Chemosphere 81 (2010) 1155–1158

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Chemosphere
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Technical Note

Electromigration of arsenic and co-existing metals in mine tailings

Pirjo Isosaari a,⇑, Mika Sillanpää b,c
a
Department of Civil and Environmental Engineering, Aalto University School of Science and Technology, P.O. Box 16200, FI-00076 Aalto, Finland
b
Department of Environmental Science, Laboratory of Applied Environmental Chemistry, University of Eastern Finland, Patteristonkatu 1, FI-50100 Mikkeli, Finland
c
Faculty of Technology, Lappeenranta University of Technology, Patteristonkatu 1, FI-50100 Mikkeli, Finland

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this study was to investigate the feasibility of enhanced electrokinetic remediation technology
Received 2 May 2010 for controlled leaching and collection of labile arsenic fractions from mine tailings. Direct current was
Received in revised form 4 September 2010 applied to tailings for 20 d using ammonium oxalate and sodium hydroxide as enhancement solutions.
Accepted 6 September 2010
Migration of arsenic was observed, resulting in 63–71% removal near the cathode but only 6–17% overall
removal in the entire tailings matrix in 20 d. However, significant migration of arsenic towards the anode
and accumulation in a collection well near the anode was observed, especially under alkaline conditions.
Keywords:
Thus, treatment time and consumption of chemicals could probably be reduced by installing specific col-
Arsenic
Electrochemical remediation
lection or adsorption zones near the anode. A relationship between electrokinetic mobility of arsenic and
Electromigration other elements and their extractability in sequential extraction tests was established, indicating that dis-
Oxalate extraction solution or desorption of the elements and thermodynamic conditions (pH and Eh gradient) played a big-
Tailings ger role in the electrokinetic removal process than electromigration of soluble ions.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction more experience is needed to adjust the process for a specific

Arsenic is a metalloid that widely occurs in copper, lead and
gold ores but it is also associated with several other metals, includ-
ing mercury, silver, tungsten, uranium and zinc (Mandal and
Suzuki, 2002; Ahn et al., 2005; Slowey et al., 2007). Exploitation
of arsenic-bearing minerals has generated large deposits of tailings
with arsenic concentrations up to 67.3 g kg 1 (Wang and Mulligan,
2006; Lim et al., 2009). The highest risk of arsenic leaching from
tailings is related to secondary mineral phases. In unaltered sul-
phide ores, arsenic is often associated with pyrite (FeS2) and arse-
nopyrite (FeAsS) minerals that are considered to be stable in the
short term (Savage et al., 2000). However, weathering processes al-
ter the affiliation and mobility of arsenic. In oxidized layers, sec-
ondary Fe (oxy)hydroxides and arsenates are precipitated. They
adsorb arsenic, but this is a labile sink and subject to remobiliza-
tion under reduced or alkaline conditions, due to microbial activity
and leaching by organic acids (Savage et al., 2000; Salzsauler et al.,
2005; Delemos et al., 2006; Lee et al., 2010).
Electrokinetic, or electrochemical, remediation technology
could be possibly used to reduce the environmental risks of tailings
by enhanced removal and collection of arsenic from the labile
phases, while leaving the more stable phases intact. However,
⇑ Corresponding author. Tel.: +358 40 7714 711.
E-mail address: pirjomail@gmail.com (P. Isosaari).
matrix and pollutant type, taking the geochemistry into account.
Some researchers have investigated electrokinetic removal of Cu,
Zn and Pb from mine tailings and tailings-impacted soils (Kim
and Kim, 2001; Rojo et al., 2006; Garcia-Gutierrez et al., 2007;
Hansen et al., 2007). However, only few studies have been carried
out on arsenic-bearing tailings, showing problems with pH control
and precipitation of co-leaching metals (Kim et al., 2005; Baek
et al., 2009). It might be possible to avoid some of the problems
associated with arsenic mobility by using different enhancement
agents, such as ammonium oxalate [(NH4)2C2O4] that is one of
the widely used chemicals in sequential extractions (Sondag,
1981; Cardoso Fonseca and Martin, 1986; Dold, 2003). Another op-
tion would be to install a collection well near the anode to collect
arsenic before it enters the acidic zone and becomes uncharged.
These kinds of collection or treatment zones have been applied
in a few contexts before: for contaminated soil remediation using
the Lasagna technology (Ho et al., 1995), for electrodialytic cleanup
of chromated copper arsenate (CCA) -treated wood chips (Pedersen
et al., 2005) and for a remediation technology that combines elec-
trokinetics with a permeable reactive barrier (Yuan and Chiang,
2007).
The aims of this study were to assess whether electrokinetic
treatment enhanced by NaOH and ammonium oxalate could be
used to dissolve arsenic from the labile mineral phases of tailings
and transport it to the anode or a collection well, and how the
treatment affects the dissolution and transportation of co-existing
metals.

0045-6535/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2010.09.019
1156
2. Material and methods
2.1. Properties of the tailings
Tailings were excavated from a tailings pile of the former
Ylöjärvi mine (1943–1966) that was exploiting chalcopyrite
(CuFeS2), scheelite (CaWO4) and arsenopyrite, though arsenopyrite
concentrate was recovered only for 5 years. The tailings material
was mixed thoroughly in the laboratory and stored at 4–6 °C. Ini-
tial pH of the tailings was 4.8 and cation exchange capacity was
4.54 meq 100 g 1. Laser diffraction analysis showed that 63% of
the particles (volume-based) were <64 lm in diameter. Surface
area of the particles was 4.16 m2 g 1, determined using the BET
method based on gas adsorption. Initial metal and metalloid con-
centrations in tailings were analyzed by ICP-AES after aqua regia
extraction at 90 °C. All these analyses were carried out at the
laboratories of Labtium and Outotec Research.
2.2. Electrokinetic experiments
Two 600-g portions of wet tailings were mixed with 25 mL of
water purified by reverse osmosis, spread evenly into electroki-
netic cells (Fig. 1) and covered with plastic sheets. Electrolyte
chambers and a collection well were separated from the tailings
by nylon cloth. A constant current of 30 mA was applied to parallel
electrokinetic cells via inert Pt-coated Ti-mesh electrodes for 20 d.
Owing to the differences in electric conductivity, the average cur-
rents were different in Exp. 1 and Exp. 2: 15 ± 4 mA
(0.78 mA cm 2) and 16 ± 4 mA (0.86 mA cm 2), respectively. Volt-
age gradient between the working electrodes was 106 V m 1 at
its maximum at the beginning of the experiments and 41 V m 1
at its lowest after 10 d of treatment.
In Exp. 1, the cathode chamber was filled with 0.1 M ammo-
nium oxalate and adjusted daily to pH 10 with 1 mL of 10% oxalic
acid and 0.1–0.5 mL of concentrated HNO3. The anode chambers
and collection wells were filled with 0.2 M NaNO3 and adjusted
daily to pH 2 with 1.0 M NaOH. In addition, pH in Exp. 2 was raised
to 10 every 2 d. The electrolyte solutions were replaced with fresh
ones on day 10 and 15. On the other days, the electrolyte chambers
and collection well were filled with water to the original level. The
consumption of NaOH as a 1.0 M solution was 104 mL in Exp. 1 and
138 mL in Exp. 2.
The cumulative volumes of electroosmotic flow were 384 mL in
Exp. 1 and 403 mL in Exp. 2. NaOH additions probably prevented
development of excessively acidic conditions and reversal of elec-
troosmotic flow.
2.3. Sequential extraction tests
In order to predict the mobility of arsenic and other metals,
tailings material was extracted using a five-step sequential extrac-
tion procedure. Details of the extraction procedure are given in
Parviainen (2009). In brief, the following fractions were obtained
Anode (+)
collectionwell
anolyte
tailings
tailings
A (0-3 cm) B (6-13 cm) C (13-20 cm)
Fig. 1. Side view of an electrokinetic cell showing sampling sections A, B and C with
distances from the anode.
P. Isosaari, M. Sillanpää / Chemosphere 81 (2010) 1155–1158
from a 1 g sample of dried tailings: (1) ‘‘water-soluble” fraction, ex-
tracted with distilled water, (2) adsorbed-exchangeable-carbonate,
‘‘AEC’’ fraction, extracted with 1 M sodium acetate, (3) ‘‘Fe(III)
(oxy)hydroxides’’ fraction, extracted with 0.2 M ammonium oxa-
late in the dark, (4) ‘‘Fe(III) oxides’’ fraction, extracted with hot
0.2 M ammonium oxalate, and (5) ‘‘sulphides” fraction, extracted
with potassium chlorate (KClO3) and HCl and hot 4 M HNO3.
3. Results and discussion
3.1. Transportation and solubility of arsenic
Arsenic was clearly migrating from the cathode section (section
C) towards the anode, although the overall removal efficiencies
were low (Fig. 2). In Exp. 1, only 6% of arsenic was removed from
tailings while most of it accumulated in the middle section (section
B) and did not reach the anode section (section A). Actually, arsenic
content in section A decreased by 25%, which might be due to the
leaching of arsenic to the anode chamber or possibly electroos-
motic transportation to section B. In Exp. 2, arsenic migrated up
to the anode section (section A), accumulated there, and the total
arsenic removed from tailings accounted for 17% of the initial ar-
senic content. The higher removal was concurrent with the higher
pH in the middle section in Exp. 2, that facilitated As migration fur-
ther than in Exp. 1. At the end of the Exp. 2, the tailings pH was 2.8
in section A, 8.8 in section B and 10.3 in section C, whereas pH val-
ues of 2.9, 6.4 and 9.5 were measured from the corresponding sam-
ples from Exp. 1. The better mobility at higher pH might be related
to the weaker adsorption of anions to soil particles, deprotonation
reaction of H2 AsO4 to a more highly charged HAsO24 with a pKa
value of 6.8 or reduction to H3AsO3 at lower pH (Goldberg and
Johnston, 2001; Salzsauler et al., 2005). In previous electrokinetic
remediation studies, up to 66% of arsenic has been removed using
0.1–0.5 M NaOH as an anolyte solution for a more complete alka-
linisation of tailings (Kim et al., 2005; Baek et al., 2009).
In water samples, the highest arsenic contents were analyzed
from the collection wells: 22 mg in Exp. 1 and 44 mg in Exp. 2.
Some arsenic was also transported to the anolyte (1.6 and
5.5 mg), but hardly anything (<1 mg) was detected from the cath-
olyte solution. Thus, transportation to the anode via electromigra-
tion seemed to dominate over electroosmotic transportation to the
cathode, although these processes could not be distinguished. With
respect to the mass balance between the solid (tailings) and aque-
ous phase (‘‘waste water” sampled from the collection well), 71% of
the arsenic content that was removed from the tailings during the
20-d treatment, was transported to the collection well in Exp. 1
and 49% in Exp. 2, during the last 5 d. Thus, a significant quantity
seems to have been removed during the last 5 d of the experiments
Cathode (-)
catholyte
Fig. 2. Residual concentrations (final/initial concentration, c/c0) of arsenic in
tailings samples A (anode section), B (middle section), C (cathode section) and
total (average weighted by tailings mass fraction) after Exp. 1 and Exp. 2.
 P. Isosaari, M. Sillanpää / Chemosphere 81 (2010) 1155–1158
and lengthening of the treatment duration by another 5–10 d could
have resulted in the higher efficiency of the process.
According to the sequential extraction tests, a majority (80%) of
arsenic in untreated as well as treated tailings was soluble in
ammonium oxalate at room temperature, suggesting that oxida-
tion of the original arsenic-bearing sulphides had produced sec-
ondary Fe(III) oxyhydroxide minerals in which arsenic was
associated. Comparison of untreated and treated tailings showed
no major influence of the ammonium oxalate-enhanced electroki-
netics on arsenic fractionation in sequential extractions. Therefore,
it could not be confirmed whether the electrokinetic treatment re-
moved arsenic from the oxalate-extractable and more labile frac-
tions in particular, as desired, and not from the more stable
sulphides fraction.
3.2. Transportation and solubility of other elements
Transportation of elements other than arsenic was also ob-
served. The elements can be divided into four groups based on
their transportation patterns: (I) elements accumulating near the
anode, (II) elements accumulating near the cathode, (III) elements
accumulating in the middle and (IV) immobile elements (Fig. 3).
Fig. 3. Migration patterns of different elements in tailings.
1157
In group I, accumulation of Pb, to a concentration higher than
initially, was evident in the tailings section nearest to the anode,
even though the total amount of Pb in tailings remained un-
changed. S and Mo were not only transported towards the anode
but also removed from the tailings by 89–90% and 47–56%, respec-
tively. S and Mo, as well as As and B, are anion-forming elements
that are preferably desorbed under alkaline pH and transported to-
wards the anode (Smedley and Kinniburgh, 2002). Under the low-
pH conditions near the anode their migration is likely to be
retarded.
In group II, concentrations of Ca, Co, Ni and Sr increased gradu-
ally towards the cathode, suggesting that they were mainly present
as cations. Changes in the total amounts of these elements were
within 21% of the initial. Na, that was added to the anode during
the treatments, accumulated in tailings by three to fivefold, and
the highest concentrations were found in the cathode section (sec-
tion C), indicating that it was easily migrating through the tailings.
Incomplete migration either towards the anode or the cathode
resulted in concentration peaks of As, Cd, Cu, Zn, and to a lower ex-
tent, Cr and P, in the middle section (group III), but the total con-
tent of these metals in the tailings did not decrease. Boron, on
the other hand, was also removed by 36–42%. Migration of arsenic
1158 P. Isosaari, M. Sillanpää / Chemosphere 81 (2010) 1155–1158
followed this pattern in Exp. 1, but in Exp. 2 it rather fell to the
group A. The amounts of Cu and Zn increased by 30–43% and
170–208%, respectively, inferring to a source of these metals in
the applied chemicals or occurrence of some mineral particles rich
in Cu and Zn in the tailings sample.
Elements that remained homogeneously distributed within tail-
ings included Al, Ba, Fe, K, Mg and Mn (group IV). The difference in
the migration patterns of arsenic and arsenic-adsorbing Fe may be
explained by the fact that Fe was mainly associated with sulphide
fraction rather than Fe(III) oxyhydroxide fraction. In addition, re-
lease of arsenic does not require that Fe minerals are also dis-
solved, if arsenic is adsorbed on Fe minerals rather than forming
inner-sphere complexes (Cheng et al., 2009).
Previously, a strong relationship between high electrokinetic re-
moval efficiency and association of Cd, Cu, Zn and Pb with mobile
mineral fractions has been established (Kim and Kim, 2001). In our
case, the removal efficiencies were relatively low. However, the
above-mentioned migration patterns of different elements seem
to be related to the extractabilities of those elements. Based on
sequential extraction tests, the elements that were the most mo-
bile in electrokinetic tests (Ca, Co, Ni, S and Sr) were significantly
present in the water-soluble and AEC fractions (36–95%). Only
the fractionation of Pb and Mo could not be reliably assessed by
sequential extraction due to the low concentrations. The metals
that were immobile (Al, B, Fe, Mg, Mn) were associated with the
sulphide fraction (72–96%) with less than 22% in water soluble
and AEC fractions, but K was an exception that was mostly in the
AEC fraction. The semimobile fraction was not so distinctive: As,
Cd and Cr were significantly associated with the first and second
oxalate fractions (96–100%), but B, Cu and P to a lesser degree
(29–52%), and Al and Zn were mostly in the sulphide fraction.
The observed mobilities in electrokinetic tests were not well ex-
plained by the theoretical ionic mobilities of metal ions. Those ions
with the highest ionic mobilities (K+, Fe3+, Al 3+, Pb2+) did not seem
to move at all: only Pb2+ was mobile. On the other hand, Na+, Ni2+
and Zn2+ should have had lower mobilities than they had in prac-
tise (Kim et al., 2009). The results suggest that dissolution kinetics
from the mineral particles and thermodynamic conditions (pH and
Eh gradient) played a bigger role in the electrokinetic removal pro-
cess than electromigration of soluble ions.
Acknowledgements
Annika Parviainen is warmly thanked for her advice in tailing
mineralogy and geochemistry. This study was funded by the Acad-
emy of Finland, decision number 114259.
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