Mine Water and the Environment (2019) 38:517–527

https://doi.org/10.1007/s10230-019-00615-3

TECHNICAL ARTICLE

Use of Basic Oxygen Furnace (BOF) Steel Slag for Acid Mine Drainage
Treatment: A Laboratory Study
Sukla Saha1 · Sayantan Sarkar1 · Alok Sinha1

Received: 13 October 2017 / Accepted: 15 July 2019 / Published online: 19 July 2019
© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract
We investigated the feasibility of using alkaline basic oxygen furnace (BOF) steel slag to treat acid mine drainage (AMD).
Simulated AMD was treated with different doses of slag (10, 20, 30, 40, 50, and 60 g/L) for 24 h in batch reactors. A dose
of 30 g/L was considered optimal because it raised the pH to 8.6 and resulted in 99% removal of trace metals in 24 h. The
pH increased to 6.36 from the initial pH of 1.5 within 0.5 h of reaction time. Approximately 95% of all trace metals were
removed. Of the major cations and anions, Mg showed the highest percentage removal (72%), followed by ­SO4 (30%), K (8%),
and Na (2.1%) at the 30 g/L dose and 0.5 h reaction time. However, Ca concentrations increased by 28% due to leaching from
the slag. PHREEQC was used to predict the possible mineral phases precipitating during treatment. Calculated saturation
indices indicated that Fe was removed mainly as goethite, hematite, and amorphous Fe(OH)3; Al was removed as gibbsite
and amorphous Al(OH)3; Mn was removed as manganite, hausmannite, and pyrolusite; Mg was removed as Mg(OH)2; and
Ca and S ­ O4 were only minimally controlled by gypsum precipitation. Moreover, sulfate removal was increased by the pre-
cipitation of alunite, an Al-oxy hydroxysulfate mineral. Other trace elements were either co-precipitated with or adsorbed
onto the Fe, Al, and Mn precipitates. Field emission scanning electron microscope analysis of the slag after interaction with
the AMD revealed that metals and ­SO4 precipitated on the slag surface.

Keywords Neutralization · Metals · Geochemical modeling

Introduction
Acid mine drainage (AMD) is a major problem in mining
areas worldwide and affects surface waters (Prasad and Mor-
timer 2011; Rodriguez-Freire et al. 2016; Whitehead and
Neal 2005) and groundwater (Merkel and Mandy 2011; Nai-
cker et al. 2003; Ochieng et al. 2010). In India, the Makum
coalfield of Assam, the Jaintia coalfield of Meghalaya, and
the Gorbi mines of the northern coalfield are well known for
the AMD generation due to their high sulfur content (Baruah
et al. 2006; Equeenuddin et al. 2010; Prasad and Kumar
2015; Sahoo et al. 2012; Tiwary 2001). AMD with a pH as
Electronic supplementary material The online version of this
article (https​://doi.org/10.1007/s1023​0-019-00615​-3) contains
supplementary material, which is available to authorized users.
* Alok Sinha
aloksinha11@yahoo.com
1
Department of Environmental Science and Engineering,
Indian Institute of Technology (Indian School of Mines),
Dhanbad, Jharkhand 826004, India
low as 1.6 occurs in the Jaintia coalfield with the following
metal and sulfate concentrations: Al (15.2–117.8 mg/L), Fe
(38.5–290.4 mg/L), Zn (0.26–15.45 mg/L), Cr (0.17 mg/L),
Pb (0.01–1.58 mg/L), Cd (0.08 mg/L), Cu (0.01–1.82 mg/L),
and sulfate (457–4489 mg/L) (Sahoo et al. 2012). Impacts
of AMD on aquatic ecosystems reported by the Meghalaya
State Pollution Control Board, Shillong, include fish kills
in the Lukha River, at the eastern border of the Jaintia Hills
district (Chabukdhara and Singh 2016). In addition, declin-
ing populations of aquatic life, including frogs, fish, and
benthic macroinvertebrates (Ephemeroptera, Plecoptera,
and Tricoptera) have been noted in this region’s water bodies
(Swer and Singh 2003, 2004). AMD affects the availability
of freshwater resources for domestic use in the Jaintia region
(Swer and Singh 2004).
AMD can be collected and treated to minimize its impact
on receiving streams and rivers. Two types of treatment
options are available, active and passive. Active treatment
focuses on the addition of different alkaline materials, such
as lime, soda lime, hydrated lime, or soda ash to increase
the pH of the acidic solution and precipitate metals in their

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518
hydroxide form (Ziemkiewicz and Skousen 1998). Other
active treatment systems include electrolysis (Buzzi et al.
2013), ion exchange (Feng et al. 2000), and reverse-osmosis
(Zhong et al. 2007). The key advantage of an active treat-
ment system is that it can be implemented with ease and
designed with flexibility for higher flow rates. However, the
major disadvantage of active treatment is its high operation
and maintenance costs (Johnson and Hallberg 2005; Name
and Sheridan 2014).
Passive treatment systems include wetlands (Johnson and
Hallberg 2003; Rose 2010; Taylor et al. 2005) and limestone
drains (Kleinmann et al. 1998; Name and Sheridan 2014).
The main disadvantage with wetland systems is the need
for a large surface area (Johnson and Hallberg 2005; Taylor
et al. 2005). Limestone drains require regular maintenance
for maximum effectiveness. Armoring of the limestone bed,
due to the formation of ferric hydroxide coatings, causes a
barrier to effective treatment (Johnson and Hallberg 2005;
Name and Sheridan 2014; Potgieter-Vermaak et al. 2006).
Difficulties and limitations in both treatment systems led
us to explore alternative materials, including fly ash (Gitari
et al. 2008), zero valent iron (Wilkin and McNeil 2003), zeo-
lites (Prasad and Mortimer 2011), peat and humic materials
(Bogush and Voronin 2011), cement kiln dust (Mackie and
Walsh 2015), and rice husk (Chockalingam and Subrama-
nian 2006). Each of these has advantages and disadvantage
that must be considered when used in field conditions with
different mine drainage chemistries.
Basic oxygen furnace (BOF) slag is a waste product
from the steel industry that contains CaO, which provides
acid neutralization capacity (ANC) (Xue et al. 2009, 2013).
When used to treat AMD, BOF slag creates an alkaline envi-
ronment that causes metals such as Fe, Al, Cu, Ni, Zn, Fe,
Pb, Al, and Cr to precipitate as hydroxides or more com-
plex minerals such as oxy-hydroxides or hydroxy-sulphates
(Gitari et al. 2008; Sheikh Abdullah et al. 1999). However,
Fig. 1  Reaction mechanism for
removal of metals and anions
from AMD by BOF slag
Pb H Al
+
Zn +Cr
H Precipitation of metals
Fe Mn
Ni
Cd
Cu
SO42-
Slag
Acid Mine Drainage
13
Mine Water and the Environment (2019) 38:517–527
highly alkaline conditions result in the elevated solubility
of some metal hydroxides; therefore, pH values > 9 should
be avoided. Precipitation, co-precipitation, and adsorption
of metals on the precipitated mineral surfaces (Fig. 1) are
the mechanisms by which metal and anion removal takes
place (Masindi et al. 2018; Name and Sheridan 2014). The
use of slag for AMD treatment has been extensively studied
by several researchers (Feng et al. 2004; Kruse et al. 2012;
Masindi et al. 2018; Name and Sheridan 2014; Shen and
Forssberg 2003; Ziemkiewicz and Skousen 1998). However,
some previous studies focused only on reducing sulfate and
iron and ignored trace metals (Name and Sheridan 2014),
or examined the use of slag to remove trace elements from
AMD, but made no attempt to optimize reaction time (Feng
et al. 2004). Another study (Masindi et al. 2018) did not
standardize the dose of BOF slag or treatment time, and
the pH of their treated water was very high (pH 10 ± 0.05),
which is not suitable for direct discharge to the environment
without neutralization.
Materials and Methods
Characterization of the BOF Slag
BOF slag was collected from the Bokaro Steel Plant,
Jharkhand, India. The slag was ground in a ball mill and
oven dried at 105 °C for 24 h prior to use. Particle size distri-
bution of the slag was performed using sieves. The analysis
was carried out with 4.75 mm, 2 mm, 1.18 mm, 500 µm,
212 µm, 150 µm, and 75 µm sieves in a mechanical shaker
for 30 min, according to BIS (1985).
The pH of the slag was measured using a glass pH elec-
trode and an Environmental & Scientific Instruments Co.
digital meter (Model 111). The ratio of slag: Milli-Q water
was kept at 1 g of slag: 10 mL of Milli-Q water.
AlO(OH)
FeO(OH)
Cr(OH)3
Al(OH)3
Fe(OH)3
Mn(OH)2
Cu
Zn Zn
FeO(OH) Al(OH)3
SO42-
Cu
Adsorption of metals on
precipitates
Mine Water and the Environment (2019) 38:517–527 519

Acid neutralization capacity (ANC) was determined Table 1  Characterization of laboratory-prepared synthetic acid mine
by the method proposed by Sobek et al. (1978). The ini- drainage (Sahoo et al. 2012)
tial step involves the reaction of a sample with diluted Parameters (units) Value
hydrochloric acid at room temperature. A slight fizz rating
pH (SU) 1.51
was observed. After the fizz test, the correct amount of
Electrical conductivity (µS/cm) 5950
HCl with specified normality was added and the sample
Total dissolved solids (mg/L) 4186
was heated nearly to a boil; the flask was swirled in every
Al (mg/L) 126
5 min until the reaction was complete. After the complete
Co (mg/L) 1.66
reaction, distilled water was added to bring the volume
Cu (mg/L) 1.95
up to 125 mL. Then the sample solution was back titrated
Cr (mg/L) 0.354
with NaOH with the same normality to pH 7. The amount
Cd (mg/L) 0.12
of NaOH added during titration was used to determine
Pb (mg/L) 1.23
how much HCl was neutralized by the sample (Balci and
Fe (mg/L) 288
Demirel 2017; Sobek et al. 1978). The maximum potential
Mn (mg/L) 12.7
acidity (MPA) of the slag was determined from the total
Ni (mg/L) 4.97
sulfur content of the sample (wt%), assuming that all of
Zn (mg/L) 15.6
the S was associated with pyrite (Adam et al. 1997). Net
Ca (mg/L) 191
acid-production potential (NAPP) was calculated by sub-
Mg (mg/L) 72.4
traction of ANC from MPA. A negative NAPP indicates
Na (mg/L) 166
that a sample is non-acid producing, whereas a positive
K (mg/L) 27.6
NAPP indicates that a sample has the potential to release
Sulfate (mg/L) 2053
acid (Weber et al. 2005). Total acidity of the synthetic
acid mine drainage (SAMD) was determined by titration
(APHA 2012).
A field emission scanning electron microscope Treatment of SAMD with Sodium Hydroxide
(FESEM) (Supra 55, Carl Zeiss, Germany) was used to
study the morphology and microstructure of the slag sam- The SAMD was treated with NaOH, and the results were
ple. Its elemental composition was evaluated by FESEM- compared to those with slag. The reaction conditions for
energy dispersive X-ray spectroscopy (FESEM-EDX). The the mixing of SAMD-NaOH were similar to those described
mineralogical phases in the slag were detected using X-ray above for the slag–SAMD interaction.
diffraction (Bruker D8 X-ray diffractometer), operated at
40 kV and 40 mA. The chemical composition of the slag Mixing of BOF Slag with a pH‑Controlled Solution
was determined by X-ray fluorescence using a Bruker S4
PIONEER spectrometer. A solution with a higher pH was prepared with metal con-
centrations similar to those in the SAMD. The pH was
maintained at 3.5 ± 0.08 during the entire reaction. This pH
Treatment of SAMD with the BOF Slag was chosen to evaluate adsorption of metals by adsorption,
which occurs when the pH is less than 5 (Xue et al. 2013).
The AMD of the Jaintia Hills coalfield (Sahoo et al. 2012) The reaction conditions for this solution was similar to those
was simulated in the laboratory (Table 1). The SAMD was for the SAMD-slag interaction (i.e. 30 g/L dose at 0.5 h of
prepared by adding metal sulfate salts to Milli-Q (type-II) reaction time).
water. The pH of the SAMD was adjusted to 1.5 ± 0.04
with 6 N ­HNO3. The metal concentrations and pH were Analysis
generally on the high end for metals and the low end for
pH to represent the region’s most extreme acid mine drain- Treated samples were filtered through a 0.45 µm filter
age. Batch studies were conducted to treat the SAMD with (Merck) and preserved in pre-cleaned polypropylene bot-
different doses of slag (10, 20, 30, 40, 50, and 60 g/L) for tles for metal and anion analysis. The bottles used for metal
different time intervals at 30 ± 0.5 °C. Each dose of slag analysis were acidified with 6 N H
­ NO3 to keep the pH of the
was added to 100 mL of the SAMD solution and placed sample < 2. The analytical work was performed in ISO 9001
in a shaker (Remi Cis-24 plus) at 120 rpm (Sahoo et al. (2008) and ISO 18001 (2007) certified laboratories follow-
2013). Neutralization and precipitation removal mecha- ing standard protocols (APHA 2012). The pH and electrical
nisms for metals and anions were examined using two conductivity (EC) were measured using a glass electrode/
approaches: pH meter (EI, Digital pH Meter-111) and the PCTestr 35

13
520
(Eutech Instruments, Oakton), respectively. TDS was cal-
culated based an internal instrument calibration procedure
(Instruction manual, PCSTestr 35 series). Determination of
metals such as Al, Co, Cu, Cr, Cd, Fe, Mn, Ni, Pb, and Zn
was done using a GBC Scientific Avanta PM double beam
atomic absorption spectrophotometer (AAS). Ca and Mg
were determined by titration, while ­SO4 was determined
using a UV–Vis spectrophotometer (Shimadzu UV-1800).
Na and K concentrations were measured using a Micropro-
cessor flame photometer (ESiCO Model 1385). The solid
slag residue after treatment was analyzed using FESEM-
EDX and X-ray diffraction (XRD).
Saturation Indices Though PHREEQC
Saturation indices (SI) for mineral phases were calculated
using PHREEQC software (PHREEQC Interactive—version
3; Parkhurst 1995). Precipitation of minerals after 24 h of
reaction time with different slag doses was predicted using
this software. A saturation index (SI) > 0 indicates over-
saturation and possible precipitation of mineral phases; val-
ues of SI < 0 specifies the mineral phase is below saturation
and indicates possible dissolution of solid phase; and SI = 0
suggest that the mineral is at saturation in the solution (in
equilibrium with the solution).
Results and Discussions
Characterization of the BOF Slag
During the slag-MilliQ water interaction, the pH increased
from 5.5 to 11.9 and stabilized after 35 min. The high pH
was attributed to the presence of CaO in the slag (Ziem-
kiewicz and Skousen 1998). The ANC of the slag was
33.4 kg ­CaCO3/t. The sulfur content of the slag sample
was 0.397% (w/w). The MPA and NAPP of the slag was
Fig. 2  Particle size distribution 100
of BOF slag
90
80
70
Percent finer
60
50
40
30
20
10
0
0.01
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Mine Water and the Environment (2019) 38:517–527
calculated as 12.4 kg and − 21.33 kg C ­ aCO 3/t, respec-
tively. Therefore, the slag is not considered acid-generat-
ing (Weber et al. 2005). The total acidity of the SAMD was
2.47 kg (as C­ aCO3/t). Therefore, the slag has the potential
to neutralize AMD.
The particle size distribution curve for the slag sample
is shown in Fig. 2. The values of the ­D 60, ­D30, and ­D10
were 0.37 mm, 0.14 mm, and 0.075 mm, respectively. The
coefficient of uniformity (­ Cu = ­D60/D10) and coefficient of
curvature ­(Cc = D230/D60D10) were 4.53 and 0.696, respec-
tively. The C
­ u was > 4 but the C­ c was < 1, which indicates
that the slag was poorly graded.
Examination by FESEM revealed the desiccated sur-
face of the slag before treatment (Fig. S1), with some
angular, plate-like, or sub-rounded particles (Fig. 3a).
During the cooling and solidification of hot slag, gases
are entrained, causing a cellular and vesicular structure
(Chand et al. 2017). Elemental analysis (Fig. 3b) depicts
the composition (Table 2) of the slag. It reveals that the
highest elemental percentages in the slag are Ca, O, and
Fe, and the presence of other elements, including Si, C,
Mg, Mn, Al, and Ti.
XRD analysis of the slag revealed the different major
and minor mineral phases present in the sample before
(Fig. 4a) and after treatment (Fig. 4b). The most prominent
and abundant mineral phase was portlandite (Ca(OH)2) (1),
as slag contains 55.2% CaO, which converts to Ca(OH) 2
after interaction with moisture. The other phases identified
were srebrodolskite (­ Ca2Fe2O5) (2), calcite-rhodochosite
((Ca,Mn)CO3) (3), merwinite (­ Ca3Mg(SiO4)2) (4), dolo-
mite (CaMg(CO3)2) (5), and lime (CaO) (6). XRF analysis
of revealed that the major components of the slag are Ca
(55%), Fe (15.1%), and Si (7.23%) with lesser amounts
of Al (1.08%), Mg (1.43%), Mn (0.77%), S (0.307%), Na
(812 ppm), K (325 ppm), Cu (113 ppm), and Zn (115 ppm)
(Table S1).
D10 0.1 D30 D60 1 10
Particle diameter (mm)
Mine Water and the Environment (2019) 38:517–527 521

Fig. 3  Microstructure of a raw (untreated) BOF slag and b elemental analysis

Table 2  Elemental composition of BOF slag before and after interac-

tion with SAMD (30 g/L slag dose) analyzed using FE-SEM-energy
dispersive X-ray spectroscopy

Elements Weight%
Before interaction with After inter-
SAMD action with
SAMD

C 2.31 2.00
O 32.7 26.7
Mg 1.90 2.79
Al 0.54 1.66
Si 5.14 3.10
Ca 34.9 37.2
Ti 0.42 0.42
Mn 0.79 1.48
Fe 13.3 16.00
S – 3.79
Zr – 2.07 Fig. 4  XRD analysis of BOF slag a before and b after interaction
with SAMD

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522 Mine Water and the Environment (2019) 38:517–527

Treatment of AMD with Slag a

100

% Removal of metals and sulfate

Slag dose(g/L)
As the slag dose increased from 10 to 60 g/L, the pH 90
increased from 5.3 to 11.2 after 24 h of reaction time 80 10
70
(Fig. 5a). The pH increase was due to the presence of CaO 20
60
and MgO, which dissolve and create hydroxyl ions, increas- 30
50
ing the pH. After 24 h of reaction, the pH was 8.6 with a 40 40
30 g/L dose of slag, and 10.9 with 40 g/L of slag. Further 30 50
large pH variations were not observed with increasing slag 20 60
dose, and the pH stabilized at pH 11.2 at the 50 g/L dose. 10
The EC decreased with increased doses of slag (Fig. 5b). A 0
decline of ≈ 58% in EC was achieved with a 60 g/L slag dose,
due to the removal of ions by precipitation of hydroxides.
The removal of metals at different slag doses is shown b
60
in Fig. 6a, b. The Fe removal was ≈ 99% with a 10 g/L slag

% Increase in Ca concentration
dose, and remained at that level at higher slag doses. Fe 50
removal was probably due to the formation of Fe precipitates
40
(Gitari et al. 2008; Masindi et al. 2018; Name and Sheridan
2014) that start to form at pH 3.5 (Masindi et al. 2018). The 30
SI values (Table 3) show that the treated solution was over-
20
saturated with goethite (FeOOH) and hematite ­(Fe2O3) for
all slag doses. Ferrihydrite (Fe(OH)3) was undersaturated at 10
pH 5.3, oversaturated up to pH 10.9, and then undersaturated 0
at pH 11.2. Based on the SI values, Fe removal was most 0 10 20 30 40 50 60
likely due to goethite and hematite precipitation and possibly Slag dose (g/L)

Fig. 6  a Percent removal of metals and sulfate, and b percent increase
a in Ca concentration in treated SAMD with different doses of BOF
12 slag
10
8 ferrihydrite (Fe(OH)3 at neutral to moderately alkaline pH
values.
6
pH

The Al removal gradually increased with BOF slag dose

4 (Fig. 6a). At a dose of 30 g/L, 98% removal of Al took
2 place. Al can be removed as basaluminite ­(Al4(OH)10SO4),
boehmite (AlOOH), alunite (­ KAl3(SO4)2(OH)6), gibbsite
0
0 10 20 30 40 50 60 (Al(OH)3), and diaspore (AlOOH) in the pH range of the
Slag dose (g/L) study (Doye and Duchesne 2003; Gitari et al. 2008; Masindi
et al. 2018;). However, the calculated SI values showed that
b Al concentrations were likely controlled by the formation
4500
of gibbsite, amorphous Al(OH)3, and alunite at the lower
4000
3500 pH values. Gibbsite was oversaturated over the entire
3000 experimental pH range (5.3–11.2). Amorphous Al(OH)3
EC (µS/cm)

2500 and alunite were near saturation or oversaturated at the two

2000 lower pH values; at higher pH, both mineral phases became
1500 undersaturated.
1000 A total of 80.9% Mn removal was observed with the
500
0
10 g/L dose, which increased to 98.5% removal at 30 g/L.
0 10 20 30 40 50 60 Mn can precipitate as manganite (MnOOH), hausamannite
Slag dose (g/L) ­(Mn3O4), pyrochoite (Mn(OH)2), and pyrolusite (­ MnO2) or
adsorbed onto iron (oxy)hydroxide and aluminium (oxy)
Fig. 5  Variation in a pH and b electrical conductivity of treated hydroxide surfaces. Mn starts to precipitate in these forms
SAMD with different doses of BOF slag at pH values greater than 8 and is supersaturated at a pH

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Mine Water and the Environment (2019) 38:517–527 523

Table 3  Calculated saturation Slag dose (g/L) 10 20 30 40 50 60

indices for mineral phases pH
formed due to interaction of 5.3 6.8 8.6 10.9 11.2 11.2
SAMD with slag at different
Mineral phases
doses after 24 h of reaction time
Al(OH)3(a) 0.72 1.60 − 0.78 − 3.23 − 3.94 − 4.13
Alunite ­(KAl3(SO4)2(OH)6 12.1 10.2 − 2.90 − 16.8 − 20.1 − 20.9
Anglesite ­(PbSO4) − 2.50 − 2.52 − 3.01 − 6.95 − 7.90 − 8.02
Anhydrite ­(CaSO4) − 0.61 − 0.58 − 0.60 − 0.62 − 0.65 − 0.73
Cd(OH)2 − 12.2 − 9.13 − 5.32 − 1.93 − 1.84 − 1.84
CdSO4 − 10.9 − 10.9 − 11.1 − 12.1 − 12.8 − 12.9
Fe(OH)3(a) − 3.49 0.87 1.74 0.02 − 0.33 − 0.53
Gibbsite (Al(OH)3) 3.36 4.25 1.86 1.58 1.48 1.38
Goethite (FeOOH) 2.58 6.94 7.80 6.08 5.73 5.53
Gypsum ­(CaSO4, ­2H2O) − 0.36 − 0.33 − 0.35 − 0.37 − 0.40 − 0.48
Hausmannite ­(Mn3O4) − 24.1 − 12.6 − 0.78 14.9 12.1 12.2
Hematite ­(Fe2O3) 7.18 15.9 17.6 14.20 13.5 13.1
Jarosite-K ­(KFe3(SO4)2(OH)6) − 9.66 − 1.18 − 4.52 − 16.4 − 18.5 − 19.3
Manganite (MnOOH) − 10.3 − 6.01 − 1.58 4.56 3.71 3.72
Melanterite ­(FeSO4, ­7H2O) − 5.57 − 5.76 − 10.7 − 19.1 − 20.4 − 20.7
Pyrochroite (Mn(OH)2) − 9.50 − 6.67 − 4.14 − 0.20 − 1.35 − 1.34
Pyrolusite(MnO2,H2O) − 16.3 − 10.5 − 4.13 4.20 3.65 3.66
Zn(OH)2(a) − 6.94 − 5.15 − 2.89 − 2.83 − 2.92 − 2.92
Pb(OH)2 − 5.52 − 2.49 0.71 1.44 1.18 1.18

greater than 10 (Gitari et al. 2008; Madzivire et al. 2011).
The calculated SI values showed that manganite, hausaman-
nite ­(Mn3O4), and pyrolusite (­ MnO2) were undersaturated
from pH 5.3–8.6, and became oversaturated at pH 10.9 and
11.2.
The lowest slag doses (10 and 20 g/L) removed 99% of
the Cu and Zn. The SI values showed that Zn(OH)2 remain
undersaturated over the entire slag does and pH range
(Table 3). PHREEQC modeling results also showed that
the solution was oversaturated with Fe(OH)3(a), gibbsite
(Al(OH)3), and goethite (FeOOH), which indicates the pos-
sible adsorption of Cu and Zn onto iron and aluminium (oxy)
hydroxides surfaces.
The percent removal of Cd, Cr, and Pb was high with the
10 g/L slag dose, and co-precipitation or adsorption onto the
Fe, Al, and Mn minerals surfaces was likely an important
part of the removal process. The Pb concentration was below
the detection limit (0.01 mg/L) at this dose. The dominant
Cd species in solution was C­ d2+ for a wide pH range (2–9),
and shifted to Cd(OH)2(aq) and [Cd(OH)3]− at pH > 10 (Xue
et al. 2009). PHREEQC results showed that Cd(OH)2 and
­CdSO4 formation did not contribute to Cd removal. The pre-
cipitation of Pb(OH)2 could have removed Pb from solution
(Table 3). The Ni and Co was removed at ≈ 99% and 100%,
respectively, with a 30 g/L dose, possibly by precipitation
on the alkaline slag surface.
The Na and K percentage removals were observed to be
much less than the trace elements and the percent removal
did not increased with increased slag dose. A removal of
2.2% and 3.4% for Na took place at 10 and 60 g/L slag dose,
respectively. Similarly, for K, 11.2% removal was observed
at 10 g/L and 14.1% at 60 g/L. However, Ca concentrations
actually increased by about 53% with 60 g/L of slag, due
to Ca leaching from the slag surface. Mg showed strong
removal (96%) with the 60 g/L slag dose. Mg can precipitate
as Mg(OH)2 at a pH of about 8.5 (Madzivire et al. 2011).
The ­SO4 removal percentage was low. Approximately 40%
removal was achieved with a 30 g/L dose, whereas a maxi-
mum removal of 67.2% was observed with 60 g/L (Fig. 6a).
SI values (Table 3) predicted the possible formation
of gypsum (­CaSO 4·2H 2O), anhydrite (­CaSO 4), alunite
­( KAl 3(SO 4) 2(OH) 6), and jarosite-K ­(KFe 3(SO 4) 2(OH) 6.
However, the calculated SI values indicate that the treated
solution is only oversaturated with alunite at pH 5.3 and 6.8,
while all other sulfate-containing phases are undersaturated.
This indicates that ­SO4 removal could have been due to the
formation of gypsum, which is close to saturation (Table 3),
and alunite (Madzivire et al. 2011).
The 40 g/L slag dose increased the pH to 10.9, whereas
the 30 g/L slag dose resulted in a pH of 8.6. However, there
was no major difference in metal removal between the two
doses. Therefore, the 30 g/L slag dose was identified as the
optimal BOF slag dose to meet India’s effluent discharge
standards (BIS 1981). All concentrations met Indian indus-
trial discharge standards, with the exception of total dis-
solved solids and sulfate (Table 4).

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524 Mine Water and the Environment (2019) 38:517–527

Table 4  Characterization of Parameters Values of parameter after different reaction times

treated and filtered SAMD
water with slag (30 g/L) at 0.5 h 1h 2h 3h Effluent discharge standards
different reaction times (BIS 1981) for inland surface
water

pH 6.36 7.2 7.9 8.5 5.5–9.0

Electrical conductivity (µS/cm) 3917 3762 3514 3217 –
Total dissolved solids (mg/L) 2610 2610 2440 2280 2100
Ca (mg/L) 244.42 248.31 252.32 255.14 –
Na (mg/L) 162 162 161 161 –
K (mg/L) 25.2 24.9 24.6 24.1 –
Mg (mg/L) 19.72 13.29 9.35 4.63 –
SO4 (mg/L) 1520 1450 1240 1000
Al (mg/L) 5.93 2.88 2.73 2.27 –
Cu (mg/L) 0.041 0.032 0.021 0.009 3
Cr (mg/L) 0.005 0.003 0.003 0.003 2
Cd (mg/L) 0.0004 0.0004 0.0004 0.0004 2
Co (mg/L) 0.063 0.047 0.017 0.011 –
Fe (mg/L) 14.2 2.28 0.652 0.217 –
Mn (mg/L) 0.48 0.31 0.19 0.075 –
Ni (mg/L) 0.172 0.083 0.052 0.021 3
Pb (mg/L) 0.064 0.053 0.031 0.018 0.1
Zn (mg/L) 0.118 0.084 0.026 0.008 5

90 BOF Slag
a
% Removal of metals and sulfate

100 Pb NaOH
70
90 Cr
80
% Removal of metals

Cu 50
70 Cd
60 30
Co
50
40 Fe
10
30 Mn
20 Ni -10
10 Zn
0 Al -30
0 1 2 3
Time (Hrs) Fig. 8  Comparison of percentage removal of elements in SAMD
b treated by slag and NaOH
120
Na Initial con.
% Removal of alkaline metals and

100 10000
80 Final con.
K
Concentration (mg/L)

60
1000
40 Mg
sulfate

100
20
Ca
0 10
-20 0 10 20 30 Sulfate
1
-40
-60 0.1
Time (Hrs)

Fig. 7  Percentage removal of a trace metals and b alkaline metals and

sulfate in treated SAMD with respect to time at the 30 g/L BOF slag
Fig. 9  Initial and final concentration (mg/L) of elements in pH con-
dose
trolled solution during treatment by slag (30 g/L; 0.5 h)

13
Mine Water and the Environment (2019) 38:517–527
Fig. 10  FESEM images of the
surface of BOF slag after treat-
ment with SAMD a microstruc-
ture, b elemental analysis
Maximum metal removal took place within the initial
hour of reaction time (Fig. 7a–c). Figure 7a illustrates
the increase in metal removal as the reaction progressed.
Among all of the metals, Cd achieved 99.7% removal within
0.05 h of reaction time. Approximately 96% removal of the
Cu and Cr took place after 0.33 h, while it took 0.4 h for
96% removal of Co. A total of 95.1% of Fe was removed
within 0.5 h, whereas, 96%, 99%, and 99% removal was
observed for Mn, Ni, and Zn, respectively. Pb removal also
approached 99% after 0.5 h of reaction time. Therefore, all
metals achieved more than 95% removal within 0.5 h of
reaction time.
Among the alkaline metals, only Mg removal was high,
with 72.8% removal after 0.5 h and 94.1% removal after 3 h
of reaction time. Na and K removal was much less at 2.65%
and 12.7%, respectively, after 3 h of reaction time. In con-
trast, Ca leached from the slag (Fig. 7b) and ­SO4 removal
was very low. After 0.5 h, only 25.9% removal took place; it
increased to ≈ 40% after 3 h of reaction time and remained
constant for the remaining reaction period (Fig. 7c). Table 4
shows that all of the parameters except total dissolved sol-
ids and ­SO4 comply with the Indian industrial effluent dis-
charge limits for inland surface water (BIS 1981). After 3 h
525
of reaction time, ­SO4 and TDS concentration still did not
meet the guideline concentration.
The treatment mechanism was investigated by treating
the SAMD with 1 N NaOH solution. This increased the pH
to 6.86; the results for a 0.5 h reaction time are presented in
Fig. 8. NaOH is an alkaline agent that increases the pH of
the solution without lime or slag. The results showed that
metal and anion removal percentages with NaOH were com-
parable with the removal rates with the BOF slag.
Treatment results (Fig. 9) of the pH-controlled solution
with 30 g/L dose and 0.5 h reaction time showed that metal
concentrations were the same before and after treatment.
This indicates that the slag did not act as a sorbent.
These two studies verified that BOF slag acts as an alka-
line agent, which caused precipitation and co-precipitation
of metals. Similar observations were reported by Masindi
et al. (2018). The research indicates that slag does not
require high doses (Gitari et al. 2008), nor modification or
conversion, as has been reported with fly ash (Prasad and
Kumar 2015; Prasad and Mortimer 2011; Sahoo et al. 2013).
The slag can be added directly to the AMD or AMD-affected
streams as an alkaline material to remove metals and, to a
much lesser extent, anions such as sulfate (Ziemkiewicz and
Skousen 1998; Zurbuch 1996). BOF slag has the potential
13
526
to treat AMD with an extremely acidic pH (pH ≈ 1.5). Our
study successfully treated the SAMD, optimized a dose rate,
determined that only ≈ 0.5 h was required for treatment, and
found no leaching of trace metals from the slag.
Mineralogical Analysis of the Slag Sample After
Treatment
The solid residue of slag samples after treatment with a
30 g/L slag dose was analyzed using FESEM and XRD.
From FESEM analysis, it was observed that metals pre-
cipitated on the surface of steel slag, and the texture of
the slag was completely changed due to this precipitation
(Fig. 10a–c). The crystalline structure of precipitated metals
and needle-shaped and rod-like structure of gypsum was also
observed covering the BOF slag surface. EDX analysis of
the solid residue showed that metal percentages were higher
in the treated vs untreated slag (Table 2). This may be due
to the precipitation of metals such as Fe, Al, Mn, and Mg
on the slag surface after SAMD–slag interaction. Further-
more, gypsum crystals were present in the XRD analysis
of the solid residue (Fig. 4b). XRD analysis did not reveal
any other mineral phases, which may be due to either the
amorphous nature of the precipitates or their amounts may
be below detection by XRD (Gitari et al. 2008).
Conclusions
This study confirmed that the effective treatment of SAMD
with BOF slag depends on slag dose and contact time.
Approximately 95% of the trace metal removal took place
with 30 g/L of slag and only 0.5 h of reaction time. Satura-
tion indices calculated using the PHREEQC geochemical
code indicated that the Fe concentration was controlled by
the formation of goethite, hematite, and Fe(OH)3; Al by
gibbsite, Mn by hausmannite, manganite, and pyrolusite;
and Cu and Zn by adsorption onto the precipitated phases or
the slag surface. Cd and Pb concentrations may be controlled
by hydroxide formation or adsorption. The Ca and ­SO4 con-
centrations were controlled by gypsum precipitation. Alunite
formation also contributed to ­SO4 removal. However, Na and
K concentrations were not controlled by mineral precipi-
tation. The treated water meets discharge limits for Indian
inland surface water with the exception of sulfate and TDS.
Acknowledgements The authors thank the Ministry of Human
Resource Development, Government of India, for financial support.
The authors also acknowledge the Department of Environmental Sci-
ence and Engineering, Indian Institute of Technology (Indian School
of Mines), Dhanbad, for providing logistical support.
13
Mine Water and the Environment (2019) 38:517–527
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