Minerals Engineering 122 (2018) 241–250

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Performance evaluation of eggshell waste material for remediation of acid T

mine drainage from coal dump leachate
⁎
Anthony M. Muliwaa, , Taile Y. Leswifib, Maurice S. Onyangoa,c
a
Department of Chemical, Metallurgical and Materials Engineering, Tshwane University of Technology, Private Bag X680, Pretoria, South Africa
b
Department of Chemical Engineering, Vaal University of Technology, Vanderbijlpark, South Africa
c
Rand Water Research Chair in Water Utilisation, Tshwane University of Technology, South Africa

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, eggshell (ES) powder was evaluated as a cheap and biocompatible waste material for the pre-
Acid mine drainage treatment of acid mine drainage (AMD) leachate from coal dump. First, the composition of the AMD and phy-
Eggshell siochemical properties of the ES powder were determined using various standard characterization techniques.
Neutralisation Then the removal efficiency of the target metal contaminants and the acid-neutralisation effect were explored in
Removal
batch and kinetic set-ups. Thereafter, the settling rate of sludge formed after separately reacting ES and lime-
Treatment
stone powders with AMD was explored. Results revealed that the AMD leachate was highly acidic and con-
taminated with both cations and anions. Thermogravimetric analysis (TGA) and X-ray fluorescence (XRF)
analyses demonstrated that ES powder was thermally stable up to 700 °C and CaO was the main component,
respectively. Scanning electron microscopy (SEM) and EDX spectra confirmed the removal of contaminants. Both
the decrease in particle size and increase in mass of ES enhanced the treatment efficiency. Although complete Fe
and Al removal was achieved, Mn and sulphates posed a challenge as they were partially removed. Meanwhile,
ES demonstrated superior acid-neutralizing effect to limestone and the mine water clarity and pH were shifted to
acceptable levels. Both Fe and Al removal proceeded through an exothermic process while it was opposite for
Mn. Kinetics were rapid and the sludge from ES powder settled faster compared with that from limestone
powder. Cost analysis indicated that significant financial savings can be realised by substituting limestone with
ES material. The findings suggest that ES waste could be an efficient and cheap material in the pre-treatment of
AMD effluents.

1. Introduction
Mining industry plays an integral part towards the growth and de-
velopment of South Africa’s economy. However, fragmentation of sul-
phide bearing minerals (FeS2) during mining and mineral extraction
exposes them to oxygenated environment leading to a series of complex
geochemical reactions that generate acid mine drainage (AMD). Acid
mine drainage is highly acidic (pH < 3), has a high concentration of
dissolved iron, aluminium, manganese and sulphates; causing a de-
vastating impact on water resources and consequent damage to the
health of biota (Colvin and Burns, 2011; Ríos et al., 2008). Although
certain rocks, especially those containing large amounts of dolomite or
calcite can naturally neutralise AMD, this is not the situation in South
Africa’s coal and gold mine deposits as natural neutralisation effects are
overwhelmed (McCarthy, 2011). Numerous cases of highly acidic water
with elevated concentrations of metal ions and sulphates beyond ac-
ceptable standards have been reported (da Silveira et al., 2009; De Beer
et al., 2010; Enslin et al., 2010; Tutu et al., 2008). Consequently, to
ameliorate the AMD problem, pragmatic efforts have been constantly
sought to offer innovative, efficient and less costly treatment methods
that could serve as a supplement or as alternative to the existing AMD
treatment technologies and to improve the level of compliance.
Numerous methods such as lime neutralisation and precipitation
(Coulton et al., 2003), ion-exchange (Khan, 2014), adsorption (Hong
et al., 2014; Masindi et al., 2015), electrochemical (Chartrand and
Bunce, 2003) and bioremediation (Johnson and Hallberg, 2005;
Rakotonimaro et al., 2017; Sierra-Alvarez et al., 2006) are used for
AMD treatment. Amongst these, limestone/lime neutralisation and
precipitation of metals in the form of hydroxides and gypsum, followed
by a period of settling in sedimentation basins is by far the most widely
used method for AMD pre-treatment (Gitari et al., 2008; Johnson and
Hallberg, 2005; Maree et al., 2013). Although effective, chemical pre-
cipitation requires large quantity of treatment reagents, resulting in
voluminous and highly hydrated sludge, which dries and compacts

⁎
Corresponding author.
E-mail address: MuliwaAM@tut.ac.za (A.M. Muliwa).

https://doi.org/10.1016/j.mineng.2018.04.009
Received 17 January 2018; Received in revised form 28 March 2018; Accepted 14 April 2018
Available online 24 April 2018
0892-6875/ © 2018 Elsevier Ltd. All rights reserved.
A.M. Muliwa et al. Minerals Engineering 122 (2018) 241–250

poorly, posing disposal and storage challenges. Moreover, limestone collected, prepared, characterised and evaluated for the removal of
mining may have significant negative impact on the environment and main cations (Al, Fe, Mn) and anions (SO42−) present in the AMD.
the public health. Although limestone is cheap, it exhibits slow reaction Batch equilibrium and kinetic experiments were conducted to explore
time, and its properties are geologic dependant, meaning inconsistency the influence of different process variables on the overall treatment
in grade can affect the overall performance of a given treatment system efficiency. In addition, the performance of eggshell in terms of neu-
(da Silveira et al., 2009; Skousen, 2014). Due to such limitations, it is an tralisation efficiency, sludge settling rate and volume was compared
important challenge for industries and researchers to explore other with raw limestone of similar properties. Results obtained from this
natural materials for effective and economical pre-treatment/neu- study provides important insights into the possible application of the ES
tralising of AMD. Furthermore, such alternative solutions would be waste as a cheap and effective substitute material for the pre-treatment
more viable if they can be used in an existing treatment facility with of AMD.
minimal changes.
Recently, adsorption technology, employing naturally-derived ma-
2. Materials and methods
terials has received increasing attention (Bulut and Tez, 2007), as an
effective, efficient and economical method for sequestration of heavy
2.1. Materials
metals from aqueous solution (Bulut and Tez, 2007; Faur-Brasquet
et al., 2002; Gupta and Nayak, 2012; Yu et al., 2001). This is because
Eggshell waste was collected from the Tshwane University of
most of the reported synthetic adsorbents require long preparation re-
Technology restaurant. Multi-ions standards solutions and analytical
cipe and are generally expensive. Thus, there has been a shift in focus
reagent grade (AR) chemicals were purchased from Merck (Pty) Ltd-
towards low-cost agriculturally-derived materials with desirable ad-
South Africa. Limestone powder was obtained from G&W Mineral
sorptive and acid neutralisation characteristics (Oke et al., 2008). Lit-
Resources (South Africa). Before use in adsorption experiments, all the
erature reports indicate that activated carbon (Goher et al., 2015),
glassware and polyethylene bottles were firstly soaked with 10% nitric
chitosan (Bassi et al., 2000), banana and orange peels (Annadural et al.,
acid for 24 h and thereafter were rinsed with deionised water and dried
2003), sugar cane bagasse (Joseph et al., 2009), sawdust (Yu et al.,
in a clean oven.
2001) and rice husks (Hegazi, 2013) among others, have the potential
to sequestrate metal ions from polluted water.
Recently, increased egg production and processing has resulted in 2.2. Acid mine water
increased eggshell (ES) waste; a non-edible product with very limited
use and value. The disposal of ES waste is an environmental burden Acid mine drainage (AMD) samples were obtained as Toe Seep
worldwide, and especially in countries where the egg product industry Leachate from a waste coal dump in Anglo American Thermal Coal,
is well developed (Hassan and Aigbodion, 2015). According to Witbank (South Africa). Standard sampling procedures (EPA, 2007)
Windhorst et al. (2013), approximately 124,800 tons of ES waste was were followed after which the samples were filtered using 45 µm cel-
produced globally in the year 2010 as a result of industrial egg pro- lulose acetate filters and were stored in polyethylene bottles at 4 °C. The
cessing. Furthermore, statistics by the Food and Agricultural Organi- concentration of metal ions in the samples was determined using in-
zation (FAO) indicates that the global egg production is likely to hit ductively coupled plasma atomic emission spectrometer (ICP-AES,
86.8 million tons by 2030 (FAO, 2014). The projected increase in egg 9000, Shimadzu-Japan). Anions were quantified using the Metrohm
production therefore, means large quantities of ES will be produced and 861 compact ion chromatograph (Switzerland) with a Metrosep A Supp
disposed of as waste. As a result, high disposal cost will continue to 5 (6.1006.520) 150 × 4.0 mm analytical column. Before any analysis,
increase due to increase in landfill taxes and environmental concerns both instruments were calibrated using standard solutions. The pH was
(Hassan and Aigbodion, 2015). Therefore, it is necessary to find alter- measured with Orion Star A211 pH meter (Thermo Scientific). The
native ways to transform ES into a valuable item for overcoming en- meter was calibrated with 4.0, 7.0 and 10.0 buffer solutions before each
vironmental challenges. set of trials.
The main component of the ES is calcium carbonate (CaCO3), which The main chemical composition of AMD was determined and are
can be used as a complexing, binding or ions exchange agent for metal displayed in Table 1. As it can be seen, the AMD is highly acidic
ions in liquid solution. Moreover, CaCO3 is a significant alkalizing agent pH = 2.43; which was way far below the recommended values
and when equilibrated with acidic water, it neutralises it; meaning (6.5–8.5) by the World Health Organization (WHO, 2011). Also, the
heavy metals can precipitate and adsorb on ES particles’ surface. Such
characteristic make eggshell waste a potential material for removing Table 1
contaminants, especially cations from the liquid phase. Few studies Main chemical composition of raw AMD (toe seep leachate from coal discard
have explored ES as a promising scavenger for metal ions in aqueous dump) sample from Anglo American thermal coal, Witbank (South Africa).
solution (Ahmad et al., 2012; Elabbas et al., 2016; Ipeaiyeda and Tesi, Parameter Value Drinking guideline value
2014; Jai et al., 2007; Rubcumintara, 2014; Suheila, 2013; Zheng et al.,
2007). Nonetheless, there is still a lack of practical applicability because pH (at 25 °C) 2.43 6.5–8.5a
K (mg/L) 10.2 10a
previous studies focused mainly on removing dilute concentrations of
Na (mg/L) 149.7 250a
metal ions from synthetic solutions, instead of using environmental Ca (mg/L) 606 200a
water samples. Besides, adsorption alone is mainly suitable as a pol- Mg (mg/L) 648 100a
ishing step, and for it to be effective in highly contaminated waters, it Fe (mg/L) 6120 0.3b
Al (mg/L) 506 0.2b
may be considered important to supplement it with neutralisation. In
Mn (mg/L) 155 0.1b
view of the aforementioned, it can be a considerable task to examine SO42− (g/L) 28.98 0.25b
the ability of ES waste for use as an effective precipitation and ad- PO43− (mg/L) 75 10b
sorption surface for both cations and anions present in highly acidic and NO3− (g/L) 137 50b
contaminated environmental samples. EC (mS/cm) 12.41 1.4a
Turbidity (NTU) 65.32 5a
Thus the aim of this study was to examine ES waste as a cheap and
TDS (g/L) 10.27 1.0a
biocompatible material for the pre-treatment and attenuation of AMD
from toe seep coal dump leachate. To the best of our knowledge, there TDS = (0.8 * EC) + (2.2 * 10^−6 * EC^2).
a
is hardly any literature report available regarding the application of ES World Health Organisation (WHO).
b
waste for remediation of highly polluted AMD. Eggshell waste was Department of Water Affairs (DWA) South Africa.

242
A.M. Muliwa et al. Minerals Engineering 122 (2018) 241–250

AMD had a conductivity value of 12.41 mS/cm suggesting that in-
organic ions were present in reasonable concentration. Total dissolved
solids (TDS), Fe, Al, Mn and sulphates were all present in high levels
exceeding discharge limit values recommended by most environmental
regulatory bodies. Generally, the AMD was highly polluted and offered
a platform to provide factual data for application purposes.
2.3. Eggshell preparation and characterization
The collected eggshell waste was first washed with tap water and
afterwards with deionized water to remove albumin, dirt and other
impurities (organics and salts). Then, the washed eggshells were placed
in the oven and dried at 100 °C. The sample was crushed and graded
into various fractions using a series of sieves ranging between
0.053 mm and 1.000 mm. The chemical composition of unused ES (ES
before reacting with AMD) and used ES (AMD-reacted ES) powders was
analysed by X-ray fluorescence (XRF) ARL Perform'X Sequential XRF
instrument. In a typical procedure, the samples were roasted at 1000 °C
to determine Loss On Ignition (LOI). Then 1 g of the roasted sample was
placed together with 6 g of Li2B4O7 into a Pt/Au crucible and fused and
the analyses were executed using the Quantas software. The software
analysis for all elements in the periodic table between Na and U, but
only elements found above the detection limits were reported. The re-
sults were also monitored and filtered to eliminate the presence of some
of the flux, wetting and oxidising agents’ elements. Blank and certified
reference materials were also analysed with each batch of samples and
were represented in the results. The morphological and elemental as-
pects were observed by field emission scanning electron microscopy
(FE-SEM JEOL JSM-7600F) fitted with energy dispersive X-ray spec-
troscopy (EDX). The functional groups were identified by Fourier
transform infra-red (FT-IR) spectrometer instrument while thermal
properties were examined using thermo-gravimetric analyser (TGA)
and differential thermal analyser (DTA) (Perkin-Elmer Pyris 1 TGA
instrument) at 10 °C/min heating rate in an air environment. For TGA
analysis a given amount of the dried eggshell powder was loaded in the
TGA/DTA analyser and then pyrolysis was performed up to 900 °C at an
elevation of temperature 10 °C/min with continuous injection of air.
produced by ES and limestone powder (53–160 µm) was determined by
adding 8 g of each material in 400 mL of raw AMD in a beaker. The
mixtures were stirred at 180 rpm using an overhead stirrer at room
temperature for 24 h. Thereafter, the mixtures were separately in-
troduced into 500 mL graduated cylinders at the same time and the
depth of sludge blanket were monitored periodically until the final
reading remained constant. The final reading was considered as the
sludge volume. In another set of experiments, the effect of temperature
(25–45 °C) on the metal removal was explored by varying their initial
concentrations as follows: Fe (146.8–6120 mg/L), Al (12.14–506 mg/L)
and Mn (3.72–155 mg/L). For an equilibrium to be attained, 0.15 g of
ES powder was used instead of 0.5 g. Finally, the effect of contact time
on metal removal efficiency was explored by adding 20 g of ES powder
into 1 L of raw. The mixture was stirred continuously at room tem-
perature and samples were collected at predetermined time intervals,
they were filtered and analysed for residual metal ions. Thereafter, the
removal efficiency at any given time was calculated using Eq. (1). The
concentrations of the Ca2+, K+, Mg2+, Na+, SO42−, PO43−, and NO3−
in both raw and treated AMD were determined.
3. Results and discussion
3.1. Eggshell (ES) characterisation
Thermal properties of unused ES and used ES powders are shown in
Fig. 1. As shown, the weight decreased by 6% and 9% for unused ES

2.4. Batch experiments

Batch equilibrium tests were conducted to investigate the treatment

efficiency at different process conditions. The effect of ES particle size
(< 53 µm, 53–160 µm, 160–300 µm, 300–425 µm, 425–600 µm,
600–850 µm and 850–1000 µm) on the removal of Fe, Al and Mn was
explored by adding 0.5 g of ES powder in 25 mL of AMD. Then samples
were placed in thermostatic bath shaker maintained constant shaking
speed and temperature of 180 rpm and 25 °C, respectively, for 24 h. The
contents were filtered through 0.45 µm membrane filter and the re-
sidual metal concentration in the filtrate was determined using ICP-
AES. The removal efficiency, R (%) was calculated based on the dif-
ference between the initial and final concentrations as follows:

Ci−Cf ⎞
R% = ⎛ ⎜ × 100
⎟

⎝ Ci ⎠ (1)

where Ci and Cf are initial and final concentrations (mg/L) in the raw
and treated AMD, respectively.
The effect of ES dose (0.075–1.25 g) on the removal efficiency was
investigated with 53–160 µm particles; owing to their positive pre-
liminary results. After the equilibration the final pH of each treated
AMD sample solution was measured and recorded. For comparison
purposes, limestone powder (53–160 µm) was also tested under similar
conditions. The effect of initial pH (1.75–3.30) on the removal effi-
ciency was investigated by adding 0.5 g of ES into 25 mL of AMD. This
pH range was chosen to prevent precipitations of Fe and Al. Fig. 1. TGA and DTA profiles for (a) unused ES and (b) used ES powder
Meanwhile, a comparison of the settling rate and sludge volume (53–160 µm).

243
A.M. Muliwa et al.
Fig. 2. FT-IR spectra of (a) unused ES and (b) used ES powders (53–160 µm).
(Fig. 1(a)) and for used ES (Fig. 1(b)) samples, respectively, when the
temperature was increased from 34.8 to 700 °C. Further heating be-
tween 700 and 942 °C resulted in major weight losses of 42% and 38%
for unused and used ES, respectively, and at the end of the heating
process (942.6 °C), the unused sample exhibited 1% more weight loss
than the used one. The observed major weight losses were ascribed to
the removal of moisture and organics from the dominant CaCO3 at this
temperature range. According to Jai et al. (2007), at temperatures
above 700 °C, the predominant components in ES are CaCO3 and CaO.
Consequently, those weight losses appeared as endotherms on both
DTA curves and corresponded to phase transformation i.e. decomposi-
tion/calcination and oxidation of CaCO3 to CaO and CO2. Beyond
840 °C, the weight losses remained almost constant as CaCO3 under-
went pyrolysis to CaO. The difference in weight losses may have been
due to changes in compositions, especially after contaminants were
loaded onto the ES material (Kontopoulos, 1998). The ability of the ES
to withstand a wide range of temperature makes it suitable for different
applications including in less energy intensive adsorption processes.
Fig. 2 shows FT-IR spectra which were recorded in the range of
650–4000 cm−1, with the resolution of 4 cm−1. For the ES sample (a)
before AMD treatment, peaks were observed at 712, 872, 1395 and
2527 cm−1 which are strongly associated with the presence of CaCO3
(Mijan et al., 2014). The absorption bands at 1648 and 2945 cm−1
correspond to C]O from CO3 while the broad band appearing at
3310 cm−1 is associated with moisture absorption (OH group) (Manoli
and Dalas, 2000). After AMD treatment (b) the carbonate group at
1648 cm−1 is split resulting in two new IR bands at 1621 and
1652 cm−1 which were not only attributed to the dissolution of CO3 but
also a confirmation of interaction with contaminants. Similarly, the
band at 3310 split and shifted to higher wavenumbers (3398 and
3430 cm−1) due to interactions of the contaminants with the OH group
of the ES. Moreover, the strong band at 667 cm−1 may be associated
with Ca-O bond. The results showed clearly that there were interactions
between Fe, Al and Mn with the ES, thus confirming the ability of ES to
remove metal contaminants from AMD.
To determine the chemical compositions of the unused and used ES
Table 2
XRF analyses of ES powder before and after AMD treatment.
Component (%) SiO2 TiO2 Al2O3 Fe2O3
Before 0.03 < 0.1 0.01 0.02
After 0.15 < 0.1 0.74 5.39
Minerals Engineering 122 (2018) 241–250
and further confirm adsorption or precipitation of various con-
taminants, X-ray fluorescence analysis was conducted on the samples.
Table 2 shows the results obtained from XRF analyses. Based on the
results the principal component of the unused ES powder is CaO re-
presenting 51.40%. Other components included MgO (1.20%), P2O5
(0.45%) and SO3 (0.23%). After AMD treatment, the following con-
stituents compositions increased and their percent values were as fol-
lows: Fe2O3 (9.78%), Al2O3 (1.34%), MnO (0.24%), SO3 (1.48%) and
MgO (1.00%). The increase in composition after AMD treatment con-
firmed that indeed Fe, Al and Mn were adsorbed/precipitated on the ES
surface. Meanwhile, there was a decrease in compositions of CaO and
MgO which indicated that dissolution and ion exchange played a role
during the treatment process. Moreover, SO3 increase from 0.23 to
1.48% was an indication that ES was not only capable of removing
cations (heavy metals) but also anions (sulphates) from AMD. On the
other hand, there was a decrease in the LOI which may have been due
to chemical composition changes of the ES after AMD treatment.
However, the LOI results were perfectly in accordance with those on
TGA analysis. Generally, XRF analysis results on both samples con-
firmed that CaO was the main constituent of ES and contaminants’ re-
moval occurred. The results agreed with those previously reported by
Freire and Holanda (2006).
Micrographs and their related EDX spectra for unused ES and used
ES powders are presented in Fig. 3. The SEM micrograph of unused ES
shown in Fig. 3a illustrates particles of variable irregular shapes and
sizes in crystalline form. After the ES was reacted with AMD (Fig. 3b),
its surface appeared to be coated with cracked surface deposits resulting
from oxidation, adsorption and precipitation of contaminants onto their
surfaces. The precipitation has an advantage of increasing the weight of
adsorbent particles, hence enhancing settling and subsequently aiding
in the separation in sedimentation ponds. Meanwhile, the EDX spec-
trum of the unused and used ES samples are shown in Fig. 3c and d,
respectively. The presence of Ca, C, O, Mg and S in the unused ES
sample confirmed that CaCO3; in the form of calcite is the main com-
ponent in eggshell. For the used ES sample, the EDX spectra shows new
characteristic peaks of Fe (0.705 and 6.398 keV), C (0.277 keV), O
(0.525 keV), S (2.307 keV), Al (1.486 keV) and Mn (0.637 and
5.894 keV). The presence of new peaks in the spectra confirmed the
specific contaminant removal by ES powder.
3.2. Effect of ES particle size on removal efficiency
The particle size of an adsorbent is one of the factors that affect the
efficiency of the removal process. The effect of particle size of ES on the
pre-treatment efficiency of metals (Al, Fe and Mn) and anions is shown
in Figs. 4 and S1, respectively. Results show that all contaminants’ re-
moval efficiency decreased with increase in particle size. Specifically, at
a fixed ES dose of 0.5 g, the removal efficiency of Fe, Al and Mn de-
creased from 100 to 19%, 100 to 16% and 51 to 8%, respectively, when
the particle size range was varied between < 53 µm and 850–1000 µm.
Similarly, SO42−, NO3− and PO43− removal efficiency decreased from
64 to 4%, 29 to 5% and 25 to 4%, respectively (Fig. S1). The pH of the
treated water decreased from 6.81 to 3.17 in the same order (Fig. S2).
Notably for small particle size range, sample bottles appeared swollen
due to more CO2 gas accumulating as a result of the reaction between
CaCO3 of ES and the acid in water. Smaller ES particles exhibit large
physical surface area leading to increased dissolution of CaCO3 in the
ES. As a result, acid neutralisation and metal precipitation increase and
MnO MgO CaO Na2O P2O5 SO3 LOI
< 0.1 0.63 51.40 < 0.1 0.24 0.23 47.50
0.13 0.55 46.40 < 0.1 0.24 1.48 44.90
244
A.M. Muliwa et al.
Fig. 3. SEM micrographs and EDX spectra [(a) and (c)] unused ES and [(b) and (d)] used ES powder (particle size 53–160 µm).
Fig. 4. Effect of particle size on metal removal efficiency (Fe = 6120 mg/L,
Al = 506 mg/L, Mn = 155 mg/L, mass = 0.5 g, volume = 25 mL,
temp = 25 °C, speed = 180 rpm, time = 24 h).
the overall treatment efficiency improves. Moreover, small-sized par-
ticle are known to exhibit rapid rotations which could also have played
an important role in the sorption and neutralisation process.
3.3. Effect of ES mass on the removal efficiency
The solid-liquid ratio is an important variable because it relates to
the number of active sites and consequently affects the overall effi-
ciency of the treatment system. As shown in Fig. 5, removal efficiency
245
Minerals Engineering 122 (2018) 241–250
Fig. 5. Effect of adsorbent dose on metals’ removal efficiency (Fe = 6120 mg/L,
Al = 506 mg/L, Mn = 155 mg/L, particle size = 53–160 µm, volume = 25 mL,
pH = 2.43, temp = 25 °C, speed = 180 rpm, time = 24 h).
of Fe, Al and Mn increased from 47.7 to 100%, 15 to 100% and 7.1 to
68%, respectively, when the ES mass was increased from 0.075 to
1.25 g. As shown in Fig. S3, a similar trend was observed for partial
removal of anions whereby the removal efficiency of SO42−, NO3− and
PO43− increased from 0.1 to 66%, 1.5 to 35% and 1 to 28%, respec-
tively. The high removal of Fe and Al were attributed to both pre-
cipitation and adsorption (as supported in EDX and XRF characterisa-
tion results) because even at circumneutral pH values, Fe and Al are
capable of precipitating. Therefore, Fe and Al were removed pre-
dominantly as their respective hydroxides (Miller et al., 2007). In
A.M. Muliwa et al.
Fig. 6. Influence of ES mass on final pH (mass = 0.5 g, volume = 25 mL, initial
pH = 2.43, temp = 25 °C, speed = 180 rpm, time = 24 h).
addition, increase in ES mass meant increased sites for adsorption and
precipitation, which consequently resulted in an improved overall
performance. However, Mn was partially removed, and considering the
prevailing AMD pH values involved, adsorption may have been its
dominant removal mechanism. Edwards et al. (2009) and Emmanuela
and Rao (2008) observed that it is difficult to remove Mn, especially in
the presence of high concentrations of other ions. The removal followed
the order: Fe > Al > Mn, which corresponds to the electronegativity
of the respective ions.
3.4. Comparison of neutralisation effects of ES and limestone powders
Fig. 6 shows that increasing mass of ES and limestone materials
resulted in an increase in pH of the treated effluent. Both materials
showed similar trends, whereby the pH of the treated water increased
slightly up to a mass of 0.25 g, followed by rapid increase between 0.25
and 0.5 g, and thereafter a very minimal increase onwards. Low mass is
overwhelmed by the high acidity of the AMD, thus low pH values of the
treated effluent are achieved. Conversely, at high masses, the rate of
calcite dissolution decreases as the pH and activities of Ca2+ and
HCO3− increase and the partial pressure of CO2 decreases. Specifically,
a mass of 0.5 g ES raised the pH to 6.58 which fall within the re-
commended value for wastewater (WHO, 2011). However, the same
mass of limestone powder could only achieve a final pH 5.75. Gen-
erally, ES powder showed superior neutralisation performance than
limestone at all masses studied, and it was concluded that 0.5 g/25 mL
of AMD was sufficient to attain the required pH standard. Maree and du
Plessis (1994) used limestone to treat AMD and they suggested that
neutralisation and SO42− removal are achieved through dissolution of
CaCO3 and crystallisation of gypsum according to Eq. (2):
CaCO3 + H2 SO4 → CaSO4 + CO2 + H2 O
3.5. Effect of varying the pH of AMD on the metal removal efficiency
Seasonal changes affect the concentrations of contaminants and pH
of the AMD through precipitation, evaporation, flooding etc. For in-
stance, during the rainy season concentrations and pH may vary greatly
in contrast to those during summer or winter. As a result, the study of
such changes and how they impact the contaminant removal is of great
importance. Fig. 7 shows the effect of initial pH on the removal of Fe, Al
and Mn. As shown, increasing the pH from 1.75 to 3.30 resulted in an
increase in percent removals as follows: Fe (89–100%), Al (96–100%)
Minerals Engineering 122 (2018) 241–250
Fig. 7. Influence of initial pH on Fe, Al and Mn removal (Fe = 6120 mg/L,
Al = 506 mg/L, Mn = 155 mg/L, Volume = 25 mL, mass = 0.5 g,
temp = 25 °C, speed = 180 rpm, particle size = 53–160 µm, time = 24 h).
and Mn (46–74%). The increased removal exhibited on Fe and Al was
attributed to both adsorption and precipitation mechanisms while the
less removal of Mn was linked to adsorption process only. Mohan and
Chander (2006) observed that sorption mechanism alone takes place
when the pH of the solution is less than the precipitation pH of re-
spective metal ions. Precipitation of Mn begins at pH > 8 which jus-
tified its less removal while Fe and Al precipitations occurs even at
pH < 4 (Al-Muhtase et al., 2008; Motsi et al., 2009; Yan et al., 2014).
In addition, Fe and Al ions hydrolyse more easily to form Fe(OH)3, Fe
(OH)4− and Al(OH)3 and Al(OH)4− respectively, as the solution pH
tends from medium to neutral, corroborating their increased removal.
Furthermore, the degree of hydrolysis in liquid solution is a step-wise
process which strongly depends on solution pH. Hence protons get lost
from water of hydration when pH increases and for Fe, the following
bonds are formed: FeeOHeFe bonds (olation) and FeeOeFe bonds
(oxolation) (Dizz et al., 1999; Stumm and Morgan, 1981).
3.6. Effect of temperature and initial concentration on removal efficiency
Fig. 8 shows the effect of temperature on equilibrium uptake, qe (mg
of contaminant removed per g of ES powder) of Fe with that of Mn
shown as Fig. 8 inset. The results indicate that Fe uptake decreased
from 690.33 to 623.15 mg/g while that of Mn increased from 3.83 to
4.22 mg/g when the temperature was increased from 25 to 45 °C. The
decrease in Fe uptake as temperatures increased was attributed to in-
crease in solubility of the ferric carbonate (Yeddou and Bensmaili,
2007). Similar results were obtained for Al (not shown), thus, at those
prevailing conditions, the removal of Fe and Al was favoured by room
temperatures while that of Mn was slightly favoured by high tem-
peratures. In addition, increase in the initial concentration for all con-
(2)
taminants resulted in a decrease in the removal efficiency. This was due
to the presence of limited active sites, and therefore, increasing con-
taminant concentrations resulted in complete occupation of the ES sites
and excess contaminants remained as residues.
3.7. Effect of contact time on removal efficiency
Contact time helps in determining the rate at which contaminants
are removed from solution, and this also determines the residence time
and the size of precipitation/adsorption chamber. Fig. 9 shows the
metal removal rates from the raw AMD using ES material. Fe and Al
were removed rapidly, and under the prevailing experimental
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Table 3
Overall AMD pre-treatment efficiency using ES (mass = 0.5 g, particle
size = 53–160 µm, volume = 25 mL, Temperature = 25 °C).
Parameter Untreated Pre-treated % Change WHO
AMD AMD standards

pH (at 25 °C) 2.43 6.58 – 6.5–8.5

K (mg/L) 10.2 6.88 32.5 10
Na (mg/L) 149.7 156.6 -4.6 250
Ca (mg/L) 606 832 -37.3 200
Mg (mg/L) 648 679 -4.8 100
Fe (mg/L) 6120 0.52 99.9 0.3
Al (mg/L) 506 0.16 99.9 0.2
Mn (mg/L) 155 75.95 51.0 0.1
SO42− (g/L) 28.98 10.86 62.5 250
PO43− (mg/L) 75 60 20.0 10
NO3− (mg/L) 137 102 25.6 50
Appearance Deep-brown Colourless – Not visible

of AMD as well as ion-exchange which probably occurred during the

Fig. 8. Effect of temperature and initial concentration on removal efficiency
(Fe = 146.80–6120 mg/L, Al = 12.14–506 mg/L, Mn = 3.72–155, mass = 0.15 g,
volume = 25 mL, pH = 2.45, speed = 180 rpm, particle size = 53–160 µm,
time = 24 h).
treatment process. In particular, SO42− reduction was due to gypsum
crystallisation (Maree and du Plessis, 1994). However, sulphates was
partially removed, because only sulphates associated with free acids
could precipitate during the neutralisation process. Meanwhile, the pH
of the treated AMD was found to be 6.58; a value that was well within
the limits recommended by the WHO (2011). These results agreed with
those obtained from EDX analysis. To support the above findings, a
photograph caption of the raw and pre-treated AMD is included in Fig.
S4 of the supplement which shows that the colour of raw AMD changed
from deep-brown to colourless after treatment with ES material. The
findings demonstrated the strong ability of ES adsorbent in amelior-
ating contaminants from AMD contaminated sites. However, due to the
partial removal of some of the contaminants, this process could in-
tegrate as a pre-treatment method.

3.9. Comparison of settling rates of ES/AMD and limestone/AMD sludge

The study of the rate of sludge formation and settling during water
treatment process is an important undertaking because it provides in-
formation regarding the sizing of the sedimentation and drying ponds.
In order to evaluate this characteristic, ES and limestone powders of
same particle sizes (53–160 µm) were continuously contacted with
AMD for 12 h. Fig. 10 shows that complete settling of the ES/AMD
sludge was achieved within 10 min whilst about 40 min was required

Fig. 9. Effect of contact time on metals removal efficiency by ES (AMD:

Fe = 6120 mg/L, Al = 506 mg/L, Mn = 155 mg/L, pH = 2.45, volume = 1 L,
mass = 20 g, speed = 180 rpm, particle size = 53–160 µm).

conditions, it required 60 min and 40 min, respectively, to achieve

complete removal. The shorter removal time of Al can be attributed to
its lower initial concentration compared to Fe. On the contrary, Mn
removal was a slow process and only 50% removal was achieved over
the studied period despite its low concentration. However, dynamic
profiles show that the rate of Mn removal improved immediately after
Al and Fe were completely removed, indicating that the Al and Fe
precipitates played a role in adsorbing Mn.

3.8. Overall pre-treatment efficiency using optimal conditions

The overall pre-treatment efficiency using 0.5 g ES powder of

53–160 µm particles size is presented in Table 3. It was found that the
treated AMD became colourless with the following contaminants de-
creasing as follows: Fe (99.9%), Al (99.9), Mn (51.0%), SO42− (62.5%),
PO43− (20.0%) and NO3− (25.6%). However, the concentration of Ca, Fig. 10. Comparison of settling rate of sludge generated by ES/AMD and
Na and Mg increased after treatment. This increase was attributed to limestone/AMD systems (Fe = 6120 mg/L, Al = 506 mg/L, Mn = 155 mg/L,
the dissolution of a portion of the ES powder (calcite) due to the low pH particle size = 53–160 µm, volume = 400 mL, mass = 8 g, temp = 25 °C).

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A.M. Muliwa et al. Minerals Engineering 122 (2018) 241–250

for complete settling of limestone/AMD sludge. The faster settling of Table 4

ES/AMD sludge can be attributed to its higher density than that of Comparison of pre-treatment cost between eggshell and limestone.
limestone/AMD system. In addition, the ES/AMD sludge occupied less Parameter Toe Seep Leachate pre-treatment cost
volume (35 mL) and was easily filterable compared to that produced by analysis
limestone/AMD system (50 mL). However, in both experiments, clear
liquids were obtained. Considering an up-scaled treatment system, de- Eggshell Limestone

creased sludge volume (as it was the case with ES/AMD system) can AMD flow rate (Ml/day) 1.75 1.75
lower the capital cost in terms of sizes and number of sedimentation Optimal pre-treatment dosage (mg/L) 20,000 20,082
ponds and filter presses, as well as the operation cost in terms of ef- Monthly eggshell preparation cost (ZAR) 956,340 –
fluent volume treated in a short period. Since sludge constitutes a sig- Price per ton (ZAR/t) 910 1200
Cost of pre-treating one cubic metre 18.2 24.10
nificant proportion of the overall treatment costs, it is important to
(ZAR/m3)
suggest appropriate management options. In this study, authors suggest Total daily pre-treatment cost (ZAR/day) 31, 850 42, 172
that the ES/AMD sludge may be used as a raw material for pigment Total annual pre-treatment cost 11, 625,250 15, 392,853
production, or alternatively, it could be disposed-off appropriately, (ZAR/year)
Cost ratio 1 1.32
reprocessed, solidified/stabilised, or reused as discussed comprehen-
sively by Zinck (2006). These results demonstrated the ES powder could Note: ZAR symbolises South African Rand; t stands for metric ton; m3 stands for
serve as a low-cost material for the pre-treatment of AMD. cubic metre; the cost will depend on assumptions made and/or factors con-
sidered for each scenario.
Key assumptions considered here: 1 kwh = ZAR 1.96; Transport unit cost = ZAR
3.10. Proposed flow sheet for continuous pre-treatment of AMD using
16/t/km; miscellaneous cost = 10% of the material preparations cost;
eggshell Equipment for ES preparation are supplied by SHANGHAI SCM MACHINERY
CO., Ltd.
Fig. 11 shows the proposed two-phase flow sheet for the pre-treat-
ment of AMD using ES material. In the first phase (the main focus of the
present study), the ES material is used as a limestone substitute to
provide CaCO3 for the pre-treatment/neutralisation (to raise pH to 6) of solid contents and avoid mixing the sludge produced at each stage. The
the highly acidic AMD to remove free acid, Fe, Al (main dissolved ca- proposed treatment process will utilise the existing treatment facility
tions of AMD) and for partial removal of SO42− (gypsum crystal- without major alteration in design. The suitability of this will be ad-
lisation). The second phase (not explored in this study) is expected to dressed in follow-up paper.
utilise commercial grade lime to further neutralise (raise pH to 9.5) to
remove Mn and other metals present, such as Ca and Mg. The entire 3.11. Approximated AMD pre-treatment cost analysis
treatment process is operated under atmospheric conditions to provide
oxygen for complete metal ions oxidations. The two-phase process may The estimated cost analysis for pre-treating AMD using the ES ma-
be less costly compared to a process that uses lime only because the use terial was done based on the previous limestone cost analysis data by
of ES waste in the first phase of the treatment process will substantially Maree et al. (2013). Table 4 shows a comparison of the cost of pre-
reduce the amount of commercial lime required in the second phase. treating toe seep leachate using ES and limestone at the feed flow rate
Each phase comprises a clarifier to allow sufficient settling time for of 1.75 megalitres (Ml)/day. More details on treatment cost (excluding

Fig. 11. Proposed two-phase flow sheet for AMD treatment using ES waste and commercial grade lime.

248
A.M. Muliwa et al.
capital cost) are provided in the supplementary file. Results show that
20,000 mg and 20,082 mg are the respective dosages for ES and lime-
stone, required to pre-treat 1 L of the toe seep leachate. The price of one
metric ton of limestone is 1100 South African Rand (ZAR) while the
estimated cost of ES powder will be ZAR 910/ton. Consequently, the
unit cost of AMD pre-treatment will be ZAR 18/m3 when using ES
material and ZAR 24/m3 when using commercial limestone. This
translates to total pre-treatment costs of ZAR 11.6 million and ZAR
15.4 million per annum (p.a), respectively. The results indicate that
significant financial saving could be gained using ES material.
4. Conclusions
This study examined the suitability of ES waste to pre-treat and
neutralise highly acidic and contaminated AMD leachate from coal
mine dump. Standard characterisation techniques such as TGA, FT-IR,
XRF, SEM and EDX revealed that ES underwent physiochemical
changes after it was reacted with AMD. Process variables such as par-
ticle sizes, mass and pH greatly influenced the ES pre-treatment effi-
ciency. Low temperature favoured Al and Fe removal while Mn removal
efficiency slightly improved when temperatures were increased.
Although Fe and Al were completely removed, Mn and anions proved
difficult and only partial removal was achieved. Kinetic results revealed
that shorter contact times were required for complete removal of both
Fe and Al than for Mn. The sludge formed by ES settled faster compared
to that from limestone counterpart, thus demonstrating the possibility
applicability of the ES waste in sedimentation ponds. Generally, results
obtained in this study indicate that ES waste could add value in en-
vironmental remediation by serving as an inexpensive material for
neutralisation and pre-treatment of AMD polluted sites. However, since
water treatment systems operate either semi-continuously or con-
tinuously, it is desirable a pilot system to be designed and optimised in
order to determine the technical and economic feasibility of using ES
waste in pre-treating AMD.
Acknowledgements
Authors wish to acknowledge financial support received from Rand
Water, South Africa through the Rand Water Research Chair in Water
Utilisation.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.mineng.2018.04.009.
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