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ISSN 0734242X
Waste Management & Research
2010: 28: 430435
DOI: 10.1177/0734242X09351905

Effect of natural pozzolans as mineral admixture on

the performance of cemented-paste backfill of
sulphide-rich tailings
Bayram Ercikdi, Ferdi Cihangir, Ayhan Kesimal, Haci Deveci, brahim Alp
Department of Mining Engineering, Faculty of Engineering, Karadeniz Technical University, Trabzon, Turkey

This paper presents the effect of the natural pozzolans as mineral additives on the short- and long-term strength and stability
performance of cemented paste backfill (CPB) samples. Prior to their use in CPB studies, the natural pozzolans the volcanic
tuffs (Akkus Trass [AT] and Fatsa Trass [FT]) and pumice (KP) were tested for their pozzolanic characteristics. These tests
revealed that the pozzolanic activity of the natural pozzolans is closely inter-related with their content of reactive silica and,
accordingly, KP has the highest pozzolanic activity. The addition, or increasing the amount, of natural pozzolans in the binder
phase resulted in a slower rate of strength development of CPB samples. The deterioration in stability of CPB samples prepared
from Portland cement (PC) alone (i.e. a strength loss of 24.6%) occurred following 56 days. The replacement of PC with FT and
AT led to even higher losses in strength. However, the addition of KP (up to 30 wt%) mitigated, to a certain extent, long-term
strength and stability problems with the losses in strength of CPB samples consistently lower than 20%. It can be inferred that
the performance of the natural pozzolans as a mineral additive in CPB is dependent intimately on their pozzolanic character-
istics.

Keywords: cemented paste backfill, natural pozzolan, sulphide tailings, waste management, mine and environment

Introduction
Increasingly, large quantities of potentially hazardous sul-
phide tailings (e.g. 3.5 and 5 million tonnes in 2005 and 2008,
respectively) are annually produced in base metal mining
and milling operations in Turkey (DPT 2007). In recent years,
some mining projects have not been further developed due
to the public concern for the environmental issues associ-
ated with the management of mine waste and mill tailings
(Hill 2008).
The management of tailings is a costly operation, typically
accounting for 1.52.0% of total operating costs in both zinc
and copper operations (Knapman 2001). The improper dis-
posal/storage of the tailings under atmospheric conditions
may lead to environmental problems (i.e. the formation of
acid mine waters and the release of heavy and toxic metals).
In recent years, cemented paste backfill (CPB) technology
has gained importance, since all the mill tailings produced in
mineral processing operations can be placed safely into the
underground openings created during ore production (Yilmaz
et al. 2004). This reduces the tailings disposal and rehabilita-
tion costs, and renders the mining operations more environ-
mentally friendly.
CPB is produced from dewatered process tailings (70
85% solids by weight), a hydraulic binder (38% by weight)
and mix water. The long-term stability problems experienced
with CPB made with high sulphide tailings are probably asso-
ciated with the formation of acid and sulphate via the oxida-
tion of the pyrite present (i.e. acid and sulphate attack; Kesi-
mal et al. 2004). The resistance of the binder to sulphate
attack was identified as the most influential factor determin-
ing the performance and stability of CPB when sulphide-rich
tailings were used (Ercikdi et al. 2009a).
The addition of binder (38% by weight) provides strength
and stability to CPB, which is required to produce an uncon-
fined compressive strength of 0.72 MPa at 28 days (Brake-
busch 1994). Binder costs represent 5080% of the operat-
ing costs (approximately US$1.00 per ton of paste backfill)

Corresponding author: Bayram Ercikdi, Mining Engineering Department, Engineering Faculty, Karadeniz Technical University, 61080 Trabzon, Turkey
E-mail: bercikdi@ktu.edu.tr
Received 4 December 2008; accepted in revised form 22 September 2009

430
 Natural pozzolans and the performance of cemented-paste backfill

in a CPB plant (Benzaazoua et al. 2004). In this regard, the
optimization of binder dosage and/or the utilization of cost-
effective binders without affecting the performance of CPB
are of practical importance. The use of pozzolanic materi-
als was driven mainly by the availability of these materials
at low cost and by their potential to improve binder proper-
ties (in particular, workability, permeability and resistance
to sulphate attack) and, hence ultimately, to enhance the
strength and durability performance of CPB (Ercikdi et al.
2009b).
Natural pozzolans (e.g. volcanic tuff, pumice, etc.), which
are extensively used in the production of blended cements,
may be considered as an alternative and cheap source of poz-
zolanic material for CPB. These natural materials are also
readily available in countries such as Turkey, which has vast
resources with almost 155,000 km2 of the country being cov-
ered by rocks of volcanic origin (Turkmenoglu & Tankut
2002). Despite extensive research on artificial pozzolans, the
use of natural pozzolans in CPB has received apparently no
attention. In this study, the performance of natural pozzo-
lans (volcanic tuffs and pumice) for the partial replacement
of Portland cement in CPB was evaluated over 7360 days of
curing periods. The physical, chemical and pozzolanic char-
acteristics of the natural pozzolans were examined and cor-
related with their performance in CPB.
Materials and methods
Tailings material
The experimental sample was obtained from the tailings
stream of a copperzinc mill located in the northeast of Tur-
key. Fines (20 m) content of the tailings was determined to
be 40% using a Malvern Mastersizer.
The tailings were rich in sulphide (sulphide content
26.2%) and pyrite was identified as the major sulphide com-
ponent of the tailings sample. Further detailed physical,
chemical and mineralogical properties of the tailings used in
this study can be found elsewhere (Ercikdi et al. 2009a,b).
Binder reagents
Ordinary Portland cement (CEM I 42.5) was used alone and
in combination with the natural pozzolans at different replace-
ment levels (1030% by weight). Two different volcanic tuffs
(Akkus Trass [AT] and Fatsa Trass [FT]) and pumice (KP)
were used as natural pozzolans. The physical and chemical
characterization of the natural pozzolans (Table 1) were per-
formed according to the methods specified in TS EN 196-2
(2002) and TS EN 196-6 (2000). Reactive silica content of
the natural pozzolans was determined as specified in TS EN
197-1 (2002). Pozzolanic activities of the samples (AT, FT
and KP) were determined using graded standard sand as pre-
scribed by TS 25 (1975).

Table 1: Chemical and physical properties of Portland cement (CEM I) and the natural pozzolans (volcanic tuffs, AT and FT, and pumice, KP)
used in the tests.

Characteristic PC (%) AT (%) FT (%) KP (%)

Chemical composition
SiO2 20.3 55.8 57.3 62.8
Reactive SiO2 35.0 25.9 55.9
Al2O3 5.9 16.1 18.6 16.2
Fe2O3 2.8 6.9 4.7 3.8
CaO 61.0 8.6 5.7 2.9
MgO 1.2 4.0 1.5 0.8
SO3 3.0 0.2 0.2 0.1
Na2O 0.3 2.2 2.8 2.9
K2O 1.1 2.2 4.0 2.5
TiO2 0.5 0.8 0.7
Cl 101 ppm 67 ppm 85 ppm 18 ppm
Free CaO 1.1 ND ND ND
Residue 1.2 ND ND ND
Loss-on-ignition 3.8 3.1 3.7 6.8
Physical properties
Specific gravity (g cm3) 3.01 2.65 2.58 2.41
2 1
Specific surface (cm g ) 4345 4940 6975 7710
Grinding time (min) ND 90 90 45
Retained on 200 m sieve (%) 0.6 0.2
Retained on 90 m sieve (%) 2.2 17.3 10.7 1.0
Retained on 45 m sieve (%) 15.8 40.3 27.7 11.8
ND, Not determined.

431
B. Ercikdi, F. Cihangir, A. Kesimal, H. Deveci, . Alp

Table 2: Chemical and mechanical properties of the natural pozzolans compared with TS 25.

Loss on 7th day flexural 7th day compressive

SiO2 + Al2O3 + Fe2O3 MgO SO3 Reactive
TS 25 ignition strength strength
(%) (%) (%) SiO2
(%) (MPa) (MPa)
TS 25 > 70.0 < 5.0 < 3.0 < 10.0 > 1.0 > 4.0
FT 80.6 1.5 0.2 25.9 3.7 1.2 6.4
AT 78.8 4.0 0.2 35.0 3.1 1.6 8.1
KP 82.8 0.8 0.1 55.9 6.8 2.6 13.3

Preparation and testing of CPB samples compressive strengths were directly proportional to reactive
To prepare CPB samples at 5 wt% binder dosage (240 in total), SiO2. This is consistent with the findings in this study.
the tailings, binder (PC and PC/natural pozzolan) and tap
water were homogenized in a mixer (Univex SRMF20 Stand Effect of addition of natural pozzolans on the performance
model) equipped with a double spiral. The mixture were of CPB
poured into plastic cylinders (10 20 cm), which were then When PC was used solely as the binder phase (i.e. no addi-
sealed and allowed to cure in a humidity room (80% humid- tion of the natural pozzolan), the development of the uncon-
ity) for periods of 7360 days. After curing, the CPB samples fined compressive strength (UCS) of CPB was rapid and
were subjected to UCS tests according to ASTM C 39 (2002) peaked at a curing period of 56 days (Figure 1). Thereafter, a
using a computer-controlled mechanical press (ELE Digital trend of decline in UCS was apparent as an indication of the
Tritest), which had a load capacity of 50 kN and a displace- onset of the loss of stability of CPB. The mechanical behav-
ment speed of 0.5 mm min1. iour of CPB samples produced from the volcanic tuffs (FT
and AT) at different replacement levels for PC was similar in
Studies on microstructure and mineralogy of CPB character (Figure 1A,B). However, these samples produced
Scanning electron microscope (SEM) analyses were performed consistently lower UCSs than those prepared from PC alone
to characterize the microstructure and texture of the various over 360-days. The loss of strength of CPB samples contain-
360-day CPB samples using a LEO scanning electron micro- ing AT and FT was also more severe than those containing
scope. Energy dispersive spectrometry (EDS) of an X-ray PC only (Table 3). It can be inferred that AT and FT are not
probe coupled to the SEM was also used to aid the identifi- particularly suitable as mineral additives for CPB of the sul-
cation of mineral phases present. X-ray diffraction (XRD; phide-rich tailings.
Philips Xpert PW 3040 Diffractometer) analyses of the ace- Figure 1C illustrates the performance of CPB samples of
tone-treated CPB samples were also carried out to investi- pumice, KP as the pozzolanic additive in partial replacement
gate the crystalline phases present with particular reference (up to 30 wt%) of PC. As also observed for the volcanic tuffs
to the secondary minerals formed during the curing process. (Figure 1A,B), the development of strength of CPB samples
became slower with adding or further increasing the pro-
Results and discussion portion of KP in the binder phase (Figure 1C). This could
Pozzolanic characteristics of the volcanic tuffs and pumice be linked with the inherent slowness of pozzolanic reactions
The chemical composition of volcanic tuffs (AT and FT) and
pumice (KP; Table 1) suggest that these materials fulfil the
Table 3: Comparison of the extent of loss of strength of CPB samples
specifications of TS 25 with a SiO2 + Al2O3 + Fe2O3 content
using PC and natural pozzolans (FT, AT and KP) as partial
of > 78% (Table 2). The results of pozzolanic activity tests are replacement of PC at different levels (1030 wt%).
also shown in Table 2 where the standard values (TS 25 1975)
are also presented for comparison. The compressive and flex- Strength loss (%) Reactive SiO2
ural strengths of the mortar samples produced from KP were PC 24.6
found to be 2.6 and 3.3 times, respectively, higher than those 10% FT 36
specified in TS 25 (1975). The findings also indicated that the
20% FT 40 25.9
volcanic tuffs (AT and FT) had pozzolanic activities lower
30% FT 43
than KP (Table 2). The relative degree of pozzolanic activity
shown by these natural pozzolans appeared to be intercon- 10% AT 35
nected with their respective reactive silica content (Tables 1 20% AT 24 35.0
and 2). avdar & Yetgin (2007) found that the pozzolanic 30% AT 36
activity of natural pozzolans increased with an increase in 10% KP 20
SiO2 content and decreased with an increase in Al2O3, Fe2O3,
20% KP 15 55.9
MgO and K2O content. Papadakis et al. (2002) reported that
30% KP 10
the pozzolanic activity of natural pozzolans and hence their

432
 Natural pozzolans and the performance of cemented-paste backfill

Fig. 1: The strength development of the CPB samples produced from the tailings sample using PC (CEM I) and the volcanic tuff, FT (A), AT (B)
and KP (C), as mineral additive (up to 30 wt%) at 5 wt% binder dosage.

433
B. Ercikdi, F. Cihangir, A. Kesimal, H. Deveci, . Alp
occurring during the curing of CPB samples. Furthermore,
the activation of pozzolanic material in the binder phase is
dependent on the presence of alkaline phases such as port-
landite (Ca(OH)2), which would become available as the
hydration of PC progressed. However, the incorporation of
KP into the binder phase appeared to improve the stability
of CPB samples between days 90360 (i.e. strength losses of
20% c.f. 24.6% for PC alone; Table 3). Increasing the dosage
of KP (up to 30 wt%) in the binder phase increased further its
beneficial effect on the long-term performance of CPB sam-
ples with only a 10% loss of strength at 30% replacement level
over the same period. The binder dosage can be increased
beyond 5 wt% to improve the strength acquisition/stability
characteristics of CPB samples containing KP.
Based on the relative strength and stability performance
of CPB samples, KP as a pozzolanic admixture appeared
more suitable than volcanic tuffs, AT and FT (Figure 1AC).
This was consistent with their relative pozzolanic activities as
shown in Table 2. In effect, the performance of these natural
pozzolans can be correlated well with their content of reac-
tive silica (Table 3).
Microstructural and mineralogical assessment of CPB
samples
The beneficial effect of the addition of pozzolanic materials
on the strength and stability of concrete/backfill can be
attributed mainly to the consumption of Ca(OH)2 liberated
during the hydration of PC through pozzolanic reactions to
produce secondary CSH with bonding properties. This
could also improve the microstructure producing a denser
packing with the likely reduction in porosity and permeabil-
Fig. 2: SEM micrographs showing CPB sample textures produced from the tailings using PC alone (CEM I) (A) and the natural pozzolans (KP, AT
and FT; BD, respectively) at 20 wt% replacement level and at a fixed binder dosage of 5 wt%.
434
ity. In this regard, a visible densification around the natural
pozzolan grains was observed to occur, apparently due to the
hydration of these grains and hence the formation of addi-
tional cementitious phases such as CSH (Figure 2BD).
The tailings sample used in this study is composed pre-
dominantly of pyrite. Ouellet et al. (2006) confirmed that the
oxidation of sulphide phases such as pyrite present in CPB
could occur under the curing conditions in the presence of air
and moisture. The oxidation of pyrite would lead to the forma-
tion of acid and sulphate (Equation 1) that could react with the
hydration products (Equations 2 and 3), i.e. the phenomenon
known as sulphate attack (Yilmaz et al. 2004). The sulphate
attack could culminate in the formation of expansive phases
such as gypsum (Equation 2) and ettringite (Equation 3) and in
the decalcification/destruction of CSH with the eventual loss
of stability (Kesimal et al. 2005, Ercikdi et al. 2009a,b).
4FeS2 + 15O2 + 8H2O 2Fe2O3 + 8SO42 + 16H+ (1)
Ca(OH)2 + SO42 + 2H2O CaSO4.2H2O + 2OH (2)
3CaO.Al2O3 + 3CaSO4.2H2O + 30H2O
3CaO.Al2O3.3CaSO4.32H2O (3)
Formation of secondary gypsum was confirmed in CPB sam-
ples. In this regard, the deterioration of stability of CPB sam-
ples observed following an initial curing period of 56 or 90
days (Figure 1AC) could be ascribed to the oxidation of
pyrite and, consequently, to the acid and sulphate attack.
Visual observations on CPB samples after 360 days of curing

indicated the development of cracks presumably due to the
formation of expansive phases.
Conclusions
Cemented paste backfill (CPB) allows the placement of all
the plant tailings underground with significant reductions in
tailings disposal and rehabilitation costs, and aids the con-
trol of environmental pollution associated otherwise with the
storage of such tailings under atmospheric conditions (i.e.
the formation of acid mine waters and the release of heavy
and toxic metals).
In this study, the use of natural pozzolans as a partial
replacement of Portland cement (PC) in CPB of sulphide-rich
tailings was examined. The pozzolanic activity of the natural
materials was found to be closely related to their reactive sil-
ica content. The addition of the natural pozzolans at 1030
wt% levels was shown to slow down the rate of the devel-
opment of strength of CPB samples over 90 days of curing
period. CPB studies have also revealed that PC is not a par-
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