Accepted Manuscript

Title: Enhanced removal of high Mn(II) and minor heavy

metals from acid mine drainage using tunnelled manganese
oxides

Authors: John G. Outram, Sara J. Couperthwaite, Graeme J.

Millar

PII: S2213-3437(18)30239-2
DOI: https://doi.org/10.1016/j.jece.2018.04.063
Reference: JECE 2359

To appear in:

Received date: 10-1-2018

Revised date: 23-4-2018
Accepted date: 27-4-2018

Please cite this article as: John G.Outram, Sara J.Couperthwaite, Graeme J.Millar,
Enhanced removal of high Mn(II) and minor heavy metals from acid mine
drainage using tunnelled manganese oxides, Journal of Environmental Chemical
Engineering https://doi.org/10.1016/j.jece.2018.04.063

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Enhanced removal of high Mn(II) and minor heavy metals from acid mine drainage using
tunnelled manganese oxides

John G. Outram, Sara J. Couperthwaite*, Graeme J. Millar

Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001,

Australia.

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Fax: +61 7 3138 1804; Tel +61 7 3138 4766;

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E-mail: sara.couperthwaite@qut.edu.au

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Highlights

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 1x1 tunnel and 2x2 tunnel MnO2 had poor capacity for Mn(II), while 3x3 tunnel MnO2 had
high capacity

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Todorokite (3x3 tunnel) was the only MnO2 to show resistance to reductive dissolution by
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Fe(II);

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Increasing Mg ratio increased Mn(II) removal capacity but lowered overall structure stability;
 Todorokite showed significant selectivity for Mn(II) when treating lime-dosed AMD;
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 Todorokite showed removal capacity for trace heavy metals - Co(II), Cr(II), Cu(II), Ni(II), Zn(II).
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ABSTRACT
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This study developed improved manganese oxide coated media based on the todorokite
structure which are an effective means to remove a range of heavy metal ions from acid mine
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drainage (AMD) solutions. As a consequence, limitations of conventional acid mine drainage

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treatment wherein use of oxidants is required, substantial quantities of alkali are used and
sorbents which exhibit stability issues when Fe(II) is co-present in the water, are mitigated.
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This study investigated three synthetic MnO2 phases: pyrolusite, cryptomelane and
todorokite with a specific focus on identifying a preferred MnO2 phase for Mn(II) removal
from AMD wastewaters. Pyrolusite was found to have low capacity for Mn(II) removal and
was sensitive to reductive dissolution by Fe(II). Cryptomelane, similarly showed relatively
small capacity for Mn(II), and also impacted by reductive dissolution. Todorokite was

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discovered to exhibit significant capacity for Mn(II) (75-80 mg/g) in the pH range 5.5 to 7; a
value which increased to 130 mg/g when a lower Mn:Mg ratio todorokite material was used.
The todorokite materials studied also showed resistance to reductive dissolution and a
marked selectivity for Mn(II), along with further capacity for Cr(III), Cu(II), Co(II), Ni(II) and
Zn(II) removal when treating simulated discharge AMD and lime-dosed AMD.

KEYWORDS: Acid Mine Drainage; Heavy Metal; Exchange; Manganese Oxide; Todorokite

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1. INTRODUCTION

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Numerous mining sites have acid mine drainage (AMD) stored in dams and ponds, which

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represents a potential environmental hazard. AMD is typically highly acidic and comprises of
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high concentrations of dissolved sulfate, heavy metals, and metalloids [1-3]. Conventional
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treatment processes such as lime addition can remove most of the ferrous (Fe(II)) and toxic
contaminants (such as cadmium, chromium and arsenic), however solvated manganous
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(Mn(II)) contamination is often more challenging to remove from solution [2, 4, 5]. If not
adequately treated, Fe(II) and Mn(II) species can cause scaling and fouling of pipes and
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membranes, and create problems if released into the environment [5]. Current treatment
methods such as lime dosing and aeration work well for Fe(II) removal, however these
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technologies may not readily control Mn(II) due to its high solubility in alkaline conditions,
slow redox reaction rate, and the operational and financial considerations surrounding
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mineral sludge disposal [4, 5]. As a result, there is a need for more robust Mn(II) removal
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techniques that can be employed for AMD treatment.

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The use of manganese greensands (colloquially referred to as “greensands”) is a treatment

strategy that has been shown to successfully treat Mn(II) contaminated groundwater [5, 6].
Commercial manganese greensands were historically composed of a manganese dioxide
(MnO2) coated phyllosilicate clay called glauconite. However, these materials are presently
characterised as either MnO2 coated silica or solid MnO2 of various grade, depending on the

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supplier [7, 8]. Regardless, the MnO2 surface has been reported to facilitate effective Mn(II)
adsorption due to its microporous structure, high surface area and low point of zero charge
(PZC), which promotes a net negative surface charge in neutral conditions [9, 10].
Complicating the application of greensands is the fact that some commercial greensands have
relatively poor surface areas and adsorption potential [8], thus these materials require bleach
activation which introduces associated costs. Additionally, MnO2 has also been found to be
sensitive to reductive dissolution by Fe(II), which can lead to dissolution of the oxide to

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produce solvated Mn(II) [11, 12]. Notably, recent studies have revealed that commercial

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greensands can be comprise of several phases of MnO2, with each greensand having a unique
composition and removal capacity [8].

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Thus, an understanding of the activity of each manganese oxide phase is required if greensand
performance is to be optimized. Several phases of MnO2 have been reported with each

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material possessing a unique spatial arrangement of the MnO6 octahedra that make up the
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MnO2 solid [13]. The differences in the MnO6 octahedra arrangements manifest into MnO2
having significantly different frameworks that form tunnels/channels and layered sheets with
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various physical characteristics [13].

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Posselt et al. [14] studied the sorption behaviour and capacities of selected cations (Ag+, Ba2+,
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Ca2+, Mg2+, Mn2+, Nd3+ and Sr2+) on porous manganese oxide. The authors used manganese
dioxide which was synthesised by oxidising Mn(II) with sodium permanganate [14]. The
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results suggested that the produced MnO2 had notable sorption capacities for all the
elements tested, whereby an increase in capacity was noted for Group II cations which
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corresponded with decreasing ionic radii [14]. This latter observation was attributed to
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stronger binding of the lower radii cations to the MnO2 surface [14]. Manganese(II) was also
found to have a unique sorption behaviour on MnO2 due to an equilibria that exists between
the oxide surface and the solvated Mn(II) (Equation 1) [14].
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Equation 1: Mn2+ + MnO2 + 2H2 O ⇄ 2MnOOH +2H+

This behaviour allowed Mn(II) to be adsorbed in larger capacities (mole-ratio basis) than the
other divalent adsorbates studied [14]. This latter article provided a comprehensive analysis

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of MnO2 adsorption capacities for various cations, however the authors only studied one
MnO2 material and further, the synthesised material was not characterised.

Single phase manganese oxides such as birnessite [15], cryptomelane [16, 17], hausmannite
[17] and todorokite [16-18] have been investigated for various applications related to
solvated heavy metal removal. Feng et al. [17] reported the capacities of birnessite (2x∞
layer), cryptomelane (2x2 tunnel), todorokite (3x3 tunnel) and hausmannite (low oxide) MnO2

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phases for selected divalent heavy metal adsorption, namely Pb2+, Cu2+, Cd2+, Co2+ and Zn2+

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[17]. In summary, it was shown that birnessite had the highest capacity for all tested cations.
In contrast, hausmannite exhibited the lowest capacity for all cations excluding Cu2+;

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cryptomelane displayed the poorest Cu2+ adsorption capacity [17]. Although the study by

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Feng et al. [17] compared various single MnO2 phases for their respective heavy metal
adsorption capacities, minimal discussion focussed on the implication of the different

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structural properties of these phases on removal performances. Dyer et al. [16] investigated
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the sorption behaviour of cryptomelane and todorokite for various trace radionuclides and
related their results to the MnO2 tunnel structures. Eight radionuclides were studied (137Cs,
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89 57 54 59 65 110 236
Sr, Co, Mn, Fe, Zn, Ag and Pu) and the results suggested that selectivity was
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largely governed by the substrate’s framework structure [16]. Cryptomelane showed an

affinity for 110Ag+, but lacked selectivity for the other radionuclides. Todorokite, on the other
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hand, showed affinity for numerous radionuclides with a notable affinity for 59Fe2+ (which was
postulated to be due to reductive dissolution) [16]. An important observation was made
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when calcium (Ca) was used as the templating cation for todorokite, where the removal
137 89 57
performance increased markedly for Cs (in acidic conditions), Sr and Co [16]. The
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primary mechanism for the observed radionuclide removal was proposed to be ion exchange
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with the intercalated cations (Mg/Ca for Todorokite and K for cryptomelane) [16].

The todorokite phase possesses a 3x3 MnO6 tunnel structure with a tunnel size of 7.3 x 7.3 Å
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[19]. This tunnel structure is large enough to allow mono and divalent ions into the tunnel
cavity [13]. Todorokite is commonly used as a molecular [13, 20, 21] or ionic sieve [13, 16,
17], as a catalytic substrate for oxidising organic compounds [22-24] or more recently, for use
as a battery cathode material [25, 26]. Todorokite is normally synthesised using methods that
use templating cations (such as Mg2+ and Ca2+) [13, 19, 27-30]. Despite the aforementioned

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demonstrated effectiveness of todorokite, relatively few articles have been published
regarding todorokite removal capacities for heavy metal cations. Indeed, minimal
information exists regarding the potential of todorokite as a wastewater treatment media,
specifically in the context of AMD treatment. Consequently, this investigation aimed to
determine the performance of todorokite for manganese removal from solution and to
compare this data with related manganese based materials. The critical hypothesis was that
the design of greensand material comprising of specific MnO2 phases would promote removal

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of Mn(II) and Fe(II) species from solution. Research objectives to address included: (1)

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synthesis of single phase materials of pyrolusite (1x1), cryptomelane (2x2) and todorokite
(3x3); (2) determination of the effect of tunnel size and framework substitution upon Mn(II)

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and Fe(II) removal performance; (3) identification of the most active phase for selective Mn(II)

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removal in the presence of Fe(II), where resistance to reductive dissolution and process
implications will be considered; (4) optimisation of the framework of the desired phase to

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enhance Mn(II) removal capacity; and (5) evaluation the removal efficiency and selectivity of
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the desired phase in raw and lime-treated AMD water.
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2. MATERIALS AND METHODS
2.1. Materials:
The manganese chloride tetrahydrate (MnCl2·4H2O), potassium permanganate (KMnO4),
magnesium chloride hexahydrate (MgCl2·6H2O), manganese sulfate monohydrate
(MnSO4∙H2O), and sodium persulfate (Na2S2O4) used in the synthesis of the single phase MnO2
materials were purchased from Chem-Supply as analytical reagent (AR) grade. No further
purification or chemical treatment was used prior to use. Stock solutions for the equilibria

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studies were comprised of AR grade MnCl2∙4H2O and laboratory reagent (LR) grade ferrous

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chloride dihydrate (FeCl2∙2H2O). Hydrochloric acid (HCl) and sodium hydroxide (NaOH) used
for pH adjustment were purchased from Chem-Supply in concentrated form (32 and 40 wt%,

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respectively) then diluted to give 0.05 M solutions of each. AMD water was sourced from Mt

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Morgan Mine Open Pit, Mt Morgan, Queensland, Australia.

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Simulated AMD discharge water [Table 1] was prepared as a representative sample of the
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typical heavy metal content achieved by on-site AMD lime treatment at Mt Morgan Mine Site
(pH 6.59, Mn – 78.14 mg/L, Zn – 0.425, Co - 0.255, Al - 0.386, Mg - 2138, Ca - 645.7). This
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water was prepared by adding selected AR grade (Chem-Supply) metal sulfate and chloride
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salts to 10 L of deionized (DI) water. Alkali and alkaline earth metal salts were added first,
followed by the addition of sulfuric acid (H2SO4) for the desired sulfate (SO42-) concentration.
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The pH was then adjusted to pH 6.5 with 40% NaOH, where the heavy metal salts were added
subsequently to avoid irreversible precipitation of metal oxides.
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Lime dosed AMD was prepared by the addition of a calcium hydroxide (Ca(OH)2, ca. 20 g/L)
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slurry to 500 mL of AMD (collected February 2017), under constant stirring until the target pH
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was reached (pH 6.5 – 7.0). The resulting suspension was left to settle for 15 h and the
supernatant was decanted. This water was used to directly compare the effect of lime dosing
on adsorbent removal capacities for AMD.
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Table 1: Elemental composition of the raw AMD, lime-treated and simulated discharge AMD
waters used in this work
Elemental Lime Treated Simulated
Raw AMD
Concentration* (mg/L) AMD Discharge Water
Al 1091 0.020 0.402
B 0.239 0.094 0.011
Ca 522.1 661.6 568.4

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Cd 0.263 0.052 0.007

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Co 4.036 0.546 0.229
Cr 0.048 0.026 0.026

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Cu 79.47 0.041 0.026

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Fe 8.29 0.007 0.011
K 10.06 3.145 10.73
Mg 2436 720
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Mn 167.9 54.36 74.17
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Mo 0.023 0.01 0.012
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Na 650.6 247.1 1804

Ni 1.172 0.089 0.234
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S 6758 2009 1071

Si 26.19 0.848 0.625
Sr 0.852 0.56 0.433
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Zn 52.62 0.434 0.394

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pH 3.78 6.91 6.15

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Conductivity (mS.cm-1) 15.65 7.59 21.01

* Determined by ICP-OES analysis (Section 2.3)
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2.2. Experimental procedure:

2.2.1. Single Phase MnO2 Synthesis
The three single phase MnO2 solids were synthesised by adapting a hydrothermal method
used by Chen et al. [22]. Pyrolusite (1x1) was synthesised by mixing MnSO4∙H2O (39.075 g,
0.231 mol) and Na2S2O4 (54.537 g, 0.229 mol) in a large beaker where DI water (1000 mL) was

7
added and stirred to dissolve. Similarly, cryptomelane (2x2) was synthesised by mixing
MnSO4∙H2O (23.789 g, 0.141 mol) and KMnO4 (14.684 g, 0.093 mol) in a separate large beaker
wherein DI water (1000 mL) was added and stirred until all reagents were dissolved.

The resulting solutions were then each decanted into 20 x 50 mL capped, polypropylene (PP)
digestion tubes, and left to age at 90°C for four days. Each of the reaction mixtures were
collectively filtered and washed well with DI water and dried in an oven at 105°C overnight.

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The resulting products were then calcined at 300°C for 6 hours. The pyrolusite reaction

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yielded 12.17 g of blue-black solid and the cryptomelane reaction yielded 21.18 g brown solid.
The synthesised powders were subsequently labelled as MnO-P and MnO-C, respectively.

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Todorokite was synthesised by mixing MnCl2∙4H2O (39.521 g, 0.20 mol) and MgCl2∙6H2O
(16.441 g, 0.08 mol) in a 2000 mL PP beaker wherein DI water (400 mL) was added and the

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solution was stirred for 10 minutes. Subsequently, NaOH solution (500 mL, 5 M) and KMnO4
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solution (400 mL, 0.20 M) were added sequentially to the PP beaker. The solution turned to
a beige coloured slurry on addition to the NaOH, then olive green after the KMnO4 was added.
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The resulting suspension was stirred at room temperature for 10 minutes, then covered and
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left to age for five days at room temperature.

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The resultant suspension was then vacuum filtered and washed well with DI water. The wet
solid was transferred to a 10 L polypropylene (PP) vessel containing MgCl2 solution (5000 mL,
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1 M). This suspension was stirred for 24 hours then decanted into 5 x 1000 mL polyelthylene
(HDPE) capped bottles and aged at 90°C for 6 days. The suspension was then collectively
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filtered, rinsed well with DI water and dried at 105°C overnight. The resulting product was
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then calcined at 300°C for 6 hours. The reaction yielded 33.03 g of olive green to black,
calcined product; identified as MnO-T(L).
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2.2.2. Framework Substituted Todorokite Synthesis

The framework substituted todorokite was synthesised by adapting a method described by
Tian et al. [31]. Two different starting conditions were used to produce two modified
todorokite solids, labelled MnO-T(M) and MnO-T(H). MnO-T(M) and MnO-T(H) solids were
synthesised by mixing MnCl2∙4H2O (13.2 g, 0.07 mol) and MgCl2∙6H2O (13.504 g (0.07 mol) or

8
19.011 g (0.09 mol), respectively) in a 1000 mL PP beaker where DI water (130 mL) was added
and the solution was stirred for 10 minutes. Subsequently, NaOH solution (165 mL, 5 M) and
KMnO4 solution (130 mL, 0.20 M) were added sequentially to the PP beaker. Again, the
solutions turned to a beige coloured slurry on addition to the NaOH, then olive green after
the KMnO4 was added. The MnO-T(H) was a darker green than the MnO-T(M) solid. The
resulting suspension was stirred at room temperature for 10 minutes, then covered and left
to age for five days at room temperature.

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The suspension was then vacuum filtered and washed well with DI water. The wet solid was
transferred to a 2000 mL PP vessel containing MgCl2 solution (1600 mL, 1 M). This suspension

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was stirred for 24 hours. The suspension was decanted into separate 2000 mL HDPE capped

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bottles and aged at 90°C for 6 days. The suspensions were then filtered, rinsed well with DI
water and dried at 105°C overnight. The resulting product was then calcined at 300°C for 6

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hours. Overall, the 3 todorokite syntheses: MnO-T(L), MnO-T(M) and MnO-T(H) had starting
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respective Mg:Mn molar ratios of 0.4:1 (0.4), 1:1 (1.0) and 1.3:1 (1.3).
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2.2.3. Equilibria Experiments

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Batch equilibria experiments were conducted at room temperature (22 ± 1°C). Increasing
masses of each adsorbent were placed in 50 mL polypropylene Falcon tubes [32] with 40.0
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mL of either Mn(II) and Fe(II) containing solutions, or AMD and discharge waters. Equilibrium
tests were thus conducted using the constant concentration bottle point method which does
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not introduce experimental artefacts such as when the constant mass bottle point method is
used [33]. Solutions were pH adjusted to either pH 5.5 or pH 7.0 using HCl (0.05 M) or NaOH
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(0.05 M). Each adsorbent (ca. 0.1 g) was also agitated in DI water (40.0 mL) for 24 hrs to
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measure the stability of each adsorbent as a control experiment. The suspensions were
agitated for 24 h on a rotary wheel, then the supernatants were analysed by inductively
coupled plasma optical emission spectroscopy (ICP-OES). The remaining solid for each
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experiment was sampled and dried at 60°C and characterised using Raman spectroscopy. To
assist in determining the equilibrium loading capacity of the materials, the MnO-T removal
data was fitted by using the Aranovich-Donohue model (Equation 2) which has been
demonstrated to be applicable for sorption processes which are characterized by both
monolayer and multilayer uptake [34]. In all cases, non-linear least squares (NLLS) analysis

9
was used to fit the experimental data in order to avoid errors introduced by linearization of
equations [35, 36].

qmax KL Ce
Equation 2: qe = n
(1+KL Ce )(1-Ce⁄Co)

Where: qe = equilibrium loading of the ion (mg/g); KL = Langmuir equilibrium coefficient

(L/mg); Ce = equilibrium concentration of ion in solution (mg/L); Co = initial concentration of

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ion (mg/L); and n is a fitting constant.

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2.3. Characterisation techniques:

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Powder X-ray diffraction patterns were collected using a Rigaku SmartLab diffractometer (Cu
source, 40 kV 40 mA) operating in divergent beam mode using Rigaku’s CBO-α unit which
houses a divergent mirror. The detector was a Hypix 3000 operating in 1D mode. Patterns
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were collected from 4 – 75 °2θ at a step size of 0.015° for 1 hr over the Theta/2-Theta axis.
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Incident optics consisted of a 5° Soller slit, 10 mm incident slit and a 0.1° divergence slit.
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Receiving optics were a 5° Soller slit and 20 mm receiving slit. Samples were back-pressed
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into sample holders using a fine mesh as a surface that minimised preferred orientation.
Samples were spun at 120 rpm during analysis. Quantitative phase analysis was performed
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using Rietveld refinement as implemented in TOPAS (V5). An instrument function was

determined from Certified Reference Material (CRM) 640C Silicon Powder from the National
Institute of Standards and Technology (NIST). Qualitative reference patterns for pyrolusite,
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cryptomelane, todorokite, and corundum were sourced from the Inorganic Crystal Structure
Database (ICSD). The ICSD reference pattern ID’s were 98-00-0393, 98-005-9159, 98-005-
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4113, and 98-000-9770, respectively.

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Raman spectra were obtained using a Renishaw inVia Raman Microscope using a 785 nm
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Renishaw 300mW PLC HPNIR laser. Calibration of the microscope was achieved by adjusting
the Raman vibration of a silicon wafer to 520.5 cm-1 at 10% laser power. Sample spectra over
the range of 800-200 cm-1 were obtained using 0.5% laser power (1.5mW) with 16x 40 second
single scan acquisitions. Spectral manipulation such as baseline correction, smoothing and
normalisation was performed using the GRAMS software package. Spectral deconvolution

10
was carried out using the GRAMS AI program so that a minimum spectral correlation (r2) of
0.99 was achieved.

Brunauer-Emmett-Teller (BET) surface area measurements were obtained using a

Micrometrics TriStar II 3020 surface area and porosity analyser. The N2 gas adsorption
isotherm used a 99 data point BET curve. Samples were degassed in ⅜ inch samples tubes at
105°C for 72 hours under vacuum. Adsorption data was analysed using the software package

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MicroActive.

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Multi-element quantitation was performed using a Perkin Elmer 8300DV ICP-OES fitted with

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an ESI SC-4DX autosampler and PrepFAST 2 sample handling unit for online internal

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standardisation and auto-dilution of samples and calibration standards. Purified nitric acid
was used for the preparation of all standards and blank solutions used throughout the

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analysis. Instrument calibration was performed using multi-element standards prepared in-
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house from Inductively Coupled Plasma Mass Spectrometer (ICP-MS) grade single element
stock solutions (High Purity Standards, Charleston, USA). Trace elements were calibrated at
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50, 500 and 5000 µg/L and major elements were calibrated at 0.050, 0.500, 5.000, 20.0 and
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200 mg/L all with an r2 value of >0.99998. Method robustness, accuracy and precision was
verified by continuing analysis of a number of Certified Reference Materials (CRM’s) and
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external validation samples covering a range of common matrices and analyte concentrations
(NIST, Gaithersburg, MD, USA, United States Geological Survey, Reston, VA, USA). Samples
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submitted for ICP-OES analysis were diluted 1:10. Three CRM’s were used: Certified Waste
Water Samples – Trace Metals – A, B and D (CWW-TM-A, CWW-TM-B & CWW-TM-D); and
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two external validation samples: Initial Calibration Verification – 1A and 1B (ICV-1A & ICV-1B).
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X-ray fluorescence (XRF) elemental quantification of the solid samples was analysed using a
Panalytical Axios Wavelength Dispersive (WD) XRF instrument equipped with a 1 kW rhodium
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tube. Instrument intensities for major elements were normalised to the primary calibration
using four AUSMON glass disc monitors. Sample intensities were acquired and the oxide
concentrations were determined against a Panalytical standard WROXI procedure. Samples
were prepared as fused lithium borate discs using a 50:50 LiM:LiT flux with a lithium iodide
(LiI) releasing agent. Glass discs were prepared with a sample concentration of 7 wt%.

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3. RESULTS AND DISCUSSION
3.1. Material Characterisation
X-ray diffraction patterns of the synthesised solids showed that they were comprised of
different crystalline phases, and the synthesis variations in the MnO-T solids resulted in slight
changes in the corresponding patterns (Figure 1). The solids were all somewhat disordered
due to the broad peak shapes and contained non-negligible amorphous content. Meaningful
quantitative data was difficult to achieve, however the recorded data was sufficient for

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qualitative analysis.

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Figure 1: X-ray diffraction patterns of the synthesised MnO2 products: (a) MnO-P, (b) MnO-C,
(c) MnO-T(L), (d) MnO-T(M) and (e) MnO-T(H). Reference patterns sourced from ICSD.
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MnO-P was primarily pyrolusite (β-MnO2, 61.9 wt%), with approximately 34.1 wt% of non-
diffracting/unidentified material and the observed pattern matched well with the reference
pattern for pyrolusite. The small inconsistencies seen between the recorded pattern and the
pyrolusite reference, especially for the peak at 2.4 Å, were attributed to structural variations
of β-MnO2. The MnO-C solid was determined to be approximately 77.4 wt% cryptomelane

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(K+ form α-MnO2) with remaining 22.6 wt% being non-diffracting/unidentified material. Once
again, framework discrepancies were detected which resulted in poor agreement between
relative intensities of the measured pattern and the reference. Nevertheless, the target
phases of both MnO-P and MnO-C were successfully synthesised, and no other major phases
of MnO2 were detected.

The MnO-T solids were more difficult to characterise, mainly due to poor crystallinity, high

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amorphous content, and lack of robust literature on the structural variations of todorokite.

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Quantitative analysis of the MnO-T solids indicated a small amount of crystalline Mg-
todorokite with potential pyrochroite (Mn(OH)2) content. The crystal parameter constraints

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were relaxed significantly in an attempt to match peak intensities, therefore, quantitative

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results were not reported for these samples. What was concluded from the quantification
results was that the MnO-T phases appeared to be a form of disordered todorokite.

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Examination of the pattern for MnO-T(L) solid revealed two prominent peaks at 9.5 (I/I0 =
0.45) and 4.7 Å (I/I0 = 1.0) which have been reported as diagnostic peaks for todorokite [37-
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40]. Ching et al. [38] also indicated that in todorokite, the 4.8 Å peak was dominant, which
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matched the relative peak intensities from this study. Furthermore, the 9.6 Å peak was
reported to be dominant in the buserite (Mg intercalated 1x∞ MnO6 layered structure)
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pattern; an intermediate phase during the todorokite synthesis route [38]. Additionally, the
primary intermediate during todorokite synthesis, birnessite (Na intercalated 1x∞ MnO6),
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was reported to have a major peak at 7.1 Å [38]. Both of these departures from the todorokite
pattern were not observed in this investigation, indicating the target phase of todorokite was
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achieved.
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Intensity ratios of the 9.5 and 4.7 Å peaks in MnO-T(M) and MnO-T(H) solids were shown to
decrease (I9.5/I4.7 = 0.20 and 0.12, respectively) when compared to the MnO-T(L) pattern
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(I9.5/I4.7 = 0.45). The decreasing intensity of the 9.5 Å peak indicated a decline in crystallinity
which agreed with observations by Tian et al. [31] where higher concentrations of starting
MgCl2 diminished product crystallinity.

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Raman spectroscopy was used to compliment the X-ray diffraction patterns and to further
elucidate any structural differences between the synthesised todorokite phases (Figure 2).
The broad peak shapes recorded for each synthesised solid were deconvoluted and the sub-
band positions annotated (Figure 2).

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U
N
A
M
ED
E PT

Figure 2: Raman spectra of the synthesised MnO2 solids with spectral deconvolutions: (a)
CC

MnO-P; (b) MnO-C; (c) MnO-T(L); (d) MnO-T(M) and (e) MnO-T(H).
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The MnO-P solid showed 3 major Raman peaks at 758, 657 and 575 cm-1 and four minor bands
at 521, 486, 399 and 276 cm-1 (Figure 2a). The peaks at 758, 657, 575, 486 and 392 cm-1 were
consistent with vibrational modes of pyrolusite (β-MnO2), with the peaks at 657 and 575 cm-
1
attributed to Mn-O lattice vibrations and the lower Raman shifts were due to the
deformation vibrational mode of the Mn-O-Mn chains [41, 42].

14
The major peaks at 634 and 575 cm-1 and the minor peaks at 517 and 387 cm-1 for the MnO-
C solid were ascribed to the vibrational bands of hollandite; however these values were
shifted slightly when compared to the peaks reported in literature [42]. Julien et al. [42]
attributed peak dampening to the presence of heavy metal ions in the hollandite tunnel
structure. Therefore, a possible explanation of the inconsistencies observed may be due to
attenuation of the MnO6 vibrations from the intercalated K+ in the 2x2 tunnel. Furthermore,
use of low laser power such as used in this study has been reported to sacrifice peak position

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accuracy slightly [43].

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Juilen et al. and Feng et al. [39, 42] reported todorokite to exhibit two major peaks at 640 and

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590 cm-1, however in this investigation, the MnO-T solids were observed to be characterized

SC
by one large, board peak centred around 630 - 640 cm-1 with minor, broad bands from 530 to
300 cm-1 (Figure 2c-e). These three samples did not give well defined Raman spectra, likely

U
owing to the lack of crystallinity and disorder noted from the XRD analysis, which is known to
N
lower spectroscopic symmetry [44]. Deconvolution of the spectra simulated the underlying
vibrations which revealed major contributions at 690 – 680, 645 – 615 and 595 – 570 cm-1 for
A

the MnO-T solids, where the strongest bands were located between 614 – 588 cm-1. These
M

peak positions encompassed a large range which can be harmonious to various precursor or
intermediate MnO2 phases that formed during todorokite synthesis (such as Na-birnessite or
ED

Mg-Buserite). However, the overall spectra of the MnO-T solids were unique from the various
intermediate phases that were recorded after initial precipitation, Mg treatment and
PT

hydrothermal treatment (see supplementary data for spectra (S1)). This observation
indicated that intermediate phases that formed during synthesis were not present in the final
E

product; XRD results also supported this statement. It was postulated that the Raman
CC

vibrations at 645 – 615 and 595 – 570 cm-1 were attributed to MnO6 stretching vibrations of
the todorokite framework, based on similar vibrational characterisation of birnessite by Julien
et al. [42]. It is proposed that variations in the intensity and position of these peaks was an
A

indication of framework substitution, likely by Mg2+.

15
The BET surface area measurements were 22.49, 43.89, 36.24, 32.49 and 35.47 m2/g for MnO-
P, MnO-C, MnO-T(L), MnO-T(M) and MnO-T(H), respectively (full BET isotherms were
reported in Supplementary Data S2). These results suggested that the MnO-C solid was most
likely to have the highest adsorption capacity as it had the highest surface area of the analysed
solids. Nevertheless, all the solids analysed were had a relatively low surface area in
comparison to adsorbent materials like granular ferric hydroxide (GFH) and synthetic iron

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oxide adsorbents which exhibit surface areas >200 m2/g [45]. The relatively lower surface

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areas reported in this work may be a topic of future optimisation of the synthetic products to
improve removal performance.

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SC
The elemental compositions of the synthesised MnO2 solids, reported in Table 2, supported
the phase identifications from the XRD and Raman results.

U
N
Table 2: Elemental composition of MnO2 phases
Elemental Weight Percent (wt%)
A
Sample
Mn K S Si Mg Na
M

MnO-P 62.89 0.01 0.16 0.08 0 0.05

MnO-C 59.41 4.81 0.16 0.03 0 0.03
ED

MnO-T(L) 40.72 0 0 0.02 16.64 0.05

MnO-T(M) 39.46 0 0 0 16.07 0.03
PT

MnO-T(H) 34.41 0 0 0 19.56 0.03

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MnO-P was shown to only have manganese (Mn) as the major cationic component (62.89
CC

wt%) of the solid which was indicative of pyrolusite, which lacks any intercalated ion in the
1x1 tunnel structure. The MnO-C solid was shown to contain 4.81 wt% potassium (K),
A

concurrent with a majority percentage of Mn (59.41 wt%), which is consistent with the K
intercalated in the cryptomelane tunnel structure. Similarly, all the MnO-T solids were shown
to have varying levels of magnesium (Mg) in conjunction with a majority Mn content. This
result further supported the identification of todorokite for these samples. The 0.78 Mn/Mg
molar ratio of MnO-T(H) was the lowest of the synthesised todorokite solids which was

16
expected due to the higher Mg content in the starting mixture (1:1.3 Mn:Mg). Interestingly,
the similar Mn/Mg ratios of the MnO-T(L) (1.08) and MnO-T(M) (1.09) solids was not
harmonious with the starting ratios of 0.4:1 and 1:1, respectively. Tian, et al. [31] reported
that starting concentrations of MgCl2 between 0.1 and 0.5 M produced similar todorokite
structures, outside of this range variations in the todorokite structures were observed. This
study used 0.2, 0.5 and 0.7 M starting concentrations for the MnO-T(L), MnO-T(M) and MnO-
T(H) materials, respectively, thus the similar Raman spectra and elemental compositions of

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the MnO-T(L) and MnO-T(M) solids was in accord with previous literature. Measurement of

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the leachability of the MnO-T(L), MnO-T(M) and MnO-T(H) solids in pH 7 water over 24 hrs
showed that the solid leached 9.98, 14.69 and 21.25 mg/g Mg, respectively, with the effluent

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pH also becoming more alkaline (pH 8.95, 9.25 and 9.74). This was an indication that the

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increased Mg in the starting reaction also increased the amount of exchangeable Mg in the
final product.

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3.2. Effect of MnO2 Phase on Removal
The removal capacities of the three synthesised MnO2 phases were evaluated and the
A

isotherm results reported in Figure 3. The three phases exhibited different capacities for
M

Mn(II) removal: wherein MnO-P lacked any removal capacity, MnO-C was effective for low
concentrations of Mn(II) and MnO-T(L) displayed significant affinity for Mn(II) removal. MnO-
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P was observed to leach 0.65 mg Mn(II) per gram of material (0.024 meq/g) in the control
experiment in DI water through dissolution. Translating this to the measured isotherm
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results, a higher equilibrium Mn(II) concentration was expected if no removal was present.
Rather, the results indicated that some Mn(II) removal was achieved, however the dissolution
E

of the MnO-P substrate dominated any beneficial activity. Further supporting this, the pH
CC

was shown to decrease from pH 6.0 to 5.5 across the adsorbent mass range. This was an
indication of Mn(II) adsorption according to Morgan and Strumm [46] due to the release of
protons from the hydrated MnO2 surface. The increased acidity of the equilibrium
A

environment was also thought to further aid in the dissolution of the MnO-P substrate. In
contrast, the MnO-C was not found to leach Mn(II) during the control experiment in DI water.
The MnO-C showed capacity for Mn(II) removal at low adsorbent masses which is likely an
effect of the higher dissolution stability, however the produced protons from Mn(II)
adsorption appeared to have induced MnO2 dissolution at higher mass concentrations.

17
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A
M
ED

Figure 3: Removal of Mn(II) from aqueous solution adjusted to pH 7 using: (a) MnO-P @ 0.15
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ppm Mn(II), (b) MnO-C @ 0.50 ppm Mn(II), (c) MnO-T(L) @ 25ppm Mn(II) and (d) MnO-T(L) at
pH 5.5 @ 25ppm Mn(II)
E
CC

The MnO-T(L) phase was shown to have a significantly higher Mn(II) capacity and different
removal behaviour when compared to the former two adsorbents. Firstly, the substrate was
A

shown to effectively remove Mn(II) from a markedly increased stock concentration and,
secondly, Mg was increasingly present in the equilibrium solution which correlated with the
increasing adsorbent mass used. Once corrected for the background Mg leaching (9.98 mg/g
from control experiment in DI water), the equilibrium Mg concentration was equi-molar with
the amount of removed Mn (Figure 4).

18
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Figure 4: Molar comparison of exchanged Mg and removed Mn from solution when using

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MnO-T(L): (a) 25ppm Mn(II) at pH 7, (b) 25ppm Mn(II) at pH 5.5

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This latter behaviour was an indication that an ion exchange mechanism dominated MnO-T(L)

U
Mn(II) removal (Figure 5), which was consistent with previous literature regarding todorokite
N
and heavy metal uptake [40]. Another notable observation was that the equilibrium pH
increased when removing Mn(II), rather than producing an acidic environment. Moreover, a
A
significant pH increase was observed when 100 % Mn(II) removal was achieved, which
M

plateaued for subsequently higher masses. When comparing the control experiment in DI
water to the removal results, the equilibrium pH increased to 9.06 when 0.1g of MnO-T(L)
ED

was used; the removal isotherm produced a higher equilibrium pH (pH 9.81) when using less
adsorbent (0.025g). This result indicated that Mn(II) removal using MnO-T(L) promoted an
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increased hydroxide concentration in the liquid phase.

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The MnO-T(L) media was also used to remove Mn(II) from slightly acidic solution (pH 5.5) to
CC

observe any environmental factors that may influence removal performance (Figure 3d). The
results showed a similar behaviour to the removal experiment at neutral pH, whereby Mn(II)
was effectively removed while Mg was exchanged into solution (Figure 4b). The released Mg
A

concentration and equilibrium pH for the slightly acidic experiment were noted to be lower
in comparison to the case at neutral pH; however, the corrected Mg molarity remained in
parity with the amount of Mn removed.

19
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Figure 5: Proposed exchange mechanism of Mn(II) for Mg(II) using Mg-Todorokite

U
N
The measured data appeared to follow Type II adsorption behaviour and the Aranovich-
Donohue model acceptably fitted isotherms for both pH 5.5 and 7 experiments, each giving
A
coefficients (r2) of 0.98 (Figure 6).
M
ED
E PT
CC
A

Figure 6: Aranovich-Donohue NLLS fitted isotherms for Mn(II) removal using MnO-T(L) at pH
5.5, and pH 7
The model also calculated respective loading capacities for MnO-T(L) under the two pH
conditions of 2.7 and 2.9 meq/g. The initial removal (at Ce = 0) appeared to be irreversible

20
and relatively consistent in terms of Mn(II) loading (approximately 3.0 meq/g); postulated to
be the ion exchange mechanism. Beyond this point, there appeared to be an extended period
of saturation, which was longer for the pH 5.5 experiment, before a secondary removal
mechanism was observed. This indicated a secondary surface adsorption mechanism after
this period, which would be less favoured at lower pH, considering Mn(II) adsorption
increases at higher pH [14, 46].

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The Fe(II) removal capacities and dissolution stabilities of the synthesised solids were also

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investigated and the results reported in Figure 7. Each of the solids were shown to remove
Fe(II) effectively from solution, however MnO-P and MnO-C were observed to be affected by

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reductive dissolution (Equation 3).

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Equation 3: MnO2 (s) + 2Fe2+ + 4H+ → Mn2+ + 2Fe3+ + 2H2 O(l) [12]

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The MnO-P solid was found to once again leach Mn(II), however the measured concentration
A
was on average 5 x 10-3 meq/L above the expected level from MnO2 leaching alone. The
increased Mn(II) level was likely due to reductive dissolution which was calculated (from 0.16
M

mg/L Fe(II) stock) to result in approximately 3 x 10-3 meq/L increase of liquid-phase Mn(II).
The additional 2 x 10-3 meq/L Mn(II) was probably due to an increased rate of dissolution from
ED

a more acidic environment (pH 4.5 – 5.0) [46].

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Similar behaviour was observed with the MnO-C solid whereby Fe(II) was effectively removed
and Mn(II) was detected in the liquid-phase. The liquid-phase Mn(II) concentration was less
E

than the MnO-P experiment, which was attributed to the increased stability of the MnO-C
CC

solid. However, at larger masses the increased acidity of the liquid-phase promoted further
MnO2 dissolution.
A

21
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U
N
A
M

Figure 7: Removal of Fe(II) from aqueous solution using: (a) MnO-P @ 0.16 mg/L Fe(II), (b)
MnO-C @ 0.16 mg/L Fe(II) and (c) MnO-T(L) @ 25 mg/L Fe(II)
ED

The MnO-T(L) solid showed marked resistance to reductive dissolution, however at low
masses, the solid was shown to release Mn(II) into solution. The pH of the equilibrium
PT

solution was shown to steadily increase with increasing substrate mass, along with the Mg
concentration. This indicated that Mg was exchanging off the MnO-T(L) solid either for Fe(II),
E

solvated Mn(II) or both. At the point of complete Fe(II) removal, the equilibrium pH reached
CC

6.5 which would have provided an unstable environment for solvated Fe(II), thus the ferrous
ions likely precipitated out as ferric (hydr)oxides, leaving the Mn(II) removal possibility the
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most plausible. At full iron removal, the calculated difference between the Mg leaching levels
from the control experiment (9.98 mg/g) and the observed concentration for MnO-T(L) in
Figure 7c was 1.1 meq/L (2.2 x 10-5 moles Mg), which represented the level of exchanged Mg.
The level of produced Mn(II) from reductive dissolution (Equation 3) was calculated to be
approximately 0.5 meq/L (9.5 x 10-6 moles Mn), which accounted for half of the observed

22
exchangeable Mg concentration, assuming a 1:1 exchange ratio. However, the implication of
MnO2 dissolution by Fe(II) needed to be considered. For every milli-equivalent of Mn(II)
produced by Equation 3, 8.683 x 10-1 milli-equivalents of Mg was also released from the
structure (due to dissolution). This translated overall (when the produced Mn(II) was
exchanged back into the remaining tunnel structure) to an equilibrium solution of 1.8683
milli-equivalents of Mg per milli-equivalent of produced Mn(II). Relating this value to Fe(II),
for every milli-equivalent of Fe(II) removed, 9.342 x 10-1 milli-equivalents of Mg should be

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released into solution (through dissolution and Mn-exchange) (Figure 8).

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Comparison of the observed Mg concentration at total Fe removal (2.8 x 10-5 meq Mg) to the

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calculated Mg concentration (3.6 x 10-5 meq Mg), revealed there was a small discrepancy of

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(-0.8x10-5 meq Mg); meaning less Mg was released from the MnO-T(L) solid when modelling
Fe(II) removal by reductive dissolution alone. This may be an indication that some Fe(II) was

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precipitated from solution as a result of the increased OH- concentration (increased solution
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pH).
A
M
ED
E PT
CC
A

Figure 8: : Proposed removal mechanism of Fe(II) using Mg-Todorokite (MnO-T(L)): (1)

reductive dissolution of MnO2 by Fe(II) producing Fe(III), solvated Mn(II) and structural Mg(II);
(2) produced Fe(III) is precipitated out as an (hydr)oxide; (3) solvated Mn(II) is exchanged with
Mg by remaining todorokite solid unaffected by dissolution from (1).

23
Considering the resistance to reductive dissolution, the competitive removal of Mn(II) and
Fe(II) from solution of the MnO-T(L) solid was investigated. The experiment used the same
driving force as the mono-ion solution experiments to preserve comparability and the results
are shown in Figure 9.

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Figure 9: Competitive removal of 25 mg/L Mn(II) and 25 ppm Fe(II) from aqueous solution
using MnO-T(L) at pH 5.5
A
M

Once again, similar removal behaviour was observed where Mg was exchanged off the solid
and the pH increased when larger masses were used. Notably, both the Mn(II) and Fe(II)
ED

content of the water was removed completely when using an adequate solid concentration
(approximately 5 g/L). This latter outcome was also indicative of the phenomenon noted
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earlier where the produced Mn(II) from reductive dissolution was scrubbed out of solution by
the todorokite solid. In terms of selectivity, it appeared that Fe(II) removal was favoured over
E

Mn(II), which was likely due to a separate removal mechanism, such as reductive dissolution
CC

and precipitation, rather than ion exchange.

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3.3. Effect of Mg Content in Todorokite on Removal

The concentration of Mg in the todorokite structure was also compared in terms of Mn(II)
and Fe(II) removal performance. The MnO-T(M) and MnO-T(H) materials were tested under
similar conditions as the MnO-T(L) and removal performance for Mn(II) and Fe(II) were
reported in Figure 10.

24
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U
N
A
M
ED
E PT
CC
A

Figure 10: Comparison of the removal behaviour of the MnO-T(L), MnO-T(M) and MnO-T(H)
solids when treating solutions of 25 mg/L Mn(II) or 25 mg/L Fe(II) at pH 5.5

25
The increased Mg content of the todorokite solids had a marked effect on the removal
performance of Mn(II) from solution (Figure 11). The Mn(II) loading capacities (Aranovich-
Donohue qmax) for the MnO-T(L), MnO-T(M) and MnO-T(H) solids were calculated to be 2.7,
3.6 and 4.7 meq/g, respectively.

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N
A
M
ED
E PT

Figure 11: Aranovich-Donohue isotherm models for the MnO-T(L), MnO-T(M) and MnO-T(H)
CC

materials when treating 25 mg/L Mn(II) solution at pH 5.5

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This latter behaviour indicated that there was more Mg in the todorokite inter-tunnel spacing
available for exchange. Alternatively, examination of the Raman spectra of Mn(II) exhausted
MnO-T(M) and MnO-T(H) solids, indicated that a sharp peak at 650 cm-1 (Figure 12) appeared
which was attributed to hausmannite; a decomposition product of todorokite (tunnel
collapse) [42, 47]. This observation inferred that the higher Mg:Mn todorokite solids

26
experienced irreversible structural instability when treating Mn(II) containing solutions
beyond capacity. The MnO-T(L) solid was significantly more stable when used beyond capacity
due to the similar structural features between Mn(II) exhausted and virgin material (Figure
12). Hausmannite was not expected to retain the Mn(II) removal capacity of todorokite due
to its spinel-like structure; which would have an inherently smaller cavity/tunnel size and in
light of previous work by Feng et al. outlining the reduced capacity of hausmannite for heavy
metal removal [17, 42, 47]. Therefore, to preserve the ability to regenerate exhausted

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todorokite for re-use, the original todorokite framework must also be persevered; accepting

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the compromise of a lower Mn(II) removal capacity. The Fe(II) removal behaviour showed a
similar trend of increasing removal capacity from MnO-T(L) to MnO-T(H) (Figure 10). The

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exchanged Mg level remained reasonably consistent across the MnO-T(L) and MnO-T(M)

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solids. However, the MnO-T(H) solid was found to release more Mg into solution.
Furthermore, the pH was noted to become alkaline at lower masses for the higher Mg:Mn

U
ratio solids. The amount of leached Mn(II) by reductive dissolution steadily decreased when
N
higher Mg:Mn ratio solids were used; likely a residual effect of having a more alkaline
environment for Fe precipitation rather than reductive dissolution.
A
M

The Raman spectra of the Fe(II) exhausted MnO-T(M) and MnO-T(H) solids showed minor
structural changes compared to the virgin material; the MnO-T(L) product, however,
ED

remained congruent with the corresponding virgin solid (Figure 12).

E PT
CC
A

27
Figure 12: Raman spectra of the post-treatment MnO-T solids: (bottom) MnO-T, (middle)
Mn(II) exhausted and (top) Fe(II) exhausted.
The Fe(II) exhausted MnO-T(M) solid showed similar structural contributions to the virgin
material, however a slightly less intense band at 690 – 680 cm-1 and an increased band at 570
cm-1 were observed. Similarly, the MnO-T(H) solid also exhibited an increased contribution
for the band at 570 cm-1 and a decrease in intensity for the 690 – 680 cm-1 peak. Overall, the
major spectral features remained consistent with the virgin MnO-T(M) and MnO-T(H) solids,

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indicating little or no phase change occurred during treatment.

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Summarising the key outcomes of this section, it was shown that the higher Mg:Mn ratio of

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the material increased the removal capacity of the todorokite material for both Mn(II) and

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Fe(II). When treating Mn(II) solutions, however, the higher Mg:Mn ratio solids (MnO-T(M)
and MnO-T(H)) showed significant instability in that a phase change occurred, collapsing the

U
todorokite structure to hausmannite. The MnO-T(L) solid was not observed to undergo a
N
phase change while treating Mn(II) solution. All three solids studied showed a high stability
when treating Fe(II) solutions, showing only minor structural changes as indicated from the
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Raman spectra after use. The todorokite solids showed a high capacity for Mn(II) removal,
M

thus the performance of the material when treating AMD was further studied.
ED

3.4. Treatment of Acid Mine Drainage using Modified Todorokites

The heavy metal removal capacities for MnO-T solids treating simulated AMD discharge, raw
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AMD and lime treated AMD were evaluated and the removal percentages at 2.5 g/L dosing
were reported in Table 3. Overall, the MnO-T solids completely removed Mn(II) from the
E

discharge waters (simulated and lime dosed AMD), however, performance was diminished
CC

when treating actual AMD samples. The treatment of open pit AMD was shown to leach
Mn(II) into solution through substrate dissolution: however, cobalt (Co), copper (Cu) and zinc
(Zn) were shown to be removed in small amounts (<30%); whereas solvated iron was removed
A

almost completely from solution (96 – 98.5%). Treatment of the simulated discharge water
showed a marked improvement in removal results where complete removal of Co, Mn and
Zn were observed. Partial removal of Cr (26 – 38.5%), Cu (44 – 65.5%) and Ni (75%) were also
noted. The increased capacity when treating the simulated discharge water was attributed

28
 to the neutral solution pH. Perhaps the most significant result was the selectivity for heavy
metals which was shown by the MnO-T solids.

Table 3: Removal Percentages of the MnO-T solids when treating AMD, lime treated AMD and
simulated discharge water.
Heavy Metal
Co Cr Cu Fe Mn Ni Zn
Contaminant

T
2.5 g/L Simulated Discharge Water (pH 6.15)

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Stock Water (mg/L) 0.229 0.026 0.029 0.00 74.17 0.234 0.394
MnO-T(L) 100% 38.5% 44.8% NA 100% 76.5% 100%

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MnO-T(M) 97.8% 30.8% 65.5% NA 100% 75.6% 100%

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MnO-T(H) 100% 26.9% 65.5% NA 100% 74.8% 100%
2.5 g/L AMD Open Pit Surface Water (pH 3.78)
Stock Water (mg/L) 4.036 0.048 79.47
U
8.29 167.9 1.172 52.62
N
MnO-T(L) 18.0% 0% 18.8% 96.7% -17.6% 0% 1.2%
A
MnO-T(M) 15.8% 0% 23.1% 98.3% -16.5% 0% 11.3%
MnO-T(H) 21.4% 0% 31.1% 98.5% -28.1% 0% 15.3%
M

2.5g/L Lime Treated AMD Open Pit Surface Water (pH 6.92)
ED

Stock Water (mg/L) 0.546 0.026 0.041 0.00 54.36 0.089 0.436
MnO-T(L) 95.73% 39.29% 75.00% NA 100% 77.50% 100%
MnO-T(M) 99.26% 28.57% 70.45% NA 100% 100% 100%
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MnO-T(H) 93.69% 39.29% 72.73% NA 100% 100% 100%

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The liquid phase Mg concentration for the MnO-T(L), MnO-T(M) and MnO-T(H) was found to
CC

increase from 1970 mg/L (stock) to 2042, 2075 and 2078 mg/L, respectively. This result again
indicated Mg exchange, however the driving force for the exchange of Mg with the heavy
A

metal contaminants was quite low (considering the brackish composition of the solution).

The open pit AMD was also lime dosed to pH 6.92 and clarified to simulate a conventional
industrial neutralization process. The treatment effluent chemistry was reported to have a
large concentration of residual Mn(II) (54.36 mg/L, or 1.98 meq/L) with various low levels of

29
Co and Zn (< 1 ppm) and trace levels of Cu, Cr and Ni (Table 3). The same dosing conditions
were used to treat this water and similar results were obtained when compared to the
simulated discharge water, whereby Mn and Zn were completely removed and Co was mostly
removed (> 95%). Similarly, with the simulated discharge experiment, the high selectivity of
the MnO-T solid for heavy metals was demonstrated with the solid exchanging Mg into 1012
mg/L Mg containing liquid phase. Comparison of the calculated loading capacities of the
MnO-T solids for Mn(II) (Table 4) showed that the lime dosed AMD rendered lower removal

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capacities compared to the simulated discharge water. This was likely due to the increased

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stock concentration of Co, Cu and Zn which could have occupied exchange sites for Mn.

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Table 4: Loading capacities (meq/g) of the MnO-T solids when treating lime treated AMD and

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simulated discharge water at 0.5 g of material per litre.

Heavy Metal Contaminant Mn

U
Co Zn
N
0.5 g/L Simulated Discharge Water
A
MnO-T(L) 2.23 0.011 0.020
MnO-T(M) 2.94 0.011 0.017
M

MnO-T(H) 3.87 0.013 0.021

0.5g/L Lime Treated AMD Open Pit Surface Water (pH 6.92)
ED

MnO-T(L) 1.06 0.026 0.021

MnO-T(M) 1.86 0.027 0.022
PT

MnO-T(H) 2.71 0.027 0.022

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The results reported in this investigation showed that todorokite-type manganese oxides can
CC

potentially be used to remedy the high Mn(II) residual contamination of AMD after post-lime
treatment. Further, the solids showed additional capacity to simultaneously remove trace
A

heavy metals such as Co, Ni and Zn from solution. Similar to the todorokite removal capacities
of the simulated solutions (Section 3.3), the higher the Mg:Mn ratio of the solid, the higher
Mn(II) removal capacity that was observed.

30
In general, an ion exchange material that exchanges heavy metals (in particular Mn(II)) for Mg
may not be solely appropriate for drinking water applications where hardness needs to be
controlled. In the context of AMD treatment where high Mg and Ca levels are observed in the
effluent, an Mg exchanging material that removes high Mn(II) content may be acceptable due
to the relatively small increase in effluent Mg content. If hardness is a factor in the overall
treatment process, existing softening processes are available to alleviate the slight increase
in Mg. The immediate benefit of todorokite as an ion exchange material (as opposed to a

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commercial resin, greensand media or batch adsorbent) was that todorokite required no pre-

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treatment or activation steps prior to use. Future work should focus on providing a full risk-
reward comparison between todorokite and commercial ion exchange resin, and also the use

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of todorokite as a batch or fixed bed process.

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4. CONCLUSIONS

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Three phases of MnO2 (pyrolusite, cryptomelane and todorokite) were evaluated for removal
N
performance and stability when treating solutions containing Mn(II) and Fe(II). Pyrolusite was
shown to have the lowest capacity for Mn(II) and be the least stable; being sensitive to both
A

acidic and reductive dissolution. Cryptomelane showed a small capacity for Mn(II) removal,
M

and was sensitive to reductive dissolution by Fe(II). Todorokite was found to be significantly
more effective at removing Mn(II) than the former two phases which was thought to operate
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through an ion exchange mechanism with tunnel intercalated Mg. Todorokite was sensitive
to reductive dissolution: however, the material was found to negate the negative effects of
PT

reductive dissolution by exchanging Mg for the solvated (or produced) Mn(II); ultimately
removing both Mn(II) and Fe(II) from solution.
E
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Treatment of AMD with todorokite like MnO2 materials was shown to be an effective means
for purifying AMD discharge effluents due to the high selectivity and capacity of the material
for Mn(II) and other trace heavy metals. Of the modified todorokites investigated, it was
A

shown that the MnO-T(H) sample was the best performing Mn(II) removal substrate, which
was attributed to the increased Mg content of the solid. This outcome was postulated to
result from the inter-tunnel cavity of the solid, however this material was shown to suffer
from compositional changes when used beyond capacity. The MnO-T(L) solid, while showing

31
the lowest capacity of the todorokite solids for heavy metal removal, maintained structural
integrity when used beyond capacity.

5. ACKNOWLEDGEMENTS
The financial and infra-structure support of the Energy and Process Engineering Discipline of
the Science and Engineering Faculty, Queensland University of Technology is gratefully
acknowledged. Some of the data reported in this paper was obtained at the Central Analytical

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Research Facility operated by the Institute for Future Environments (QUT), with access to

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CARF was supported by funding from the Science and Engineering Faculty (QUT). Particular
acknowledgement is given to Dr. Henry Spratt for his assistance with the structural

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refinement of the synthesised products presented in this study. The Queensland Government

SC
is thanked for supporting the acquisition of some of the instrumentation used and funding
Dr. Couperthwaite through an Accelerate Fellowship grant (2014 - 2017). Department of

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Natural Resources and Mines personnel are thanked for their support and assistance in the
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collection of samples from Mount Morgan mine open pit.
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Department of Natural Resources and Mines

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