Applied Geochemistry 18 (2003) 97–108

www.elsevier.com/locate/apgeochem

Aqueous geochemistry in the Udden pit lake,

northern Sweden
Madeleine Ramstedta,*, Erik Carlssonb, Lars Lövgrena
a
Inorganic Chemistry, Department of Chemistry, Umeå University, SE-901 87 Umeå, Sweden
b
Division of Applied Geology, Luleå University of Technology, SE-971 87 Luleå, Sweden

Received 3 April 2001; accepted 17 January 2002

Editorial handling by B.A. Kimball

Abstract
The Udden pit lake in northern Sweden was studied from June 1998 to February 1999 in order to increase knowl-
edge of the geochemistry in lakes created as a result of decommissioning open pit mines. The vertical water profile in
the lake was sampled on 4 different occasions, in June, August, September and February. Water samples were analysed
for total concentrations of Fe, As, Cu, Cd, Zn, Pb, Al, Ca, K, Mg, Na, Mn, S, Cl, N and P. Temperature, concentra-
tion of dissolved O2, conductivity, pH, and redox potential were measured in situ at different depths. Four layers could
be observed in the lake during summer, and 3 layers during winter. A thermocline was observed during summer at a
depth of 5 m and on all 4 occasions a halocline was observed at a depth of
20 m, and a redoxcline at
35 m. Oxygen
concentration decreased dramatically at a depth of 20 m. pH increased downwards in the lake from 4.8 at the surface
to 6.4 at the bottom of the lake. Geochemical processes occurring in the lake, the origins of the layers, the metal con-
centrations and the anion concentrations are discussed in this article. # 2002 Elsevier Science Ltd. All rights reserved.

1. Introduction results in a pronounced stratification and with time, the

Decommissioning of open pit mines in order to pre-
vent acid mine drainage often involves flooding the open
pit and thereby creating an artificial lake. In many cases
waste rock is deposited in the pit prior to flooding. By
flooding it is expected that O2 will be prevented from
diffusing into mine wastes and rock walls, leading to a
minimised oxidation of sulphide minerals and a subse-
quently minimised release of heavy metals and acidity
(MEND, 1989). However, oxidation can still occur in
the absence of O2 but with Fe(III) as the oxidising agent
(Herbert, 1999).
These artificial lakes are called pit lakes and usually
have a small diameter to depth ratio compared to nat-
ural lakes. This, together with the saline waters, often
* Corresponding author. Fax: +46-90-786-9195.
E-mail address: madeleine.ramstedt@chem.umu.se
(M. Ramstedt).
0883-2927/03/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0883-2927(02)00068-9
development of an anoxic bottom layer (Miller et al.,
1996; Tempel et al., 2000). Doyle and Runnells (1997)
stated that one of the most important variables con-
trolling water circulation in lakes is the relative depth
(the relation between the depth and the diameter of the
lake). Other important variables are the length of free wind
action and the wave fetch (Klapper and Schultze, 1997).
The distribution and speciation of trace metals in
stratified lakes are influenced by 3 major geochemical
processes; cycling across redox boundaries, sorption and
coprecipitation on/with particles and formation of metal
complexes in aqueous solution with inorganic ligands
(e.g. OH, HS) and organic matter (Balistrieri et al.,
1994). Iron and Mn are important metals for controlling
the dissolved concentration of trace metals in oxic
waters since particles of Fe (oxy)hydroxides and Mn
(oxy)hydroxides act as scavengers for trace metals.
Adsorption of metal ions onto Fe (oxy)hydroxides
increases with pH (Dzombak and Morel, 1990), while
elements like As, forming oxo-anions, are preferably
98 M. Ramstedt et al. / Applied Geochemistry 18 (2003) 97–108
adsorbed at lower pH (Miller et al., 1996; Lützenkirchen
and Lövgren, 1998). The objective of the present work
was not only to study and describe the aqueous geo-
chemistry in a pit lake by field sampling and in situ
measurements but also to discuss the obtained results in
terms of geochemical processes such as weathering of
rock walls, adsorption and coprecipitation of heavy
metals on Fe and Mn (oxy)hydroxides, sulphide pre-
cipitation and oxidation of organic material.
2. Site description
The Udden open pit is situated approximately 70 km
west of Skellefteå in northern Sweden (Fig. 1). The
Udden sulphide ore deposit was part of the Skellefte
district volcanic series. The bedrock in the area consists
mainly of tuffite, some amphibolite and quartz-sericite
rocks, containing quartz and sericite with subordinate
amounts of chlorite. The Udden ore deposit was part of
a greater vein, which is called Kedträskfältet. This vein
also includes 3 other ore deposits: Kedträsk, Åsen and
Svansel (Boliden, 1955, 1971, 1980). The principle sul-
Fig. 1. The location of the Udden pit lake in Sweden. Sampling localities marked with A, B and C.
phide minerals at Udden were pyrite (FeS2), pyrrhotite
(Fe1-xS), sphalerite (ZnS), chalcopyrite (CuFeS2), galena
(PbS) and arsenopyrite (FeAsS). The average grade of
the ore is shown in Table 1. The mining in Udden star-
ted in 1971 with an open pit. After 3a of mining the
surface deposit was depleted and the mining operations
continued underground. The mining ended in 1991. A
total of 690 000 ton ore and 1000 000 ton of waste rock
was excavated from the open pit (Boliden, 1980).
The major waste rock deposits are situated south of
the pit lake and cover an area of 12 ha (Fig. 1). The
waste rock consists of approximately 1 wt.% S and 25
wt.% rocks with a buffering ability. The calculated
concentration of calcite is less than 0.5 wt.% of the
buffering rock. The waste rock deposit has been covered
with till (Boliden, 1991). The decommissioning pro-
gram, based on flooding the open pit, started in 1991.
All buildings, including the shaft tower, were demol-
ished and the ground at the northern side of the open pit
was levelled out. The excavated material and the waste
material from the buildings were deposited into the pit
(Boliden, 1990) together with waste rock from the
closely located Kedträsk mine. The waste rock from
 M. Ramstedt et al. / Applied Geochemistry 18 (2003) 97–108
Kedträsk had previously been stored in open air and
was thus significantly oxidised (T. Göransson, Boliden,
pers. comm.). The average grade of the ore in Kedträsk
is also shown in Table 1. The surrounding rock has a
SiO2 content higher than 52 wt.% (Boliden, 1982). The
composition of the waste rock from Kedträsk was
unknown but, considering the composition of the ore,
the waste rock most likely had a high sulphide content.
The shafts leading down to the underground mine in
Udden were covered with blocks of concrete prior to the
remediation. Natural sand and tailings were disposed of
in the western part of the open pit. All surrounding
areas were sown with grass. Due to a high inflow of
groundwater the pit was filled within 2a (Boliden, 1990).
Today, the pit lake is approximately 390 m long and
150 m across (Fig. 1). The maximum depth of the
lake was found to be 50 m using a sonic altimeter.
Because of p the large
ffiffiffi p ffiffiffiffiffiffi relative depth (18%) (relative
depth ¼ 50zm
= A0 where zm is maximum depth and
A0 is surface area. Doyle and Runnells, 1997) the lake is
possibly meromictic.
The only inflows to the lake are rainwater, surface
runoff and groundwater. There is no outflow of surface
water except at the northern side, where the lake over-
flows into a small creek during periods when the water
surface is elevated. A site-monitoring program collects
samples for analysis of the water quality when surface
water flows out from the lake. This happened in 1993,
1994, 1995 and 1998.
3. Methodology
The water quality at different depths in the Udden pit
lake was examined by collecting water samples and per-
forming in situ measurements with a probe. Measure-
ments were carried out on 4 different occasions during
1998 and 1999. Water samples were collected in June,
August and September for analysis of metals and major
anions. The in situ measurements were performed on
the same occasions with additional measurements in
February. The transparency of the water was estimated
by measuring the Secchi-depth with a Secchi disk and
water binoculars.
Table 1
Average grade of the ore in Udden and Kedträsket
Element Udden Kedträsket
Zn (wt.%) 4.72 2.86
Cu (wt.%) 0.41 0.31
Pb (wt.%) 0.35 0.22
As (wt.%) 0.1 0.22
Ag (g/ton) 41 21
Au (g/ton) 0.8 0.4
S (wt.%) 25.6 35
99
3.1. In situ measurements
Conductivity, temperature, concentration of dissolved
O2 (DO), pH and redox potential were measured in situ
with a probe (Hydrolab MiniSonde) (The MiniSonde
measures redox as a potential between a Pt electrode
and a AgCl reference electrode immersed in a KCl
solution. Conductivity is measured as a current between
2 electrodes held at a fixed potential. Dissolved O2 is
measured as a current resulting from the electrochemical
reduction of O2 at a Au membrane. For measuring pH
the probe has a glass electrode.). The probe was cali-
brated in the laboratory prior to the measurements and
the measurements were performed at 3 locations in the
Udden pit lake, points A, B and C (Fig. 1). In June
measurements were done only at point A, in August and
September, points A and B and in February, point C.
The DO data were recalculated into O2 saturation (%)
according to the equation given by Weiss (1970).
3.2. Water samples
Water samples were collected using a metal free
Ruttner sampler at different depths at two locations in
the Udden pit lake, points A and B. Point A corre-
sponds to the deepest part of the lake. Some duplicate
samples were collected at point B to study possible var-
iations in metal concentration towards the shore. Sam-
ples were collected at depths from 0.5 to 45 m.
Replicates were taken at a depth of 10 m at point A.
Equipment blanks and travel blanks were collected. The
recovery of Cu, Cd, Pb and As in spiked samples was
between 89 and 96%. Water samples were collected on 3
different occasions during the period June–September
1998; 22–26 June, 3–10 August and 7–14 September. To
estimate natural background concentrations in the area,
samples were also collected in a nearby natural lake,
Lake Ljusträsket.
Water samples were collected in 50 ml acid washed
polypropylene tubes. Two samples were taken at each
depth, one filtered immediately through a 0.22 mm
MILLEX1-GS MILLIPORE filter, to remove the par-
ticulate phase, and one which was not filtered. Both
samples were acidified with concentrated suprapure
HNO3 to obtain pH <1. The tubes were filled to the top
to avoid, as much as possible, prolonged exposure to
air. Samples collected for the determination of S, Cl, N
and P were neither filtered nor acidified and the samples
collected for analysis of N and P were collected in tubes
that had not been acid washed. The sample tubes for
collection of S and Cl samples were not completely filled
since they were to be stored frozen until analysis. The
other samples were stored in the dark at 4  C until ana-
lysis. TOC samples were collected in September at the
depths 3, 10, 30, 45 m and in L. Ljusträsket at 3 m. They
were collected in 15 ml polyethylene tubes, preserved
100 M. Ramstedt et al. / Applied Geochemistry 18 (2003) 97–108
using 200 ml 1.2 M HCl and stored in the dark at 4  C.
None of the samples had any smell and no particulate
phase or colour could be observed during the sampling,
except for a few white particles below a depth of 30 m in
September.
3.3. Chemical analysis
The different samples collected were analysed accord-
ing to Table 2. Samples analysed using inductively cou-
pled plasma mass spectrometry (ICP–MS) were diluted
with Millipore water (Super Q plus) and acidified. The
concentration of As was corrected for interference with
ArCl. The total concentration of Fe was determined
after reduction of Fe3+ in the samples. For reduction,
0.3 ml of 6 M HCl / 1.2 M NH2OH–HCl was added to
15 ml of sample and the solution was kept at
60  C
for 45 min and 5 ml of the reduced sample were mixed
with 5 ml phenanthroline in 40 ml of acetate buffer. The
absorbance was measured at 510 nm using UV/vis
spectrometry.
The August samples were also analysed with ICP–
AES by SGAB Analytica, Luleå, Sweden for validation
and to obtain data for additional elements. (All data are
not shown in this article, for a complete dataset see
Ramstedt et al., 2002).
4. Results and discussion
4.1. In situ measurements of physical parameters
All physical parameters measured in situ, except for
temperature and conductivity, appeared to be rather
constant during the period June–February (Fig. 2). The
temperature was constant at 5  C below 20 m but
showed some variation in the upper 20 m of the water
column. During summer the surface water was heated to
a temperature of 16  C and was cooled during autumn
and winter. In the water column between 5 and 20 m,
warming was observed from June to September and
Table 2
Techniques used for analysis of different elements on different sampling occasions during 1998 in Udden
Analysis Elements
ICP–MS As, Cu, Cd, Zn, Pb
UV/vis Fe
ICP–AESa Li, Na, K, Ca, Mg, Mn, Al, Si, Ba, Sr, Co, Cr,
Mo, Ni, S, V, B, Zn, Cu, Cd, As, Pb, Fe
Ion chromatographyb S, Cl
Continuous flow analysis—UV/visc N, P
Pt- catalysed high temperature combustionc C (TOC)
a
The analyses were performed at SGAB, Luleå, Sweden.
b
The analysis was performed at SLU, Umeå, Sweden.
c
The analysis was performed at UMF, Norrbyn, Sweden.
cooling from September to February. In February, the
uppermost part of the water column showed lower tem-
peratures than the rest of the lake.
During summer a thermocline and a halocline were
developed at 5 m. The uppermost part of the water col-
umn had a higher degree of O2 saturation during sum-
mer due to contact with the atmosphere and mixing by
wind and waves. The conductivity increased stepwise
downwards in the lake from
1 to
2 mS/cm. Between
June and September, a halocline was found at the ther-
mocline and another one was found at a depth of 20 m.
In February there was only one halocline at a depth of
20 m. According to Levy et al. (1997), the distribution
of O2 and other constituents in a lake may be affected
by the circulation patterns. In Udden, dissolved O2 was
found down to 20 m, thus indicating a possible seasonal
turnover of the top 20 m in the lake. The February
measurements, showing a rather homogenous top 20 m,
support this assumption.
pH showed the lowest value,
4.8, at the surface of
the lake. Below the halocline (at 20 m) pH increased to

5.5 and remained rather constant down to 35 m,
where it increased to
6.4. Pit lakes created from mines
where sulphide ore has been extracted are often acidic.
Two examples of this are the Spenceville Cu pit in
Nevada USA, with a pH around 2.5 (Levy et al., 1997),
and the Berkeley pit in Montana USA with a pH
around 3 (Davis and Ashenberg, 1989). The reason for
the relatively high pH in Udden is thought to be the
rather strong buffering ability of the surrounding rock,
the shaft tower and the blocks of concrete covering the
underground mine. Another important factor is that
comparatively small areas of sulphurous rock are
exposed at Udden, thus making the continuous produc-
tion of acid rather limited (Nils Eriksson, Boliden, pers.
comm.). The relatively low pH at the surface of the lake
is likely caused by oxidative weathering of mainly pyrite.
From the in situ measurements, 4 distinct layers could
be defined in the pit lake during summer and autumn, as
a result of differences in temperature and salinity (Doyle
and Runnells, 1997). The layers are indicated in Fig. 3
Sampling period
June and August
June, August and September
August
June and August
June, August and September
September
 M. Ramstedt et al. / Applied Geochemistry 18 (2003) 97–108
and will be referred to as layer I, II, III, IV in the fol-
lowing text. In Udden, layer I reaches from the surface
down to the thermocline situated at a depth of approxi-
mately 5 m. Layer II reaches between
5 m and the
halocline at
20 m. Layer III is defined as the section of
water between
20 and
35 m. In this layer the O2
saturation decreases dramatically to reach a value of 0.3
mg/l at 35 m depth. Layer IV stretches from
35 m and
downwards. It is anoxic and the redox potential in this
layer is lower than in the other 3. In February the
uppermost layering, i.e. the thermocline, had dis-
appeared. The different layers found in the Udden pit
lake can be compared with redox layers found in natural
meromictic lakes reported in the literature, e.g. Hall
Lake in Washington, USA. Hall Lake is 15 m deep with
3 redox layers (oxic, suboxic and anoxic layer) which are
each approximately 5 m deep (Balistrieri et al., 1994).
The redox potential (Eh) measured was rather stable
at
500 mV down to a depth of approximately 30 m. In
layer IV Eh decreased with depth to a value of
300 mV
close to the bottom of the lake. The redox readings in
June were unstable and are thus excluded. The degra-
Fig. 2. Physical parameters measured in situ during the period June 1998–February 1999.
101
dation of organic material requires an oxidising agent
and, since there is no mixing vertically, O2 and other
oxidising agents will be depleted. The redox potential is
thus expected to decrease towards the bottom of the
lake in a similar manner as was observed in Udden. The
redox level in the 4 different layers is thought to be
governed mainly by dissolved O2 in layer I and II and
by Fe in layer IV. Which species govern the redox level
in layer III is yet an unresolved question as is the small
but consistent increase in Eh at 20 m. One should bear in
mind that redox potentials measured in natural systems
may be difficult to interpret due to the fact that natural
waters seldom are in internal equilibrium, and the redox
potential measured should rather be viewed as an indi-
cation of the overall redox state of the water. Apparent
redox levels can be calculated based on equilibria
between different redox ‘‘indicator’’ species e.g. dis-
solved O2, Fe(II)/Fe(III), HS-/SO2- 4 etc. (Lindberg and
Runnells, 1984). From these apparent levels, saturation
indices can be calculated for the redox reactions in
question. This approach will result in a constant in
which all uncertainties are accumulated such as errors in
102 M. Ramstedt et al. / Applied Geochemistry 18 (2003) 97–108
redox measurements and non equilibrium status of
the water. Such calculations, with respect to Fe2+/
FeOOH(s) equilibria, will be reported in a later section
of this paper.
4.2. Nutrients and organic carbon
The total concentration of N increased with depth
through the upper 3 layers of the lake, but appeared to
decrease downwards in layer IV (Fig. 4). The con-
centration of N in Udden was much higher compared to
L. Ljusträsket; the concentration near the surface was
twice as high, and at a depth of 30 m almost 5 times
higher than the surface water in L. Ljusträsket (surface
concentrations:
0.5 mg/l in Udden and 0.2 mg/l in L.
Ljusträsket). Although none of the values can be regar-
ded as high for surface waters one should bear in mind
that the Udden pit lake has mainly been filled by a large
inflow of groundwater, which in this area generally
exhibits very low N concentrations. A possible source of
the high total concentration of N is diffusion of remnant
undetonated explosives from the rock walls and the
deposited waste rock. The concentration of N decreases
below 30 m, which can possibly be explained by deni-
trification, i.e. reduction of NO
3 to elemental N2, which
in turn can escape the lake in the gaseous phase.
Fig. 3. Visualisation of the observed layers in the lake. The
layers are numbered from the surface and downwards. Data
from measurements in August 1998 (O2 sat=saturation in %,
cond=conductivity in mS/cm, Eh=redox potential in mV).
The total concentration of P was below 5 mg/l on all 3
sampling occasions. Doyle and Runnells (1997) stated
that meromictic lakes generally are oligothrophic and
have low biological productivity, which also was
observed in Udden. Simultaneously with this study of
the geochemistry of the Udden pit lake, an investigation
of the phytoplankton community in the two lakes was
made (not reported here). The amount of algae was
much lower (
1/10) than in L. Ljusträsket and some of
the plankton species found in Udden are species that are
known to be able to survive in waters with high metal
content (Sofie Absér, pers. comm.).
The concentration of total organic C was measured in
the September samples from each layer of the lake. In
layer I, at 3 m, the concentration was 0.6 mg/l. At 10 m
it was slightly less, 0.4 mg/l. Further down in the lake
the content of organic C increased and at 30 and 45 m it
was 1.0 and 2.7 mg/l, respectively. A comparison of
these concentrations with the concentration in Lake
Ljusträsket shows that the content of organic C in
Udden was low, 0.6 mg/l compared with 5.8 mg/l at 3 m.
The low content of particles and total organic C was also
reflected in the water transparency. The Secchi depth
was 9 m in June and 12 m in September and August.
The lower transparency of the water in June is thought
to be due to an increased amount of algae at that time.
Fig. 4. Concentration of N at different depths in Udden.
 M. Ramstedt et al. / Applied Geochemistry 18 (2003) 97–108 103

4.3. Main elements at that depth and presumably the white particles
observed in September were small particles of gypsum.
For most water samples no significant difference in
concentration could be found comparing the filtered 4.4. Iron, manganese and trace metals
(0.22 mm) and the non filtered samples from the same
depth. Nor could any significant difference be found The concentrations of Fe in mine waters are often
between sampling points A and B. These two observa- high due to the slow oxidation of Fe(II) in acidic water
tions indicate that the water is well mixed horizontally (Nordstrom and Alpers, 1999) and the origin is often
and that the metals present in the water either occur as considered to be weathering of the rock walls (e.g. Davis
soluble species or the colloidal phase passes through the and Eary, 1997; Miller et al., 1996; Levy et al., 1997).
filter. Previous studies by e.g. Kimball et al. (1992) have Bacteria increase the oxidation rate of sulphide miner-
shown that particulate material can pass through the als, especially at low pH (MEND, 1995), and since bac-
filters and, thus, we have chosen to include discussions teria are ubiquitous, the oxidation of rock walls in the
considering possible sorption onto a colloidal particu- Udden pit lake can be considered as micro-organism
late phase although we do not have any data supporting mediated.
this. The concentration profile for Fe in Udden corre-
The profiles for SO2 4 and Cl concentrations sponds well with what could be expected from the redox
strongly resemble those for the conductivity measure- profile, with a rather constant concentration in the
ments (Figs. 2 and 5). The concentration of Cl upper 20 m and a sharp increase in Fe below 35 m
increased downwards in Udden but appeared to be (Fig. 6). It can be expected that Fe(III) dominates under
rather stable within each layer. The origin of this Cl is oxidised conditions, while Fe(II) is stable at greater
probably weathering of Cl-containing silicate minerals. depths with anoxic conditions. However, the high Fe
The largest difference in concentrations was found at the concentrations found in the filtered samples from the
border between layers I and II and between layers II and upper 20 m,
3 mg/l, are much higher than the
III. The concentration of Cl was 5 times as high as in thermodynamic solubility of Fe (oxy)hydroxide in the
L. Ljusträsket at the surface, and 9 times as high in the
bottom water. The SO2 4 concentration profile showed
exactly the same pattern but with a higher concentration
difference between the pit lake and Ljusträsket (Udden
140 – 400 mg/l; L. Ljusträsket 0.7 mg/l). The origin of
SO24 is obviously oxidation of sulphide containing
minerals in the rock walls and waste rock.
The authors attempted to distinguish between SO2 4
and reduced S species in the water samples. However,
samples collected in June and August for analysis of Cl
and SO2 4 , although stored in a freezer until analysis,
showed signs of oxidation in the sense that an Fe oxide
precipitate had formed. This might indicate that the
analysed concentration of SO2 4 possibly represents the
total concentration of S.
The concentrations of Na, K, Mg and Ca increased
downwards in the lake and the depth profile resembles
that of the conductivity. Calcium was the dominating
cation with concentrations of 140 mg/l at a depth of 3 m
and increased levels downwards in the water column to
a concentration of 440 mg/l at 45 m depth. The second
most common cation in the lake was Mg with con-
centrations between 24 and 45 mg/l. The positive
charge, formed by those major cations, is mainly
balanced by SO4 ions. The high concentrations of Ca
and SO2 4 implies that formation of gypsum is possible.
Thermodynamic calculations (using equilibrium con-
stants from Ball and Nordstrom (1991) adjusted with
respect to temperature and ionic strength) result in
saturation indices close to zero in the fourth layer of the Fig. 5. Concentrations of Cl and SO2
4 at different depths in
lake, which indicates that gypsum is likely to be formed the pit lake.
104 M. Ramstedt et al. / Applied Geochemistry 18 (2003) 97–108

current pH-range. This can be caused either by a pro-
nounced disequilibrium explained by slow oxidation
kinetics or by the presence of colloidal Fe(III) (oxy)-
hydroxides which have passed the filter ( <0.22 mm). At
a depth of 20 m, the aqueous concentration of Fe
decreases to below the detection limit and remains low
down to layer IV where the redox conditions are such
that Fe(II) is the stable form.
The distinct decrease in redox potential below a depth
of 32 m is reflected in a sharp increase in dissolved Fe.
This observation agrees with previous findings by Ball
and Nordstrom (1989). One possible explanation for
this observation is reductive dissolution of Fe (oxy)-
hydroxide. Such a reduction can be the result of oxida-
tion of dissolved organic matter (Stumm and Morgan,
1996). The concentration of total organic C at 45 m in
September was of the same order of magnitude as the Fe
concentration i.e. 2.7 mg C/l (0.225 mM), and 27.2 mg
Fe/l (0.49 mM). For each mole of organic C oxidised by
FeOOH, 4 moles of Fe2+ are formed. Thus, the Fe in
solution could be a result of degradation of natural
organic matter. Alkalinity titrations, performed without
complete absence of O2, gave alkalinity values of 0.01
mM at 0.5 and 5 m, 0.45 mM at 25 m and 2.3 mM at 45
m. Since a possible oxidation of reduced species, such as
Fe(II) and Mn(II), by dissolved O2 would result in
release of protons, these values represent a minimum
alkalinity and should not be considered as the actual
alkalinity of the lake. However, the alkalinity trend also
supports the hypothesis of reductive dissolution of
FeOOH. Another possibility is reduction of Fe(III) in
secondary precipitates during oxidation of reduced S
species, such as pyrite, since it is well known that Fe3+
ions are actively involved in sulphide oxidation (e.g.
Moses and Herman, 1991; Herbert, 1999). A third
option might be dissolution of Fe-containing sulphide
minerals without involvement of redox processes.
Saturation indices (SI) have been calculated based on
the aqueous concentrations of Fe in layer IV and the
corresponding pH and Eh values, in order to examine
wheter reductive dissolution (1) of Fe (oxy)hydroxides is
a likely origin of Fe2+ in layer IV.
(oxy)hydroxide and crystalline goethite (constants from
Ball and Nordstrom, 1991) under the assumption that
Fe was present in the aqueous phase as Fe(II). SI for
amorphous Fe (oxy)hydroxide, calculated for condi-
tions at the depths 40 and 47 m, was 1.2 at both depths.
SI for goethite was 1.8 at 40 m and 1.7 at 47 m. These
SI-values indicate a super-saturation at the bottom of
the pit lake. Similar results have been reported by
Nordstrom and Alpers (1999) and Holmström et al.
(2000). There are several possible explanations for
deviations of SI from zero, e.g. presence of colloidal Fe
(oxy)hydroxides and existence of mixed Fe (oxy)hydr-
oxide phases with unknown solubility. Another uncer-
tainty is related to temperature effects. Since no H
value is available for the reductive dissolution of
Fe(OH)3 no attempt was made to correct this calcula-
tion with respect to temperature. Finally, uncertainties
in the redox measurements may result in significant
deviation of SI from the ideal value of zero. However,
the calculations indicate that the origin of the high con-
centrations of Fe in layer IV might be reductive dis-
solution of FeOOH(s) to form Fe(II).
The observed aqueous concentration of Mn in Udden
was between 4 and 9 mg/l and increased downwards
through the water column in the same way as the con-
centrations of Ca, Mg, K and Na (Fig. 6), i.e., Mn is
apparently not influenced by changes in redox potential
in Udden, unless the oxidation results in formation of
colloidal sized particles. The Mn present in the lake is
most likely in the form of Mn2+ ions, since Mn(III) and

Fe2þ þ 2H2 O $ FeOOHðsÞ þ 3Hþ þ e ð1Þ

SI is defined according to Eq. (2).

IAP
SI ¼ log ð2Þ
K

where IAP is the ion activity product and K is the equi-

librium constant for formation of the solid phase. SI for
a solution in equilibrium with a particular solid phase is
ideally zero, while super-saturation is reflected by posi-
tive values and under-saturation by negative values. In Fig. 6. Concentration of Mn, Fe and As at different depths
this case, SI was calculated for both amorphous Fe during June, August and September.
 M. Ramstedt et al. / Applied Geochemistry 18 (2003) 97–108
Mn(IV) (oxy)hydroxides dissolve at lower pH. Besides
being more thermodynamically stable than Fe(II), the
oxidation of Mn2+ is known to be a considerably slower
process than Fe2+ oxidation (Stumm and Morgan, 1996).
The concentration profile for As in Udden shows
similarities to the profile for Fe (Fig. 6), i.e. low con-
centrations down to a depth of 35 m and increasing
concentrations with depth in layer IV. This observation
may be explained by a release of adsorbed As from sur-
faces of colloidal Fe (oxy)hydroxide or could be a con-
sequence of reductive dissolution of FeAsO4 and/or
oxidative dissolution of FeAsS by Fe(III) originating
from secondary Fe minerals in the deposited waste.
Arsenic can exist either as As(V) or as As(III), either
way it is present as oxyanions, HnAsO3n3 or
HmAsO4m3 (n, m=0,1,2,3).
Both forms can be adsorbed onto surfaces of Fe
(oxy)hydroxides, a process which is to some extent pH
dependent. Arsenic has been shown to adsorb onto Fe
(oxy)hydroxide within a wide pH range (pH 3–10),
although the adsorption is strongest at lower pH (Lüt-
zenkirchen and Lövgren, 1998). The pH of the Udden
pit lake (pH 4.5–6.5) is within the range of pronounced
As adsorption and, thus, if colloidal Fe (oxy)hydroxides
are present, the origin of As is likely to be the reductive
dissolution of these.
The concentration of Pb was rather constant around
1 mg/L through the first two layers and decreased in the
upper part of layer III, where the O2 concentration also
decreased (Figs. 2 and 7). The concentration remains
Fig. 7. Concentration of Cu, Pb, Ni, Zn and Cd at different depths in the pit lake.
105
low through layers III and IV. Comparing these con-
centrations with guideline concentrations for surface
water provided by the Swedish Environmental Protec-
tion Agency (Naturvårdsverket), shows that the Pb
concentrations would be classified as low concentrations
(Naturvårdsverket, 1999).
The Cu concentration increased from
80 to
140
mg/l at the interface between layers I and II (Fig. 7). The
concentration is rather stable within layer II but
decreases dramatically in the upper parts of the suboxic
layer III and even more in layer IV.
The concentrations of Cd and Zn are higher in layer
II compared to layer I (Fig. 7). The concentrations
increase downwards through the second layer, drop
slightly just at top of the suboxic layer III and decrease
downwards in the same layer and finally, in layer IV, the
concentrations decrease to a level equal to or below the
concentration at the surface. The dip in the concentra-
tion curves for Zn and Cd at approximately 20 m
appears at the same depth as the temporary rise in the
redox profiles. Nickel concentrations are highest in layer
II (
450 mg/l) and decrease towards the bottom of the
lake similarly to Cd, Zn, Pb and Cu (Fig. 7).
Metals expected to precipitate as sulphides under
anoxic conditions are e.g. Pb, Cu, Zn, Cd and Ni. Thus,
the aqueous concentrations of these metals could be
expected to decrease across an oxic–anoxic interface.
Since the solubility of metal sulphides is increasing in
the order CuS < PbS
CdS <ZnS
NiS < FeS< MnS
(Nordstrom and Alpers, 1999), CuS can be expected to
106 M. Ramstedt et al. / Applied Geochemistry 18 (2003) 97–108

form before CdS and ZnS. At high concentrations of
sulphide, aqueous sulphide and bisulphide complexes
may be formed, which would lead to increased metal
solubility (Balistrieri et al., 1994). However, the
observed redox potentials in Udden, even at the greatest
depths, are all in a range unfavourable for SO24 reduc-
tion. Thus, the concentration of sulphides can be
expected to be low and the precipitation of metals as
metal sulphides should therefore be limited and the
formation of bisulphide complexes nonexistent. On the
other hand, the redox potential measured is an average
redox level and will mainly be influenced by the high
amounts of Fe in solution. Thus, sulphide species might
have been formed in the bottom water without affecting
the measured redox potential. Furthermore, sulphide
minerals, such as pyrite (FeS2), may dissolve to a certain
extent in contact with water and form free metal ions
and sulphide ions, as well as other reduced S anions.
Slow oxidation kinetics would allow this sulphide to
react with heavy metals in the water and form solid
metal sulphides. It seems likely, from the data obtained,
that the metals in the suboxic and anoxic region are to a
large extent associated with solids which are removed
from the water column by settling. However, the
authors do not have any data supporting precipitation
of metal sulphides and pH is too low for formation of
metal oxides. The mechanism behind trace metal
removal from the water column in Udden at large
depths is yet to be resolved.
Correlation coefficients between the different elements
and the different physical parameters were calculated.
High correlation coefficients were obtained between
conductivity, Ca, K, Na, Mg, S, Si, Mn, and Sr con-
centrations. The redox potential strongly correlates with
Cd and Fe concentrations, and Al, Ba and Cu con-
centrations are correlated with pH. The strong correla-
tion between conductivity and the different metals
mentioned is not surprising since the conductivity is a
measure of charged ions and particles.
4.5. Temporal trends
The Udden pit lake has been sampled by Boliden AB
on several occasions since 1993 as part of a monitoring
programme. A decrease in metal concentrations from
1993 to 1998 can be noticed (Table 3). This may be the
result of a number of processes. Some of the metal ions
that were leached from the deposited waste material and
the rock walls after flooding may have adsorbed onto
settling mineral particles or precipitated as secondary
minerals. Furthermore, the weathering of the pit walls
and waste rock can be expected to be substantially
reduced. The observed trend is an indication of a suc-
cessful decommissioning of the pit mine. However, it
should be noted that the exchange of water between the
pit and its surrounding soil and bedrock has not been
quantified. There is no inflow of surface water into the
lake besides the annual precipitation, which in this area
is fairly low, 518 mm in 1999 (P. Lindström, Boliden,
pers. comm.). The only other sources of water are
groundwater and the increased amount of surface runoff
during the spring when the snow melts. The rapid filling
of the abandoned pit implies a large flux of ground-
water, however, the topography of the area does not
indicate the presence of a large hydraulic gradient after
the pit was filled. The extent to which decreased metal
concentrations can be explained by an outflow of water
through the ground is an open question. However, the
stability in e.g. temperature, redox potential, SO2
4 and
Cl concentrations suggests a rather low flux of water.

Table 3
Water quality data for surface water collected in Udden pit lake previously and during 1998

Date Cu (mg/l) Zn (mg/l) Pb (mg/l) Cd (mg/l) Cond (mS/m) SO2-

4 (mg/l) pH (units)

Surfacea 93–11–16 0.17 51.6 62 0.08 160 976 4.7

Surfacea 94–08–03 0.17 81.1 10 0.13 184 1270 5.8

Surfacea 95–05–29 0.04 14.8 18 0.024 66 303 5

Surfacea 95–06–09 0.11 2.58 6 29.5 932 2.7
Surfacea 95–08–16 0.12 67.3 8 0.11 174 1081

Surfacea 98–05–19 0.03 2.15 18 34.5 172 4.3

Surfacea 98–08–12 0.10 35.0 26 98.0 746 5.9
0.5 m 98–06–25 0.076 33 0.66 0.033 93 159 5.14
98–08–06 0.086 34 1.2 0.036 95 148 4.93
98–09–14 107 4.87

Surface=surface water.
Cond=conductivity.
a
=Data collected by the monitoring programme at Boliden (unpublished data).
 M. Ramstedt et al. / Applied Geochemistry 18 (2003) 97–108
4.6. Comparison with other pit lakes
In comparison with other pit lakes described in the
literature, the water quality of the Udden pit lake is
relatively good in terms of pH and heavy metal content.
However, the concentrations for most metals are much
higher than background concentrations and guideline
concentrations given for lake and surface water by
Naturvårdsverket (1999). The extent to which the higher
pH can be explained by the acid neutralising effect of
the concrete, in e.g. the shaft tower, or a high buffering
ability of the surrounding rock cannot be deduced from
the present data. The content of Fe, Cu, Zn, Cd and
SO24 is much higher than in natural lakes due to dis-
solution of old weathering products and weathering of
sulphide minerals. Comparing the concentrations found
in Udden to those in Berkeley pit and in the Spenceville
Cu pit, the metal concentrations in the Udden pit lake
generally appear to be lower. Comparing the different
pit lakes mentioned in Miller et al. (1996), it can be
observed that pit lakes with higher pH tend to have
lower aqueous metal concentrations. This can be due to
several mechanisms: decreased solubility of both pri-
mary and secondary mineral phases and increased
adsorption to particle surfaces, mainly secondary Fe
(oxy)hydroxides. The oxidation rate of sulphides is also
higher in acidic waters. Comparison of the results from
Udden with measurements made in Hall Lake (Balis-
trieri et al., 1994) shows a similar behaviour of 3 ele-
ments measured in both lakes (Cu, As, Zn). Hall lake is
a natural lake and most metals in this lake precipitate
below the anoxic border where sulphide is generated.
5. Conclusions
Four distinct layers could be observed in the Udden
pit lake from the measurements performed during sum-
mer and autumn 1998. The layers seem to be established
due to temperature gradients and differences in salinity
in the water column. A thermocline and a markedly
increased salinity were found at a depth of
5 m during
summer, separating layer I from layer II. Layers II and
III are separated due to a change in salinity at a depth
of
20 m. A redoxcline seems to have been formed at a
depth of
35 m as a result of this layering. The strati-
fication of the lake leads to depletion of oxidising agents
and the oxidation of organic material may occur differ-
ently in the 4 layers. The metal concentrations were
rather stable throughout the entire period, but differ-
ences in concentration could be observed at different
depths. Iron and As showed a pronounced increase
below
35 m where Fe(II) is thermodynamically stable.
Lead concentrations decreased downwards in the lake.
The concentrations of Cu increased significantly at a
depth of
5 m and remained at that level down to a
107
depth of
20 m, below which they decreased. The Cd
and Zn concentration profiles showed similar patterns
to Cu but with a less striking increase at
5 m. The
decrease of Cu, Cd, Pb and Zn may be explained by
precipitation of the metals as sulphides, although it
should be noted that the measured redox potential at
this level is too high to support SO4 reduction. The
dominating anion in the lake is SO2
4 and the concentra-
tion of SO24 increases downwards in the water column
but appears to be rather stable within each layer
observed. Close to the bottom of the lake the con-
centration of SO24 is at a level corresponding to the
solubility of gypsum.
This investigation is a description of the prevailing
geochemical conditions in the Udden pit lake. For an
improved and more complete understanding it would be
necessary to also include a detailed hydrological study
to form the basis for mass balance calculations. With
more knowledge of sediment composition, sediment
depth and composition of the colloid phase together
with a detailed hydrological study, it would be possible
to gain a better understanding of different processes in
the lake.
Acknowledgements
The authors would like to thank Nils Eriksson, Johan
Ljungberg, Staffan Sjöberg, Kristina Axe, Julia Sheals
and two anonymous referees for valuable comments on
the manuscript and Milan Vnuk for help with the site-
map. The field study was financed by Boliden Mineral
AB. This work was also supported by funds from the
Foundation for Environmental Strategic Research
(MISTRA) provided to the senior author (L.L.) through
the research programme MiMi (Mitigation of the
Environmental Impact of Mining waste).
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