05
<0.03
n.d.
1.4
1.9
2.1
<0.1
8.9
0.009
12.1
0.813

0.05

0.005

0.2
1.3
4.0

10 *

0.015

0.03

0.001

0.03

Data represent individual analyses in mg/l. n.d.=Not determined; * measured as N; MCL (US)=maximum contaminant level (in
mg/l) allowed in drinking water according to the US Environmental Protection Agency (EPA, 2001); MCL (Russia)=maximum
contaminant level (in mg/l) allowed in drinking water in Russia (Eremeev, 1990), respectively.

1358

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

contents of 18 mg/l Ca and 82.5 mg/l HCO2

3 . Compared
to the upstream river water (sample B-4), the concentrations of As, Cu, Zn, Pb and Cd are signicantly higher in
the water near the waste pile (sample B-10), and generally even higher further downstream (sample B-11).
For example, the downstream concentration of Cd is
higher by two orders of magnitude than the upstream
concentration. The concentration of As in the river near
the waste pile (sample B-10) is much higher than that in
the upstream water, and specically, it is one order of
magnitude higher than the maximum contaminant level
allowed in drinking water in the US (EPA, 2001). A
similar observation can be made for the downstream
concentration of Cd. For Zn, the concentrations are
close to the maximum concentrations permitted in
drinking water in Russia (Eremeev, 1990).
The data clearly document that the waters emanating
from and running o the waste pile have a serious impact
on the water quality of the Mokry Berikul river. This
environmental impact is particularly dramatic during the
warm season, when most of the precipitation is recorded
and evaporation is most intense. During the major part
of the cold season, the waste pile is covered by snow, which
reduces the evaporation as well as the amount of runo.

5. Conclusions
Acid solutions containing high concentrations of
SO2

4 , Fe, As and heavy metals are generated during
sulde oxidation in the Berikul waste pile. The mobility
of As, Cu, Zn and Pb within the waste pile is controlled
by precipitation of these metals as secondary phases.
Arsenic is precipitated in the form of amorphous Fesulfoarsenates, which form a matrix with inclusions of
jarositebeudantite. These inclusions show lower concentrations of As than the matrix. On the surface of the
waste pile, As co-precipitates with sulfates containing
trivalent Fe. Copper and Zn are precipitated together
with melanterite and rozenite, because these metals substitute for Fe2+ in sulfates. Within the eorescent crusts,
Zn is accumulated in dietrichite. Most of the Pb is captured by jarositebeudantite solid solutions. A sequential
increase in Al, As, Zn and Pb in both amorphous sulfoarsenates and jarositebeudantite inclusions suggests that
the concentrations of these elements increase in the pore
solution when the solid phases precipitate, a feature that
can be explained by slow water evaporation.
This study has established that the main pathway of
element migration is via surface drainage during and
after rainstorms. In dissolved form, a few tens of kilograms of As and Zn, several kilograms of Cu, and subkilogram quantities of Pb and Cd are removed by surface waters and transported into the Mokry Berikul
river during the warm season of the year. This discharge
results in a dramatic increase in the As, Cu, Zn, Pb and

Cd concentration in the river water, where some of these

metals reach concentrations near or in excess of the
maximum levels permitted for safe drinking water.

Acknowledgements
The authors are grateful to Dr. Richard Wanty, Dr.
Pierfranco Lattanzi, and an anonymous reviewer for
providing constructive reviews. Their valuable suggestions and thoughtful criticism of an earlier version
helped us to improve the quality of this paper. We further would like to thank Carl Hager for his assistance at
the Purdue University electron microprobe.

References
Abeledo, M.E.J., Benyacar, M.A.R., 1968. New data on sarmientite. Am. Mineral. 53, 20772082.
Al, T.A., Blowes, D.W., Jambor, J.L., 1994. A geochemical
study of the main tailings impoundment at the Falconbrige
Limited, Kidd Creek Division Metalurgical Site, Timmins,
Ontario. In: Jambor, J.L., Blowes, D.W. (Eds.), Short
Course Handbook on Environmental Geochemistry of Sulde Mine Waste. Mineral. Assoc. Can, Waterloo, pp. 59
102.
Alpers, C.N., Nordstrom, D.K., Jambor, J.L., 1994. Secondary
minerals and acid mine-water chemistry. In: Jambor, J.L.,
Blowes, D.W. (Eds.), Short Course Handbook on Environmental Geochemistry of Sulde Mine Waste. Mineral. Assoc.
Can, Waterloo, pp. 247270.
Ardau, C., Frau, F., Dadea, C., Mattusch, J., Wennerich, R.,
Titze K., 2001. Solid- state of arsenic in waste materials and
stream sediments from abandoned mine area of Baccu Locci
(Sardinia, Italy). In: Proc. Int. Conf. WRI - 10. Villasimius,
Italy, pp. 11731176.
Ball, J.W., Nordstrom, D.K., Zachmann, D.W., 1987.
WATEQ4Fa personal computer FORTRAN translation
of the geochemical model WATEQ2 with revised data base:
US Geol. Surv. Open-File Rep. 87-50.
Blowes, D.W., Jambor, J.L., 1990. The pore-water geochemistry and the mineralogy of the vadose zone of sulde tailings, Waite Amulet, Quebec, Canada. Appl. Geochem. 5,
327346.
Blowes, D.W., Reardon, E.J., Jambor, J.L., Cherry, J.A., 1991.
The formation and potential importance of cemented layers
in inactive sulde mine tailings. Geochim. Cosmochim. Acta
55, 965978.
Emlin, E.F., 1991. Technogenesis of pyrite deposits of Ural.
Publication of Ural State University Sverdlovsk (in Russian).
EPA, 2001. United States Environmental Protection Agency,
Oce of Water. Available from: www.epa.gov/safewater.
Eremeev, A.N. (Ed.), 1990. Handbook of Geochemical
Exploration of Mineral Resources. Nedra, Moscow.
Frau, F., 2000. The formation-dissolution-precipitation cycle of
melanterite at the abandoned pyrite mine of Genna Luas in
Sardinia, Italy: environmental implications. Mineral. Mag.
64, 9951006.

R. Giere et al. / Applied Geochemistry 18 (2003) 13471359

Gaskova, O.L., Bortnikova E.P., 2001. Experimental modeling
of trace element leaching from As-bearing tailings impoundments. In: Proc. Int. Conf. WRI - 10. Villasimius, Italy, pp.
12331236.
Jambor, J.L., Dutrizac, J.E., 1983. Beaverite plumbojarosite
solid solutions. Can. Mineral. 21, 101113.
Kolmogorov, Y., Trounova, V., 2002. Analytical potential of
EDXRF using toroidal focusing systems of highly oriented
pyrolytic graphite (HOPG). X-ray Spectrom. 31, 432436.
Langmuir, D., Mahoney, J., MacDonald, A., Rowson, J., 1999.
Predicting arsenic concentrations in the pore waters of buried
uranium mill tailings. Geochim. Cosmochim. Acta 63, 3379
3394.
Leblanc, M., Achard, B., Ben Othman, D., Bertrand-Sarfati, J.,
Personne, J.Ch., 1996. Accumulation of arsenic from mine
waters by ferruginous bacterial accretions (stromatolites).
Appl. Geochem. 11, 541554.
Nordstrom, D.K., 1991. Chemical modeling of acid mine
waters in the Western United States. Meeting Proc. USGS
Water Resour. Invest. Rep. # 91-4034, pp. 534538.

1359

Pouchou, J.L., Pichoir, F., 1984. Un nouveau mode`le de calcul

pour la microanalyse quantitative par spectrometrie de
rayons X. Partie I: application a` lanalyse dechantillons
homoge`nes. Recherches Aerospatiales 3, 167192.
Rattray, K.J., Taylor, M.R., Bevan, D.J.M., Pring, A., 1996.
Compositional segregation and solid solution in the leaddominant alunite-type minerals from Broken Hill, N.S.W.
Mineral. Mag. 60, 779785.
Roussel, Ch., Bril, H., Fernandez, A., 1998. Hydrogeochemical
survey and mobility of As and heavy metals on the site of a
former gold mine (Saint-Yrieix mining district, France).
Hydrogeologie 1, 312.
Shuvaeva, O.V., Bortnikova, S.B., Korda, T.M., Lazareva,
E.V., 2000. Arsenic speciation in a contaminated gold processing tailings dam. Geostand. Newslett. 24, 247252.
Sidenko, N., 2001. Arsenic and Heavy Metal Migration in
Weathering Zone of Berikul Sulde Waste. PhD thesis,
Institute of Geology SB RAS. Novosibirsk, Russia (in
Russian).