Global NEST Journal, Vol 20, No 3, pp 512-528

Copyright© 2018 Global NEST

Printed in Greece. All rights reserved

A review on treatment of acid mine drainage with waste

materials: A novel approach
Sukla Saha and Alok Sinha*
Department of Environmental Science & Engineering, Indian Institute of Technology (ISM) Dhanbad - 826004, Jharkhand, India
Received: 01/02/2018, Accepted: 17/9/2018, Available online: 26/09/2018
*to whom all correspondence should be addressed: e-mail: [email protected]
https://doi.org/10.30955/gnj.002610

Abstract minerals to water and oxygen results in generation of

AMD.
The present study systematically and comprehensively
reviewed different aspects of treating Acid Mine Drainage The reason behind AMD generation is the presence of
(AMD) with active treatment and waste materials. The sulfide mineral, in form of iron sulfide-aggregated rocks
work also critically reviews the status and the factors and exposure of these minerals to water and oxygen (Akcil
associated with the treatment process. Although, and Koldas, 2006).
conventional active methods are very efficient but they This phenomenon is more prominent in abandoned mines
are mainly associated with costly material as well as high than active mines, as in latter case water tables are kept
maintenance cost which enhances the cost of entire low by continuous pumping system. However, in case of
treatment system. Waste materials such as fly ash, abandoned mines, pumping systems are disabled and the
metallurgical slag, zero valent iron (ZVI), cement kiln dust voids generated due to mining are filled with water. This
(CKD), organic waste such as peat humic agent (PHA) and water than reacts with the pyrite present in the rocks of
rice husk can be efficiently used for the treatment of these mines and generates acidic drainage, thereby
AMD. However, efficiency of different waste material contaminating the groundwater (Johnson and Hallberg,
varied from each other due to the variation in their 2005; McCarthy, 2011). However, the reason behind the
physical and chemical characteristics. The results from the AMD production is not only restricted to the mining
investigation showed that fly ash, metallurgical slag and activities, it can also takes place in the highway, tunnel
CKD raise the pH of acidic solution more, in comparison to construction and other deep excavations. The primary and
ZVI and organic waste, due to their richness in lime secondary sources of AMD are presented in Table 1 (Akcil
content. Furthermore, fly ash can be efficiently converted and Koldas, 2006).
and utilized in its other derivative such as chemically
Table 1. Sources of Acid Mine Drainage (Akcil and Koldas, 2000)
modified fly ash and zeolite. Efficiency of ZVI is hindered
by the presence of higher concentration of total dissolved Primary sources Secondary sources
solids. PHA can treat AMD that is mild acidic in nature. Mine rock dump Treatment sludge pounds
Besides, long retention time is required for the removal of Tailings impoundment Rock cuts
heavy metals and sulfur with organic waste and sulfate Underground and open Concentrated load-out
reducing bacteria (SRB). The study also potentially pit mine workings
reviewed that metal removal from AMD varied due to Pumped/nature Stockpiles
composition of AMD and the characteristics of waste discharged underground
materials. However, waste materials demand more water
attention for its practical applicability in field conditions Diffuse seeps from Concentrate spills along roads
due to its richness, higher possibility for recycling and replaced overburden in
reuse, low installation cost and harmless nature towards rehabilitated areas
the environment. Construction rock used in Emergency ponds
roads, dams etc.
Keywords: Acid Mine Drainage; Active Treatment; Fly Ash;
Metallurgical Slag; Zero Valent Iron; Organic waste.
Figure 1 illustrates the process of AMD generation. It
1. Introduction shows that pyrite oxidation can take place through several
Acid Mine Drainage (AMD) refers to the effluent pathways including surface interactions with dissolved O2,
generated from active as well as abandoned mines. The Fe3+, and other mineral catalysts such as MnO 2 (Buzzi et
exposure of rocks consisting of ferrous or ferric sulfide al., 2013). Oxidation of pyrite (FeS2) through (1(a) and
1(b)) is key reaction for AMD generation. Pyritic oxidation
Sukla Saha and Alok Sinha (2018), A review on treatment of acid mine drainage with waste materials: A novel approach, Global NEST
Journal, 20(3), 512-528.
A REVIEW ON TREATMENT OF ACID MINE DRAINAGE WITH WASTE MATERIALS: A NOVEL APPROACH 513

leads to the formation of dissolved iron, sulfate and rock and 1.9 billion tons of tailings respectively, have
hydrogen (1). potential to generate acidic drainage (Acid report 2010).
Groundwater present in the mining district of
Johannesburg, South Africa is massively polluted and
extremely acidified because of oxidation of pyrite present
in mine tailings dumps (Naicker et al., 2003). Also, in the
areas of Witwatersrand goldfield, which is also known as
the rand, underground mine voids, surface mine tailings
dumps, waste rocks, created in the course of mining,
milling and processing of ores are the key source of acid
mine drainage generation (Ochieng et al., 2010; Merkel
and Mandy, 2011). Water pollution including AMD in
Loskop Dam, Vaal river catchment and the Olifants River
Catchment area, due to Mpumalanga coalmines, has been
reported (Acid Report 2010; Manders et al., 2009; Merkel
Figure 1. Model for oxidation of pyrite (Buzzi et al., 2013) and Mandy, 2011). McCarthy et al. (2011) also reported
that acidic drainage from Witbank and Middelburg
Fe2+, SO42-, H+ are dissolved into the drainage and act as coalmines contaminated the tributaries of the Olifants
the key indicator for the increasing total dissolved river. In India, Makum coal fields in Assam, Jaintia
concentration of metals and acidity of the drainage. H + coalfield in Meghalaya, Western Coalfield (WCL), Northern
helps to reduce the pH of the drainage. Fe2+ undergoes Coalfiled (NCL), north-eastern coalfield are prone to
further oxidation (2) if there is favorable oxidizing generate AMD by the oxidation of pyrite present in coals
condition prevails in terms of oxygen concentration, pH, (Baruah et al., 2006; Equeenuddin et al., 2010; Sahoo et
and microbial activity (Akcil and Koldas, 2006). Ferric iron al., 2012; Tiwary, 2001).
precipitates as ferric hydroxide (Fe(OH)3) and jarosite if If this acidic drainage is not treated then it can
the pH value of the reaction lies between 2.3-3.5 (4) (Akcil contaminate the surface as well as ground water, destroy
and Koldas, 2006; Simate and Ndlovu, 2014). Ferric the plant, aquatic and human life. AMD has severe
hydroxide, so formed, is not stable when the solution pH negative impact on the environment. Therefore, AMD
is less than 2, and Fe3+ remains in the solution (Dold, must be treated to ensure the safety and to minimize the
2010). Remaining Fe3+ present in the solution, that cannot environment and health risk.
be converted into ferric hydroxide (precipitated) form,
acts as an oxidizing agent for further pyrite oxidation Treatment of AMD is divided into two categories, i.e.
through (3) (Akcil and Koldas, 2006). Fe2+ produced from active and passive. To adopt the treatment options,
the similar reaction aids to continue the reaction (2) and economic factors and technical factors are always
(4) until entire ferric iron or pyrite is exhausted. considered. Economic factor comprises of price of
reagents, labor, machineries, equipment, time scale for
AMD is highly acidic in nature; pH ranges from 2-3 with treatment and rate of interest. Technical factors include
elevated concentration of different heavy metals, ferrous acidity levels, influent flow, type and concentration of
and non-ferrous metal sulfate (McCarthy, 2011). heavy metals present in AMD wastewater (Skousen et al.,
Qualitative information about the nature of AMD can be 2000). Active treatment refers to the continuous
identified through the visual examination of rock and application of alkaline materials into the drainage water
effluent. Organic stains and cloudy water indicates about to neutralize acidic mine waters and to precipitate metals.
the presence of iron with pH value above 3.5 whereas Whereas, passive treatment is the process where natural
wine-colored stains with clear effluent is strong indicator and constructed wetlands are used to treat the acidic
of iron with pH value less than 3.5. Presence of aluminium drainage (Johnson and Hallberg, 2005).
(Al) can be detected by white color stains with pH value
above 4.5. However, chocolate brown to black stains This manuscript critically reviews different active
clearly specify the presence of manganese in the effluent treatment methods that uses waste materials as the main
at a pH level greater than 7 (Fripp et al., 2000). Although component in the process. It also provides a comparative
the concentration of the metals and pH of the AMD varies, analysis among different waste materials with respect to
but sulfate concentration remains higher in all effluents metal percentage removal efficiency and a detailed
generated from various mines. knowledge about the waste materials that can be used
successfully for the treatment of AMD.
It causes major environmental pollution. Approximately
7000 km of streams in Unites States of America (USA), was 2. Treatment technology for AMD
severely damaged by AMD; 8000-16000 km of streams in Owing to the difficulties in controlling the AMD at source,
the USA are in worst condition and extremely it is rather an alternative approach to collect and treat
contaminated by AMD (Acid report 2010; USEPA 1995). AMD, thereby minimizing the impact of AMD on receiving
An investigation in metal mine and industrial-mineral streams, river and other environmental components.
tailings in Canada indicated that 6 billion tons of waste
rock and 7 billion tons of tailings; 750 billion tons of waste
514 SUKLA SAHA and ALOK SINHA

2.1. Active treatment membrane for longer operational time. Moreover, this
The most extensively used methodology to mitigate AMD process is only useful for the AMD laden with low metal
is active treatment that includes various processes such as concentrations. Therefore, the applicability of RO and
aeration, addition of neutralizing agents, reverse osmosis, nanofiltration needs to be investigated further for the
ion exchange, electro dialysis and natural zeolites (Ali, treatment of AMD with high metal concentrations as well
2011). as requirement for the pre or post treatment or another
stage of reverse-osmosis treatment for complying the
Aeration is done to introduce air into water, which environmental standards (Sastri, 1979).
facilitates the oxygen to combine with metals and forms
metal oxides, which gets precipitated. Different type of
aerators are available for this process, but mechanical
surface aerators are used for hydrated lime treatment
plants for the treatment of highly acidic and reduced
water. Mechanical surface aeration helps to incorporate
oxygen into water by rotating its blades located beneath
the water in aeration basins. Aerator creates turbulence
that disperses air bubbles and keeps the iron floc in
suspension. High velocity spray nozzles are used for in-line
aerators to improve the contact between air and water.
However, the efficiency of aeration in terms of ferrous ion
oxidation depends on pH, as inorganic oxidation reaction Figure 2. Conventional AMD treatment plant
is slow below pH 5. Therefore, this oxidation process is
combined with the addition of base, to neutralize pH Ion exchange is the reversible interchange of ions
(Skousen et al., 1998; Skousen et al., 2000). between a solid medium and the aqueous solution. Ion
For neutralization and treatment of AMD, some chemicals exchange resins or materials comprise of chemically inert
such as limestone, hydrated lime, pebble quick lime, soda polymer matrix with functional groups that are anionic or
ash briquettes, caustic soda, ammonia, magnesium cationic. For treatment of hard water, water is passed
hydroxide, magna lime are widely used. Enhancement of through a bed of ion exchange material, which is charged
pH of the solution to precipitate the insoluble metals as with monovalent cations, such as sodium. Treatment of
hydroxides or carbonates and for rapid chemical oxidation South African gold mines acidic drainage was done by
of ferrous iron is done by providing sufficient amount of heavy metal precipitation using lime followed by ion
alkalinity in the solution. Most of the metal ions except exchange for calcium and magnesium with sodium ions.
Fe3+, precipitate from water in a pH range of 6-9. (Skousen et al., 1998; Feng et al., 2000). Although, ion-
Therefore, appropriate neutralizing agents are chosen for exchange generates 98% water recovery, but it requires
specific condition. Table 2 summarizes the characteristics some pre-treatment that increases the cost of treatment
as well as the advantages-disadvantages of using different process. Feng et al. (2000) reported that an ion exchange
neutralization materials. plant with a capacity 2.5 ML/d treating AMD effluent,
requires 2.5 kg/m3 acid for regeneration of resin, 2.5
Figure 2 shows conventional treatment plant that uses
lime for the treatment of AMD (Aubé and Eng, 2004). kg/m3 of lime and produces 98% of water recovery. For
Lime is added to the reactor filled with AMD to enhance the whole operation, estimated cost is US$0.40/m3. On
other side, Gaikwad et al. (2010) carried out the
the pH of AMD which facilitates the precipitation of
metals present in AMD. Than flocculent is added and performance and design of ion exchange column treating
stirred into flocculent reactor to encourage the floc the AMD contaminated with copper. It was evaluated that
for treatment of 5.137x10-3 m3/cycle of water and resin
formation and enhance the settling rate of the
capacity of 36 kg/m3, required 9.8175 x 10-4 m3 of resin. It
precipitated metals in form of larger particles. Than the
treated water is taken out from the flocculent reactor and was also reported that the diameter of the ion-exchange
sludge disposed of. column was approximately 0.05 m and the amount of
water required for backwashing was 0.4594 m3/hr.
AMD when treated by reverse osmosis produces high
Electrodialysis (ED) unit consists of number of narrow
quality effluent water which is suitable for potable or
compartments separated by closely spaced membranes
industrial use, while the concentrated acidic brine solution
left behind contains Fe and sulfate (Skousen et al., 1998). and its each compartment is divided with cation and anion
Ultra Pressure Reverse Osmosis (ULPRO) attains 97% and membranes. Positive and negative electrodes are placed
at extreme opposite end of the unit. After filling the
96% rejections of heavy metal and total conductivity in
channels with solution, electrodes are energized and the
comparison to Nano filtration (NF) with 90% and 48%
rejection, respectively (Zhong et al., 2007). However, the ions in solution migrate towards the charged poles and
ions are collected on the membranes (Skousen et al.,
major disadvantage of this process is less water recovery
1998, Buzzi et al., 2011). Buzzi et al. (2013) has studied the
efficiency (13.8%-15.3%). High pressure is essential for
more water recovery, which in turn enhances treatment effectiveness of electrodialysis for the pretreated acidic
cost. Researchers have also reported about the fouling of drainage with microfiltration. However, if AMD contains
Fe, than it forms a precipitates at the surface of cation-
A REVIEW ON TREATMENT OF ACID MINE DRAINAGE WITH WASTE MATERIALS: A NOVEL APPROACH 515

exchange membranes, which requires increase of removal of Fe is considered as a pre-treatment for ED

membrane voltage in continuous manner. Therefore, process to treat the acidic water.

Table 2. Characteristics of different neutralization materials used for the treatment of AMD
Sl. No. Name of acid Saturation Solubility Advantage Disadvantage References
neutralization pH (mg/L) in
cold water
1. Limestone 8-9.4 14 Inexpensive Low solubility in Skousen et al.
material, safe cold water, (1996); Skousen
and easy to generate external et al. (1998);
handle coating or Skousen (2002);
armouring Taylor et al.
(2005)
2. Hydrated Lime 12.4 1300-1850 Cost effective Being hydrophobic, Skousen et al.
reagent for it requires (1996); Skousen
high flow and mechanical aerator et al. (1998);
highly acidic for mixing Skousen (2002);
AMD solution Taylor et al.
(2005)
3. Pebble Quick 12.4 1300-1850 Cost effective It is very reactive, so Skousen et al.
Lime neutralizing metering (1996); Skousen
agent equipment needed et al. (1998);
to ensure proper Skousen (2002);
mixing Taylor et al.
(2005)
4. Soda Ash 11.6 75,000 Useful for low Soda ash briquettes Skousen et al.
Briquettes flow and low absorbs moisture, (1996); Skousen
amounts of expand and thereby et al. (1998);
acidity and stick to the corners Skousen (2002);
metals of hopper in basket- Taylor et al.
hopper system. (2005)
5. Caustic Soda 14 450,000 Can be used in Incurred high cost, Skousen et al.
remote not safe to handle (1996); Skousen
location and generates high et al. (1998);
Very soluble sludge volume Skousen (2002);
and easily Taylor et al.
disperse in (2005)
water
6. Ammonia 9.2 900,000 Reactive and Cannot be handle Skousen et al.
easily soluble easily, increasing (1996); Skousen
Incurred 50- the concentration of et al. (1998);
70% less cost hazardous nitrate, Skousen (2002);
than caustic specialized persons Taylor et al.
soda are required for safe (2005)
handling of
ammonia
7. Magnesium 9.5-10.8 1-50 Cost effective Being hydrophobic, Skousen et al.
Hydroxide reagent for it requires (1996); Skousen
high flow and mechanical aerator et al. (1998);
highly acidic for mixing Skousen (2002);
AMD solution Taylor et al.
(2005)
8. Magna Lime 9.5-10.8 1-50 Cost effective It is very reactive, so Skousen et al.
neutralizing metering (1996); Skousen
agent equipment needed et al. (1998);
to ensure proper Skousen (2002);
mixing Taylor et al.
Dissolution kinetics (2005)
is marginally lower
than quick lime.
516 SUKLA SAHA and ALOK SINHA

Zeolites are known to be naturally occurring hydrated removed as Fe(OH)3 and as schwertmannite
aluminosilicate minerals. They are closely related to the (Fe8O8(OH)6(SO4).nH2O). For aluminium (Al) at pH 3.96-
group of minerals known as “tectosilicates”. The 5.9, jurbanite controlled the Al concentration at the
formation of natural zeolites is due to alteration of glass beginning stages of the neutralization process (Gitari et
rich volcanic rocks by fresh water or by seawater. Three- al., 2008). Although, many researchers have reported
dimensional frameworks of SiO4 and AlO4 formed the higher removal percentage of Cu, Zn and Cd (Gitari et al.,
backbone of zeolite structure. Size of aluminium ion is 2008; Reynolds, 2004; Bäckström and Sartz, 2011) but low
very tiny to occupy the central position of the tetrahedron percentage removal of Cu, Zn and Cd was also reported
of four oxygen atoms, and the isomorphous replacement (Jianping and Haito, 2014). The differences in removal
of Si4+ by Al3+, which in turn produce negative charge in efficiency is attributed to the characteristics of the fly ash.
the lattice. This net negative charge is balanced with the Fly ash utilized by Gitari et al. (2008) and Reynolds (2004)
exchangeable cation (sodium, potassium or calcium). was rich in calcium content (CaO 2.1-8.43%) than the fly
Cations are also interchangeable with some cations that ash used by Jianping and Haito (2014) (CaO 1.22%).
are present in the solution (Pb2+, Cd2+, Zn2+, and Mn2+). However, higher content of magnesium oxide (MgO
The best part in case of zeolite is ions, which are 2.67%), was found for the fly ash used by Gitari et al.
exchangeable and comparatively harmless which makes (2008) in comparison to the fly ash utilized by Reynolds
them a suitable component for treating the heavy metal (2004) and Jianping and Haito (2014). Therefore, CaO
laden wastewater (Erdem et al., 2004).) Adsorption rate of content plays the major role for enhancing the pH of the
heavy metal ions from solution follow the progression: solution and thereby removal of metals from the solution.
Fe3+ >Zn2+>Cu2+>Mn2+ (Motsi et al., 2009). However, the Precipitation of different metals from the solution occur
efficiency of natural zeolites is exhausted after few at different pH. Manganese oxide (Mn2+) at pH 5-5.5 and
adsorption cycles. Table 3 summarizes the advantage and Cu and Zn at pH greater than 5-5.5 are cemented on the
the difficulties associated with reverse osmosis, ion precipitated aluminium (oxy) hydroxide and iron (oxy)
exchange, electrodialysis and natural zeolites during hydroxides. The concentration of Ca and Mg initially
treatment of acid mine water. increases in the solution due to the leaching of Ca 2+ and
2.2. Treatment of AMD with waste materials Mg2+ from surface of fly ash. However, after initial
increment, Ca concentration decrease due to formation of
The above mentioned chemical treatments for the gypsum and anhydrite, which takes over the control of
neutralization of AMD are associated with high cost of the calcium concentration in the solution. Gypsum formation
adsorbents. Besides this, armoring of limestone by ferric at pH >5.5 and adsorption of high concentration of sulfate
hydroxides is a major issue which hinders the treatment by iron hydroxides at pH >6.0 are attributed for the
efficiency of oxic limestone drains and the active reduction of sulfate in the solution (Gitari et al., 2008). Fly
limestone treatment systems. All these difficulties lead Ash is not only effective for the treatment of AMD but it is
researchers to find efficient and cost effective also efficient adsorbent for the treatment of
neutralization materials (Gitari et al., 2008). Extensive circumneutral mine water (CMW) which, contains lower
research has been done for the treatment of AMD by concentration of Fe and Al but rich in Ca and Mg
various industrial wastes such as fly ash, steel slag, ZVI, (Madzivire et al., 2010). CMW is produced by AMD’s
CKD, organic waste through combination of reactions such partial neutralization due to the surrounding geology. This
as neutralization, adsorption and precipitation. process also results in precipitation of some metals while
2.2.1. Fly ash sulfate get precipitates in the form of gypsum or adsorbed
Fly ash is a low cost, environment friendly, unconventional on precipitating metal hydroxides. However, unlike AMD
and alternative adsorbent for activated carbon (Ceptin treatment with FA which removes significant amount of
and Pehlival, 2007). It can remove different heavy metals sulfate, treatment of CMW with FA is not so effective at
from wastewater (Polat et al., 2002; Erol et al., 2005; pH <10. Treatment of CMW with FA followed by seeding
Heechan et al., 2005). Researchers have reported that it of gypsum and amorphous Al(OH)3, at pH 12.25, reduced
can be used as pretreatment agent as an alternative to sulfate concentration from 4800 ppm to 1043 ppm due to
dolomite and limestone (Potgieter-Vermaak et al., 2006). the dissolution of CaO from FA. CaO present in FA,
It has been extensively used for the treatment of AMD. It dissolves and reacts with sulfate ions according to the Eq.
was reported that fly ash can decontaminate the acidic (1) and Eq. (2) (Madzivire et al., 2010).
water by removing heavy metals such as iron (Fe), CaO+H2O Ca2++2OH- (1)
aluminium (Al), manganese (Mn), calcium (Ca), 2+ 2-
Ca +SO4 +2H2O CaSO4.2H2O (2)
magnesium (Mg), zinc (Zn), copper (Cu), cadmium (Cd),
nickel (Ni), and cobalt (Co) (Gitari et al., 2008; Reynolds, Thereafter, with addition of amorphous Al(OH) 3, the
2004; Bäckström and Smarts, 2011; Jianping and Haito, sulfate concentration was further reduced to 213 ppm
2014; Pradhan and Deshmukh, 2008). Removal from 1043 ppm as shown in Eq. (3)
percentage of different heavy metals with fly ash is 6Ca2++3SO42-+2Al(OH)3+32H2O 3CaO. (3)
presented in Table 4. Iron removal takes place at pH 3CaSO4.Al2O3.32H2O+6H+
greater than 7. If the solution has pH from 4-4.5, Fe3+ is
A REVIEW ON TREATMENT OF ACID MINE DRAINAGE WITH WASTE MATERIALS: A NOVEL APPROACH 517

Table 3. Different active treatment technology

Sl. Methodology Membrane used Experimental Percentage Remarks Reference
No. condition removal
1. Reverse Cellulose acetate Product rate 26.2 95-99% metal Further reverse Sastri, 1979
Osmosis membrane g/hr separation osmosis required
Operating efficiency for treated water
pressure 300 psig
2. Reverse Polyamide Ultra- Feed rate at 1200 Removal No pre and post Zhong et al.,
Osmosis low-pressure L/hr percentage of Ni2+, treatment 2007
reverse osmosis 0.9-1.0 Mpa Cu2+, Zn2+ and Pb2+ required.
was 97.41%, However, higher
97.73%, 97.89% and pressure required
98.06% respectively to enhance the
water recovery,
that give
additional
treatment cost
3. Filtration Nanofiltration Feed rate at 1200 Removal No pre and post Zhong et al.,
membrane L/hr percentage of Ni2+, treatment 2007
0.9-1.0 Mpa Cu2+, Zn2+ and Pb2+ required.
was 92.45%, However, higher
93.24%, 94.37% and pressure required
95.19% respectively to enhance the
water recovery,
that give
additional
treatment cost
4. Ion Exchange - Gel type strong 100% Metal different pre- Feng et al., 2000
acidic cation removal and 98% of treatment stages
exchange resin of water recovery required, such as
the sulphonated oxidation,
polystyrene, neutralization
porous medium and precipitation
base anion with lime and
exchange resin combination with
with an acrylic different pre-
matrix treatment stages
required, such as
oxidation,
neutralization
and precipitation
with lime and
combination with
6. Electrodialysis HDX 200 anion- - Metal removal Requires pre- Buzzi et al.,
exchange and efficiency was 97% treatment such 2013
cation exchange as microfiltration.
membrane Cannot able to
treat AMD with
higher Fe
concentration
7. Natural Zeolites - 6 hrs of reaction Removal efficiency Adsorption of Motsi et al.,
time with dose of of Fe3+, Mn2+, Zn2+, elements 2009
37 g/L. and Cu- was 80%, decreases if initial
95%, 90%, and 99% pH of the AMD
respectively. solution is lower.
518 SUKLA SAHA and ALOK SINHA

Mg concentration decreased below detection limit when Moreover, solid residue generated after treatment of
the pH was increased to 12.25 because of the formation AMD with fly ash can also be converted into synthetic
of Mg(OH)2. Treatment of mine water with FA also zeolites. It has wide application such as alkylation,
reduced Mn concentration below detection limit as Mn isomerization, catalysis for hydrogenation and acts as an
precipitates in the form of Mn(OH)2 at pH 8.5-9.5 excellent adsorbents for the removal of contaminants
(Madzivire et al., 2014). Along with various heavy metals, (heavy metals, toxic gas, organic pollutants such as
sometimes AMD contains different radioactive materials benzene and alcohol) (Apiratikul and Pavasant, 2008).
such as uranium (U) and thorium (Th) from the associated Synthetic zeolites from CFA shows adsorption capacity 2-
bedrock (Madzivire et al., 2014). FA interacted with U and 25 times higher than the original CFA (Nascimento et al.,
Th present in the water and form UO2 at ph≥3 and ThO2 at 2009) and 3-5 times greater than natural zeolites (Lee et
pH >5. Formation of these compounds helps to remove al., 2000), along with 100% removal of heavy metals
more than 90% of U and Th from the water. This in turn (Koukouzas et al., 2010). Ríos et al. (2008) studied the
reduces the alpha and beta radioactivity by 88% and 75% removal of heavy metals from AMD by different
respectively. FA behaves like a sink for these radioactive adsorbents such as coal fly ash (CFA), natural clinker (NC)
materials. It was also reported that treatment of AMD and synthetic zeolites such as Natural Clinker Based
with FA, can remove 90% of Ra and Pb. Hence, it can be Faujazite (NCF), Natural clinker-based Na-phillipsite (NCZ),
used as a safe adsorbent to treat contaminated gold mine Coal fly ash faujasite (CFAF) made from natural clinker,
water as no leaching of radioactive materials from coal fly coal fly ash. NCF enhanced the pH to maximum 9.43 due
ash to acidic water was reported (Madzivire et al., 2014). to the presence of free CaO inside the faujasite network
2.2.2. Modified fly ash (Ríos et al., 2008). The order of the adsorbents with
respect to pH enhancement capability followed the trend
Although raw coal fly ash is an alternative for the chemical NCF>CFAF>CFA>NCZ>NC. Besides the pH enhancing
treatment of acid mine drainage, but sometime it shows capability, NCF and CFAF also showed higher metal
insufficient adsorption capacity, and poor pH enhancing removal efficiency because of lower SiO2/Al2O3 content
capability. Presence of higher amounts of Al and Si that brings more terminal Al-OH species at zeolite-water
reduces the efficiency of fly ash. Therefore, to enhance interface during entire reaction. The enhancement in the
the efficiency, coal fly ash is often modified by soaking in hydrophilic nature of zeolite increases the metal exchange
acid or alkaline solution. This chemically modified coal fly capacity. The principal mechanism associated with metal
ash (MFA) results with greater surface area, lower removal by the adsorbent is precipitation. With increasing
amounts of Al and Si, higher pH value, enhanced pore pH, metal concentration decreases, which reveals the
volume, more loss of ignition and higher percentage metal precipitation of metals on the surface of the sorbents
removal efficiency (Sahoo et al., 2013; Jianping and Haitao (Ríos et al., 2008).
2014; Hsu et al., 2008). 120 g/L and 180 min was
optimized as dose and reaction time, respectively, for
AMD neutralization by MFA (Sahoo et al., 2013). Table 4
presents the metal removal percentage by MFA. It also
enhances the removal efficiency of heavy metal ions like
Cd2+, Cu2+, Zn2+ due to higher specific surface area and
small pore diameter (Jianping and Haito, 2014). Figure 3
depicted the reaction chemistry behind the metal removal
by fly ash/modified fly ash. It shows that metal removal is
due to adsorption of some metals such as Cu, Pb, Ni, Zn,
Cd, Mn on the surface of adsorbent. Hydrolysis and
precipitation of several metals in the form of CaSO 4,
CuSO4, Cr(OH)3, Fe(OH)3, Mn(OH)2, Al(OH)3 and co-
precipitation of some metals in the form of Fe(OH) 3, Cu2+,
Al(OH)3, Zn2+, Mn2+ also play a major role for the metal
removal process. Adsorption of metals (Cu2+ and Zn2+) and
Figure 3. Removal of heavy metals by fly ash/modified fly ash
anion such as SO42- on the surface of secondary
precipitated phases such as ferric hydroxide and
Extensive literature review demarcates that fly ash,
aluminium hydroxide is the another major pathway for
natural zeolites and zeolites synthesis from fly ash has
metal uptake by fly ash/MFA. However, removal efficiency
potential to decontaminate the AMD. However, disposal
gradually weakened with prolonged reaction time.
of this fly ash-solid residue after treatment is a matter of
2.2.3. Fly ash synthesized zeolites concern, as it contains heavy metals on its surface that
Zeolites can be produced from coal fly ash (CFA) by has environmental impacts like water pollution, soil
hydrothermal methods (Nascimento et al., 2009). CFA pollution, etc. Therefore, safe disposal of the solid residue
contains huge amount of silica (Si) and aluminium (Al), is necessary. Zeolites synthesized from the solid residue,
which makes it suitable material for formation of zeolites. recovered after the treatment of fly ash and AMD, is
reported as a very effective adsorbent for the treatment
A REVIEW ON TREATMENT OF ACID MINE DRAINAGE WITH WASTE MATERIALS: A NOVEL APPROACH 519

of AMD (Petrik et al., 2003; Gitari et al., 2005; Somerset et steel slag. Optimum pH value for the metal sorption was
al., 2008; Vadapalli et al., 2010). Gitari et al. (2005) 3.5-8.5 for steel slags and 5.2-8.5 for iron slag. Metal
synthesized ion-exchange adsorbents, in form of zeolites, adsorption increased as soon as the pH of iron slag
through high temperature hydrothermal reaction from increased (>4.8), due to the enhancement of negative
this solid residue. It was used for comparative analysis for charge on the surface of slag which increases the metal
the removal of Ni, Zn and Pb with commercial zeolite. removal by adsorption, precipitation and co-precipitation
Although removal of Zn was not significant, however Ni represented in Figure 4. It illustrates that adsorption of
and Pb removal efficiency with the synthesized adsorbent some metals such as Cu2+, Cd2+, Ni2+, Zn2+; precipitation of
was higher than the commercial zeolites. Somerset et al. several metals in their hydroxide form (CaSO4, CuSO4,
(2008) studied removal efficiency of zeolite synthesis from Cr(OH)3, Fe(OH)3, Mn(OH)2, Al(OH)3) as well as the co-
fly ash and solid residue. It was found that zeolite precipitation of some metals in form of Fe(OH) 3, Cu2+,
produced from solid residue has the ability to remove lead Al(OH)3, Zn2+ and Mn2+ are the significant metal removal
and mercury from acidic wastewater with removal processes from AMD. Moreover, the adsorption of metals
percentage of 95% and 30%, respectively. While, zeolites (Cu2+, Zn2+) and anion such as SO42- on the surface of
synthesized from raw fly ash removed lead up to 88%, but secondary precipitated phases such as ferric hydroxide
was unable to reduce the mercury concentration. and aluminium hydroxide is one of the reason for metal
Vadapalli et al. (2010) also investigated about the reuse of removal as well. In case of steel slag similar phenomenon
the solid residue synthesized product, zeolite-P for the occurs at ph >3.2. Name and Sheridan (2014) investigated
treatment of CMW up to four number of treatment cycle. the efficiency of two type of slag, Basic Oxygen Furnace
The product had a high cation exchange capacity (178.7 slag (BOF) and Stainless Steel (SS) slag for the treatment of
meq/100 g) and surface area (69.1 m2/g). Percentage AMD. Metal removal efficiency for different metals are
removal efficiency of zeolite-P presented in Table 4. listed in Table 4. 30 g/L of slag dose and 24 hrs of reaction
Metals such as K, Ca, Sr, and Ba were efficiently removed time was optimum to enhance the pH to 6.68 and 6.32 for
by zeolite-P in the first phase of treatment. However, iron slag and steel slag, respectively, with greater sulfate
removal of Mg was insignificant. Although, it was able to removal in iron slag (Feng et al., 2004). 100 g/L dose of BOF
remove heavy metals successfully for the first treatment slag not only enhances the pH to a greater value in
cycle, but removal efficiency exhausted and the pH comparison with SS slag, but also results in higher sulfate
decreased from 8.3 to 7.5 with subsequent and rapid removal (Name and Sheridan, 2014). From the comparative
treatments, which may be attributed to the competition study, it was evident that as the dose of steel slag or BOF slag
and adsorption of the other materials on the surface of was enhanced percentage reduction of sulfate decreased
zeolite. Sodium (Na) was the most important (Table 4). So, the variation in pH enhancement and sulfate
exchangeable cation presented in the zeolite-P product as reduction was attributed to the characteristics of slags used
there was continuous release of Na found during the for the treatment. Calcium content was more in case of iron
experiments. Therefore, solid residue could be effective in slag (46.3%) than steel slag (37.5-38.7%) and SS slag (36%).
the form of synthetic zeolites for the treatment of acidic Because of higher calcium content in iron slag higher
waste water laden with high concentration of heavy reduction in sulfate was was observed due to
metals. precipitation as gypsum (Gitari et al., 2008). Metal
removal efficiency of iron slag was more than BOF slag
because of its higher surface area 31.929 m2/g than BOF
2.2.4. Slag slag 22.333 m2/g (Feng et al., 2004). Therefore, the
sequence of the adsorbents with respect to metal removal
Slag is considered as waste product from steel making was iron slag>BOF slag> SS slag. Although, the
industry. Iron ore or scrap metals are added in molten experimental results of batch experiments for the
form with limestone, dolomite or lime in different treatment of AMD with slags were very impressive, but
combination during steel making process. All these AMD treatments in slag leach beds sometimes proves
calcium components combine with aluminium, silicon, and ineffective for prolonged period of reaction time. This
phosphorous to form slag. Matrix of slag solubilize to might be due to limitation of dissolvable calcium
release calcium and magnesium oxides which in turn compounds on the surface of slag particles that lead to
enhance the pH of dissolving fluid up to 10-11 and help low alkalinity loadings. Accumulation of thick layer of
the metals to precipitate in the slag leach bed when AMD precipitation in the effluent piping as well as formation of
passes through it. The neutralization potential (NP) of precipitates within slag resulted in lower alkalinity
steel slag is in the range of 45 to 78%. For in-situ AMD values (Goetz and Riefler, 2014).
treatment, the effluent from the leach beds can infiltrate 2.2.5. Zero valent iron particles
directly into a spoil or refuse-pile (Ziemkiewicz and Zero valent iron (Fe0) is one of the common reducing
Skousen, 1998). Feng et al. (2004) conducted a study using agent, used for the removal of contaminants from
metallurgical by product, slag (Iron slag and Steel slag) for wastewater. It behaves as a strong reducing agent as well
the treatment of gold mine AMD which was highly acidic as it is cost effective and readily available material to
(pH 2.03) and contained high concentration of different reduce the sulfate and enhance the metal precipitation of
heavy metals. Iron slag, showed much higher adsorption highly stabilized metal sulfides. Even the corrosion of iron
capacity with greater increase in pH in comparison with
520 SUKLA SAHA and ALOK SINHA

promotes the generation of Fe2+ ions that in turn

sequester excess sulfide and the effluent contains
minimum concentration of toxic metals. It can neutralize
the acidity of AMD by generating alkalinity (Eq. (4))
through the corrosion of ZVI (Ayala-Parra et al., 2016).

Fe0+2H2O Fe2++H2+2OH- (4)

Figure 4. Removal of heavy metals by Slag

Table 4. Removal percentage of metals with different waste material

Sl Used Optimum Initial pH Final Reaction Percentage removal of metals References
no material Mixing pH Time
ratio/ Dose

1. Fly Ash 1:3 2.78 9.1 1440 Greater than 90% for toxic metals, 78% Gitari et al.,
mins for sulfate 2008

2. Coal Fly - 4 7.0 12 hrs. 60.4% sulfate, 53.4% Chemical Oxygen Jianping and
Ash Demand Haitao, 2014
3. Fly Ash - 2.88 12.0 - Removal of 97.0% Al, 99.9% Fe, 99.98% Reynolds,
Mn and 96.42% Zn 2004
4. FA 1:2 6.6 ± 0.21 12.25 - Removal of 79.57% sulfate Madzivire et
followed al., 2010
by
seeding
with
gypsum
crystals
and the
addition
of
amorpho
us
Al(OH)3
5. Alkaline - 3.3-5.0 8.0 7 days Removal of 99.97% of Cu, 99.78% of Zn, Bäckström
Ash 90.2% of Cd, 99.94% of Pb, 62.71% of Ni and Sartz,
Leachate and 99.41% of Co. 2011
s
6. Modified 120 g/L 1.6 2.8-6.6 180 min 89%, 92%, 94%, 96%, 60%, and 99 % for Sahoo et al.,
Fly Ash Ni, Zn, Pb, Fe, Mn, and Al respectively 2013
7. Modified - 4 36-120 82.4% of Cd2+, 91.85% of Cu2+, 57.2% Zn2+ Jianping and
Fly Ash hrs Haitao, 2014
8. Natural 0.25 gm 1.96 4.29- 24 hrs Approximately complete removal of Fe, As Ríos et al.,
Clinker- and 1 gm in 9.43 and ammonium. Partial removal of Cu and 2008
Based 20 ml Zn.
Faujasite
9. Synthetic 20 g/L 2.64 4.25- 1 hr Removal efficiency for lead is 88% Somerset et
Zeolite 4.88 al., 2008
10. Synthetic 1 g/100 ml 6.2 8.3 1 hr Removal of Al, Fe, Mn, Zn, Cu, Ni, Mg as Vadapalli et
zeolites (68%-77%), (99.1%-99.9%) (8%-64%), al., 2010
(Zeolite- (58%-69.2%), (54%-88.9%),(43%-68.6%),
P) and (7%-13%) respectively
11. Basic 30 g/L 2.03 6.32 24 hrs Greater than 90% removal of heavy Feng et al.,
Oxygen metals and anions 2004
Furnace
A REVIEW ON TREATMENT OF ACID MINE DRAINAGE WITH WASTE MATERIALS: A NOVEL APPROACH 521

Slag/Ste
el Slag
12. Iron Slag 30 g/L 2.03 6.68 24 hrs Greater than 90% removal of heavy Feng et al.,
metals and anions 2004
13. Stainless 100 gm/L 2.5 5.9 240 mins Removal of 63.6% iron,39.8% sulfate Name and
Steel Sheridan,
slag 2014
14. Basic 100 gm/L 2.5 11.3 240 mins Removal of 99.7% iron,75% sulfate Name and
Oxygen Sheridan,
Furnace 2014
Slag/Ste
el Slag
15. Colloidal 3%(w/v)/1. 2.3 6.5 250 hrs. 99.6% of Al, 64.4% of As, 97.1% of Cr, Shokes and
Iron 25 L 98.5% of Zn and 19.5% of Sulfur Moller, 1999
16. Granular 3%(w/v)/1. 2.3 5 250 hrs. 97.7% of Al, 29.6% of As, 8.2% of Cr, 3.33 Shokes and
Iron 25 L % of Zn and 4.43% of Sulfur Moller, 1999
17. Zero 0.23 gm/ml 2.3 5.7 24 hrs. Removal of 99.90% Al, 97.7% Hg, 99.42% Wilkin and
Valent As, 98.4% Cd, 99.98% Cu, 99.78% Ni and McNeil, 2003
Iron 9.81 % of Zn

18. Zero - 4.5-4.8 6.38- 60 days Removal of Fe (91.6–97.6%), Zn (>99.9%), Lindsay et al.,
Valent 6.87 Cd (>99.9%), Ni (>99.9%),Co(>99.9%) Al 2008
Iron and (>99.9%),Mn (89.9-90.6% )and Pb (94.6-
mixtures 96.9%)
of
Organic
carbon
19. Zero - 4.8 7.32- 60 days Removal of 31.3% Fe, 76.75% Co, 98.2% Lindsay et al.,
Valent 7.61 Zn, 99% Ni and Cd, and Pb (94.6-96.9%) 2008
Iron
20. Cement 25% of CKD (2.4 ±0.1) 9.5 1 minute 98% of zinc and 97% of iron Mackie and
Kiln Dust slurry Walsh, 2012
Slurry
21. Rice 1:10 2.3 4.0 24 hrs. 99% Fe3+, 98% Fe2+,98% Zn2+ , 95% Cu2+ Chockalingam
Husk and
Subramanian,
2006
22. Peat 1:500 2.7 3.1 1 hr Removal of 36% Fe, 26% Al, 20% Zn, 35% Bogush and
Humic Cu, 43% Cd, 98% Pb, 40% Ni, 21% Co Voron, 2010
Agent
23. Peat 1:500 4.1 5.3 1 hr Removal of 95% Fe, 99% Al, 21% Zn, 23% Bogush and
Humic Cu, 23% Cd, 15% Ni and 18% Co Voronin, 2010
Agent
24. Peat 1:500 4.8 7.1 1 hr Removal of 94% Fe, 99.9% Al, 96% Zn, Bogush and
Humic 99% Cu, 76% Cd, 61% Ni and 57% Co. Voronin, 2010
Agent

Abiotic removal of metals take place by different compounds from contaminated water (Blowes et al.,
processes such as adsorption onto the surfaces of Fe 0 and 1997; Puls et al., 1997; Weisener et al., 2005; Sinha and
precipitation. Iron has proved as an effective material in Bose, 2009; Moraci and Calabrò, 2010). Complete removal
changing the chemistry of acidic system towards of radioactive metal such as uranium was also reported
conditions promoting immobilization of dissolved heavy with iron particles (Gu et al., 1998). Shokes and Moller
metals, increase in pH, and decrease in redox potential (1999) carried out their study with diversified form of Fe 0
(Shokes and Moller, 1999). Extensive studies were carried such as, colloidal iron and granular iron. Wilkin and
out with Fe0 in the form of iron fillings, iron chips and used McNeil (2003) used granular iron of two different mesh
in batch study as well as in permeable reactive barrier for size; peerless iron of (-8+50) mesh particle size and fisher
the removal of different toxic metals such as chromium iron of (-100) mesh particle size for their experiment. Both
(Cr), mercury (Hg), nickel (Ni), copper (Cu) and organic the iron particles showed the enhancement of pH from
522 SUKLA SAHA and ALOK SINHA

2.3 to 5.7-6.5. AMD solution with lower initial pH, such as Ni2+ and Zn2+ form complex with hydroxide and sulfate or
3.5 and 4.5 reached to higher final pH of 9.6-10.0 after cemented on the surface of ferrihydrite.
several hours of reaction (Wilkin and McNeil, 2003). Metal Under anaerobic condition sulfate reduction leads to the
removal efficiency for both the experiments is presented corrosion of Fe0 and forms Fe (II) along with OH- and H2
in Table 4. However, metal removal efficiency of colloidal (Eq. 4). Molecular H2, is utilized by some sulfate reducing
iron is better than granular iron because of their specific bacteria (SRB) species as an electron donor for SO 42-
surface area. Surface area of colloidal iron was 0.3 m2/g reduction (Eq.5) (Karri et al., 2005; Ayala-Parra et al.,
whereas 0.005 m2/g for granular iron. As the surface area 2016).
was much less therefore, granular iron does not have
adequate surface area to enhance the pH to 7 or to SO42-+4H2+H+ HS-+4H2O (5)
maintain a reducing environment by generating hydroxyl
ions (Shokes and Moller, 1999). Shokes and Moller (1999)
reported Ni removal percentage with colloidal iron and
granular iron was 74.5% and 7.1%, respectively. Whereas,
Wilkin and McNeil (2003) reported the removal
percentage as 99.78% with granular iron. Similarly for Zn,
removal percentage was observed to be 98.5% and 3.33%
with colloidal iron and granular iron, respectively (Shokes
and Moller, 1999), in comparison to 98.81% for peerless
iron and 99.78% for fisher iron, respectively (Wilkin and
McNeil, 2003). The variation in the results might be due to
the specific surface area of both the granular iron. Specific
surface area of peerless iron and fisher iron was reported
as 3.05 m2/g and 0.05 m2/g (Wilkin and McNeil, 2003),
which is more than reported by Shokes and Moller (1999).
However, there was no significant difference in Figure 5. Removal of heavy metals by Zero Valent Iron
percentage removal for peerless iron and fisher iron. This
may be due to the same pH attained by both granular Table 5. Composition of reactive mixtures expressed as dry
irons and precipitation of the metals took place according weight percentages (dry wt.%) (Lindsay et al., 2008)
to their own precipitating pH values. Removal of sulfate Reactive Reactive mixture composition (dry wt. %)
by Fisher iron was two times more than the reduction by mixture
pearless iron at same dose level. However, Mn removal by
ZVI was insignificant (Wilkin and McNeil, 2003). This may OC Fe0 Inoculum Limestone Silica
be due to release of Mn ions from ZVI at low pH values. Ni Sand
and Zn removal took place due to the formation of
RM1 50 0 2 16 32
complexes with hydroxide and sulfate. Removal process
for antimony (Sb) was very slow and it took several hours RM2 48 2 2 16 32
to achieve 86% of removal. It was reported that the RM3 45 5 2 16 32
oxidation state of As does not changed by ZVI, it remain in
RM4 40 10 2 16 32
As(V) form in the solution (Wilkin and McNeil, 2003). It
forms complexes with iron oxide and removed by co- RM5 0 50 2 16 32
precipitation with sulfides, iron oxides and iron oxy- It was reported that some heterotropic bacteria such as
hydroxides. Cd and Cu bind on the surface of the iron by Desulfovibrio desulfuricans oxidize H2 but it requires some
reduction into its elemental metal form. Al precipitate as organic carbon (OC) source for their growth (Ehrlich,
Al(OH)3 (Wilkin and McNeil, 2003; Shokes and Moller, 2002). Permeable reactive barrier (PRB) contained
1999). Figure 5 depicted the removal process of metals by mixture of Fe0 and OC that promotes the growth of SRB,
ZVI. Adsorption is considered as the initial and most rapid which in turn reduces sulfate with buffering of pH and
metal uptake mechanism. Cu2+ and Cd2+ reduced by ZVI enhanced removal of metals/trace elements (Lindsay et
and adsorption of elemental Cu and Cd take place on the al., 2008; Ayala-parra et al., 2016). Enormous studies have
surface of ZVI itself. Similarly, precipitation of metals been done to find the effectiveness of zero valent iron
according to their hydroxide form such as Cr(OH)3, and combination of zero valent iron along with organic
Fe(OH)3, Al(OH)3, Mn(OH)2, Ni(OH)2 occur. Sulfate may be carbon mixtures for the remediation of AMD (Lindsay et
removed from the solution by precipitation of metal sulfur al., 2008; Ayala-parra et al., 2016). Compositions of
compounds such as metal sulfate (NiSO 4, CuSO4), metal reactive-mixtures (RM) are presented in the Table 5.
hydroxide compounds Fe6(OH)12SO4.nH2O or co- Experimental results showed rapid decrease in metal
precipitate as metal hydroxide (M6(OH)12SO4). Iron concentration and sharp increase in pH within 1 day.
corrodes in acidic solution and formed iron oxy hydroxide Although, metal removal under sulfate reducing condition
and iron oxides and co precipitated on the metal surface. takes place due to metal-sulfide precipitation, but other
As5+ co-precipitated with iron oxide or iron oxy hydroxide mechanisms such as (oxy) hydroxide precipitation, co-
or cemented on the surface of ferrihydrite (Fe 5HO8.4H2O). precipitation and surface complexation also acts as key
A REVIEW ON TREATMENT OF ACID MINE DRAINAGE WITH WASTE MATERIALS: A NOVEL APPROACH 523

mechanisms for metal removal. Similar sulfate reduction efficiency of CKD for acid mine water treatment. Four type
rate (SRR) was observed for RM3 and RM4. Manganese of CKD sample (CKD-A, CKD-B, CKD-C, and CKD-F) whose
(Mn) concentration eventually increase (28.3%) in RM5, at particle sizes were 34-73% smaller and specific surface
ph<8 as Mn-hydroxide was not precipitated. From the areas 2-3 times greater than the quicklime samples were
results it is inferred that except Fe and Mn, removal used in this study. Treatment of mine water with 25% of
efficiency for all heavy metal was almost similar when Fe0 CKD (w/v) removed 98% of total zinc and 97% of total iron
was used either solely or in combination with OC. Ayara- concentration. Metal removal percentage are presented
para et al. (2016) reported similar observation, with in Table 4. Surface adsorption, hydrolysis and
respect to using limestone (LS) and ZVI for the treatment precipitation of the heavy metals are the removal
of AMD. LS aids as buffer as well as inorganic food for mechanism of toxic metals (Figure 6). It illustrates that
lithoptropic SRB that can utilize CO2 as a carbon source. adsorption as well as the precipitation of metal (Cu, Pb,
Increasing sulfate reduction observed in ZVI-LS column Cd, Zn) as their hydroxide (Cu(OH) 2, Cr(OH)3, Fe(OH)3,
than ZVI column, where sulfate reduction ceased after Al(OH)3 Pb(OH)2) and sulfate form (CaSO4) are major metal
small reaction time in LS column. Metal removal efficiency removal path followed by CKD. However, among all the
in all the columns was more than 98%. In ZVI column, CKD samples, CKD-F has the highest free lime content.
metal removal took place due to the formation of metal Therefore, removal efficiency of CKD-F is slightly better
sulfides. It was observed from the solid-phase analyses than other CKDs. All CKD samples were able to achieve
that heavy metals precipitated with biogenic sulfide in the more than 98% and 97% precipitation of soluble Zn and Fe
columns packed with ZVI. However, in absence of ZVI, concentration, respectively. Moreover, CKD-treated
heavy metals were also significantly removed due to samples generated less sludge by volume (50%-60%) than
precipitation with hydroxide and carbonate ions released the sample treated with quicklime slurry. Therefore, CKD
from limestone, though LS surfaces are super saturated is a promising treatment option to reduce acidity,
after a while. Therefore, in case of permeable reactive precipitate and remove metals as they generate only 50-
barrier (PRB), small amount of Fe0 can make the system 60% of sludge compared to lime. However, increasing
efficient and cost effective. ZVI acts as an efficient settling time or polymer doses might be needed to meet
reducing agent for treatment of AMD, specifically for the treatment requirements. Even though the treatment
sulfate reduction when associated with PRB system results are significant, but to treat the mine water with
(Ayala-parra et al., 2016). CKD, much higher volumes of slurry is required to reach
It is concluded that zero valent iron is effective to the target pH of 9 with respect to quicklime slurry.
decontaminate the acid mine drainage through various
reaction mechanism from its soluble toxic metals as well
as anions such as sulfate, chloride etc. However, if
groundwater is contaminated with sulfate rich ground
water then the prime corrosion product of zero valent
iron is green rust. Regular adsorption of green rust on the
top of the iron corrosion products, co-precipitation with
corrosion products or combination of both makes the
metal uptake process much slower. Another important
factor that also hinders the efficiency of ZVI, is the
presence of high concentration of total dissolved solid
loads (TDS). Loss of permeability and high rates of mineral
precipitation, due to high loads of TDS, also acts as barrier Figure 6. Removal of heavy metals by Cement Klin Dust
for the efficiency of ZVI (Wilkin and McNeil, 2003).
2.2.7. Organic waste material
2.2.6. Cement klin dust
Organic substrates such as rice husk and peat humic agent
Cement Klin Dust (CKD) is known as caustic-material,
(PHA) are also considered as potent adsorbents for the
which is produced during the cement production in
metal ions. Humic agents are high molecular complex
cement klin. In cement production, the raw materials such
organic compounds formed due to the decomposition of
as limestone along with quicklime, eventually converts
vegetative and animal residue by microorganisms and
into lime by removal of carbon dioxide within klin.
abiotic factors (Orlov, 1990). Carboxyl group present in
Pollution control devices such as Bag house filter and
humic agent in the form of humic acid (Hu-COOH) and
electrostatic precipitator (ESP) remove the small particles
sodium humate (Hu-COONa) produce humate ion, a
of CKD, present in the exhaust gases generated from
hydroxonium ion and a sodium ion via dissociation. This
cement kiln. This waste product contains 8-61% (weight
humate ion form humate complex by reacting with metal
%) of total CaO (Mackie and Walsh, 2012). Extensive
ions (Eq. (6) and Eq.(7)) (Bogush and Voronin, 2010).
literature studies reported that CKD is able to remove the
pollutant and toxic heavy metals from the wastewater 2Hu-COOH+Me2++2H2O Hu-COO-Me- (6)
with approximately 100% removal percentage (El-Awady OOC-Hu+2H3O+
and Sami, 1997; Zaki et al., 2007). Mackie and Walsh 2Hu-COONa+Me2+ Hu-COO-Me-OOC- (7)
(2012) conducted a bench-scale study to evaluate the Hu+2Na+
524 SUKLA SAHA and ALOK SINHA

Organic materials and humic agents consist of carboxyl, Cd2+, Ni2+, Zn2+) on the surface of PHA and the
hydroxyl, carbonyl, amide and phenolic group, attached to precipitation of metals (Cu(OH)2, Cr(OH)3, Fe(OH)3,
larger organic molecules, which in turn bind the metal Mn(OH)2, Al(OH)3) in its hydroxide form are the key
ions (Bogush et al., 2007). Organic compounds act as an mechanism for the metal removal from AMD. However,
excellent energy source for the SRB. These organic co-precipitation of the metals as well as the adsorption of
compounds can be utilized as an adsorbent for the metals on the metal precipitates such as Fe(OH)3 are also
removal of heavy metals from wastewater. Chockalingam considered for the metal removal process of PHA.
and Subramaniam (2006) studied the metal ions removal Furthermore, AMD with pH 4.8 was treated with PHA at
and sulfate reduction using rice husk and SRB 1:500 ratio, it removed more than 90% toxic and other
(Desulfotomaculum nigrificans) for the remediation of metals and pH was enhanced to 7.1. Therefore, the order
AMD. AMD and simulated AMD with pH 2.3 were pre- of AMD that can be treated with PHA was as follows, AMD
treated with rice husk (10 gm/100 ml) in the study. After with pH 4.8>AMD with pH 4.1>AMD with pH 2.7. Metal
pre-treatment, pH of AMD and simulated mine water removal percentage is presented in Table 4. Although,
increased to approximately 4.5 and 6.1 respectively. For PHA are very stable in nature, not prone to
sulfate reduction tests, acid mine water of pH 2.3 were biodegradation and thermal destruction, however, in
interacted with 10, 16 and 20 g of rice husk for 1 hour so comparison with rice husk, it can only treat mildly acidic
that the final pH values became constant at 4.6, 5 and 5.3 water. Therefore, PHA is not beneficial for treating the
respectively. There was no significant sulfate removal highly acidic AMD.
after 24 hours. However, after inoculation of D. nigrificans
into AMD, sulfate reduction increased to 40% from 21% at
pH 5.3 after 31 days by using rice husk filtrate in addition
with nitrogen and carbon contents. In case of simulated
AMD, sulfate removal percentage was observed to be 73%
after 35 days. However, concentration of sulfate again
increased after the point of its reduction for both the
cases. This might be due to the co-precipitation of sulfate
and ferric (oxy) hydroxides in the acid mine water sample
and its subsequent dissolution in reducing conditions
(Christensen et al., 1996). Metal removal process by rice
husk is represented in Figure 7.
Figure 8. Removal of heavy metals by Rice Husk
The figure 7 clearly depict that adsorption of metals (Cu 2+,
Pb2+, Fe2+, Zn2+) and conversion of sulfate to sulfide by SRB 3. Discussion
is the major metal removal process of rice husk associated
with SRB. Moreover, the co-precipitation of metals with 3.1. Enhancement of pH by different type of waste
iron oxy-hydroxide as well as sulfate is the other metal material
uptake procedure form AMD contaminated water. The prime objective to treat AMD is to increase the level
of pH from acidic to neutral or basic. Researchers have
used various waste materials to enhance the pH of the
wastewater.
Fly ash, modified fly ash, metallurgical slag and cement
kiln dust have the ability to enhance the pH of AMD from
2.00 to the range of 8-12 (Gitari et al., 2008; Reynolds,
2004; Bäckström and Sartz, 2011; Ríos et al., 2008; Name
and Sheridan, 2014). However, BOF slag has more
potential to enhance the pH from 2.5 to 12.1 than SS slag,
which enhance the pH from 2.5 to 6.6 (Name and
Sheridan, 2014). Natural clinker and ZVI are unable to
increase the pH to higher alkaline pH values. They can
Figure 7. Removal of heavy metals by Rice Husk
enhance the pH only up to 3.86-5.7 from an initial value of
2.5. Raw fly ash is not able to enhance the pH of AMD if it
Treatment of acid mine drainage with peat humic agent
contains low lime content. Sahoo et al. (2013) modified
was carried out by Bogush and Voronin (2010). Three
the fly ash for the treatment of AMD due to its poor pH
PHA/AMD ratios (1:100, 1:500 and 1:1000) and three
enhancing property. It was reported that fly ash can
different type of AMDs with three different initial pHs
enhance pH up to 5.3 without any modification whereas
(2.7, 4.1, and 4.8) was used for this study. It was observed
with modification, pH value can be enhanced to 11.5.
that PHA has the ability to remove heavy metals from the
After the conversion of fly ash into zeolites, pH of the
mildly acidic AMD and contains moderate metal
acidic water can be turned into alkaline range i.e. 8.41-12
concentration by hydrolysis, physical adsorption and co-
(Koukouzas et al., 2009; Ríos et al., 2008). However,
precipitation of metals on the surface of ferric hydroxide,
organic waste such as rice husk and PHA have very low
presented in Figure 8. Adsorption of metals (Pb 2+, Cu2+,
A REVIEW ON TREATMENT OF ACID MINE DRAINAGE WITH WASTE MATERIALS: A NOVEL APPROACH 525

capability to enhance the pH. They can enhance the pH installation and adsorbent cost. Beside this, some active
from 2-3 to 3.7-4 (Bogush and Voronin, 2010; treatment such as reverse osmosis, ion exchange,
Chockalingam and Subramanian, 2006). Lindsay et al. electrodialysis need pre-treatment of the influent, which
(2008) reported that the treatment of AMD with enhances the whole treatment cost. Waste material on
combination of ZVI and organic carbon enhances pH from other side reduces environmental load and are
4.5 to 7.32 within 11 days. The difference in enhancement economically viable alternative for the treatment purpose.
of pH in acidic solution, by different adsorbents, might be After consideration and reviewing different studies, it can
due to the variation of calcium and magnesium oxide be concluded that among all the waste material, fly ash
content available within adsorbents and due to their and its derivatives such as modified fly ash and fly ash
ability to reduce water and produce hydroxide ions. synthesized zeolites, slag, CKD can be preferred among all
3.2. Effect of dose of adsorbents the waste material for the treatment of extreme acidic
AMD. They have more potential to enhance the pH of
Although all the adsorbents have the ability to extreme acidic solution as well as removal of pollutants
decontaminate AMD, but percentage removal for the from the solution. On the other side, ZVI and organic
heavy metals depends on the optimum doses of the waste can be used if the AMD is mild or less acidic in
adsorbing material. Gitari et al. (2008) carried out the nature. OC along with ZVI and SRB can be considered as
study of AMD treatment with two different ratio of potential option if the sulfate concentration in AMD is
FA:AMD i.e. 1:3 and 1:1.5, respectively. It was evaluated high. However, specific surface area, pH enhancing
that the maximum percentage removal of heavy metals capacity, adsorption capability, retention time,
(Mg, Mn, Al, Si. Total Fe, Zn and Cu) was at ratio of 1:1.5. leachability of different metals from adsorbents into the
Sahoo et al. (2013) evaluated that the maximum removal treated water, cost effectiveness, environmental impact
efficiency of metals with modified fly ash was observed at must be taken into consideration prior to the selection of
120 g/L out of 25 g/L, 50 g/L, 80 g/L, 120 g/L, and 150 g/L. the waste material as an adsorbent. This study will be
When the dose of NCF increased from 0.25 g/20 ml to 1 beneficial for the readers to choose suitable and specific
g/20 ml, pH of the solution enhanced to 9.43 from 1.96 waste material for field condition as well as it will
and the metal removal efficiency increased (Koukouzas et facilitate future research requirements for the treatment
al., 2010). Metallurgical slags such as basic oxygen slag of AMD.
and stainless steel slag were tested with different ratios
such as 20, 40, 60, 80, 100, 120 and 140 g/L for the Acknowledgement
treatment of AMD. Finally, it was concluded that for both We acknowledge Ministry of Human Resource Development,
the material, 100 g/L is optimum for maximum removal of Government of India for the financial support. In addition, we
metals (Name and Sheridan, 2014). In case of ZVI, Wilkin would like to thank Department of Environmental Science and
and McNeil (2003) carried out study with different dose of Engineering, Indian Institute of Technology (Indian School of
iron, i.e, 0.02 g/ml to 0.23 g/ml where maximum Mines) Dhanbad for the logistical support.
percentage removal was observed at 0.23 g/ml of iron
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