3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
Study of mechanisms of manganese removal from leachates
G. Bazdanis, D. Zaharaki and K. Komnitsas
Department of Mineral Resources Engineering, Technical University of Crete, Hania, Greece
ABSTRACT
In the present experimental study the manga-
nese removal mechanisms from leachates were
investigated in batch and column experiments.
Batch leaching tests were carried out in shake
flasks using zero-valent iron (ZVI), activated
carbon (AC) and natural zeolite as reactive me-
dia to obtain kinetic data. Upflow column leach-
ing tests were carried out to simulate the opera-
tion of permeable reactive barriers (PRBs) using
coarse and fine limestone as well as goat ma-
nure as reactive media. Experimental data as
well as mineralogical studies show that the re-
moval mechanisms depend on the reactive ma-
terial used in each case; the main mechanisms
are adsorption, ion exchange and/or co-
precipitation.
1. INTRODUCTION
Manganese is a common contaminant in mine
waters, industrial wastewaters and effluents.
Due to its high mobility and different oxidation
state over a wide pH range it is often difficult to
be removed. Although manganese is not consid-
ered as ecotoxic as other metals, it poses several
environmental problems (Bamforth et al., 2006).
Previous studies that were carried out to investi-
gate Mn removal from acid mine drainage,
leachates and other effluents used reactive mate-
rials such as limestone, red mud, fly ash and or-
ganic matter to increase pH and precipi-
tate/adsorb soluble Mn species (Komnitsas
et al., 2004, 2006).
Manganese oxidation and subsequent re-
moval from solutions may be described by the
following reactions (Lindsay, 1979):
24
Mn2+ + 2H2O → MnO2 + 4H+ + 2e-,
log K = -41,89 (1)
2+ + -
Mn + 2H2O → MnOOH + 3H + e ,
log K = -25,27 (2)
The rate of manganese oxidation may in-
crease when ions such as aluminum and iron are
present in solution as well as through microbial
activity (Vail and Riley, 2000).
PRBs containing zero-valent iron, natural
zeolite and activated carbon have been used to
remove contaminants such as copper (Komnit-
sas et al., 2007), hexavalent chromium (Jeen
et al., 2008), nickel (Argun, 2008), mercury
(Chojnacki et al., 2004), selenium (Sasaki et al.,
2008), cadmium (Di Natale et al., 2008), arsenic
(Chutia et al., 2009; Jeon et al., 2009) and other
elements from leachates (Bartzas et al., 2006a,
b; Gitari et al., 2008).
In the present experimental study manganese
removal from leachates was investigated in
batch and column experiments using several re-
active media.
2. MATERIALS AND METHODS
2.1 Materials
The reactive materials used in batch leaching
tests were zero valent iron (Gotthart Maier,
Germany), activated carbon (Donau Chemie,
Austria) and natural zeolite (S&B Industrial
Minerals S.A., Greece). In the upflow column
leaching tests coarse and fine limestone (Fino-
beton Mining S.A, Greece; 2 fractions 1-2 mm
and 2-5.6 mm were tested), as well as goat ma-
nure (containing N, P2O5, K2O, Ca, Mg, Fe, Mn,
3rd AMIREG International Conference (2009): Assessing the Footprint of 25
Resource Utilization and Hazardous Waste Management, Athens, Greece

Cu, B, Mo and Zn) were used as reactive media.

Chemical analyses and main properties of the
reactive materials are seen in Table 1.
2.2 Methodology
2.2.1 Batch leaching tests
Laboratory batch leaching tests were carried out
in 600 mL conical flasks under magnetic stir-
ring; the reactive media dosage (for activated
carbon, zeolite and ZVI) studied was 0.5, 1.0, 5,
10 and 20 g/L. The initial concentration of Mn Figure 1: Experimental setup for column tests.
in solution was 100 mg/L; this is considered
quite high when compared with actual Mn con- nure was mixed with silica sand in order to
centrations present in leachates and industrial avoid clogging. Two 2.5 cm thick silica sand
effluents. The solution was prepared by dissolv- layers were placed at the base and the top of the
ing the required quantity of manganese sulfate columns in order to ensure optimum flow distri-
monohydrate (MnSO4·H2O) in distilled water. bution and prevent transfer of fine particles. Up-
Adsorption was studied by using Langmuir and flow was applied in order to eliminate channel-
Freundlich equations. ing, maintain optimum contact between solution
and reactive media and increase retention time.
2.2.2 Column experiments The concentration of manganese in the feed
Column experiments were carried out in Plexi- solution was maintained as in the previous se-
glas columns (45 cm length and 5 cm internal ries at 100 mg/L. Feed solution was pumped in
diameter) filled with each reactive media. the columns from 20 L plastic vessels by using
1000 g of coarse or fine limestone and 650 g of PROMINENT GAMMA/4 peristaltic pumps.
goat manure were used in each series; goat ma- The flow rate used was 80 mL/h so that one
pore volume (350 mL) was fed every 4.4 hours.
Table 1: Chemical analysis and main properties of reac- The experimental setup is seen in Figure 1.
tive materials. Aqueous samples were taken from the efflu-
Zero
Acti-
ent of each column and analyzed immediately
valent for pH, oxidation-reduction potential using
(% w/w) vated (% w/w) Zeolite
iron HANNA pH 211 combined pH/Eh meter and
carbon
(Fe0) electric conductivity using a HANNA EC 215
Fe 92.03 Fe2O3 1.23 EC meter. Solutions were filtered using 0.45 μm
C 3.31 79.74 Na2O 1.00 aero disk filters, acidified with concentrated hy-
Si 2.04 SiO2 70.44 drochloric acid to pH<2 and stored at 4 oC until
Mn 0.63 Al2O3 13.11 analysis. Manganese concentration was meas-
Al 0.16 CaO 4.43 ured using a Perkin Elmer Analyst 100 flame
S 0.09 0.36 MgO 0.93 atomic absorption spectrophotometer.
Ni 0.06 TiO2 0.25
Cr 0.05 K2O 1.87
P 0.04 H2O 6.78 3. RESULTS AND DISCUSSION
H2O 0.4 5.45
3.1 Batch leaching tests
Paste pH 5.1-5.3 10.23 7.87
Apparent The evolution of pH vs. time for each reactive
0.85-
density 2.7-2.9 0.45 media used is as follows:
1.1
(g/cm3) Activated Carbon: Depending on the dosage
Grain size
0.2-1.0 1.5-4.0 0.2-1.0
used pH increased rapidly the first 6 hours from
(mm) the initial value of 5.5 to values ranging be-
Specific tween 5.8 and 7.7. Then pH values were stabi-
surface area 0.0482 900.67 15.58 lized and varied between 6.5 and 7.9. Dosages
(m2/g) of 10 and 20 g/L AC maintained solution pH to
3rd AMIREG International Conference (2009): Assessing the Footprint of 26
Resource Utilization and Hazardous Waste Management, Athens, Greece

8.5
340 μS/cm.
Figures 3-5 show the evolution of Mn con-
8
centration in solution vs. time for each reactive
7.5
media used.
7 Mn is effectively removed from solution
pH

6.5 when the dosage of AC is higher than 10 g/L.

6 After 7 days Mn removal is 82 % and 99 % for
5.5
Activated Carbon AC dosages 10 and 20 g/L, respectively. Lower
removal rates not exceeding 40 % are seen
5
0 50 100 150
when AC dosage is ≤5 g/L.
Time (h)
0.5 1 5 10 20
100

Figure 2: pH vs time (initial Mn concentration 100 mg/L, 80

activated carbon dosage 0.5-20 g/L).

Mn (mg/L)
60
values close to or higher than 7.5 almost from Activated Carbon
the start of the test (Fig. 2); such values favor 40

Mn adsorption. 20
Zeolite: pH increased gradually and at the
end of the test (after 7 days) values varied be- 0
0 50 100 150 200
tween 6.4 and 7.4 for various zeolite dosages Time (h)
used. 0,5 1 5 10 20
Fe0: When zero valent iron was used as reac-
Figure 3: Manganese concentration vs time (initial Mn
tive medium iron corrosion took place and
concentration 100 mg/L, activated carbon dosage 0.5-20
therefore ferrous ions were transferred into solu- g/L).
tion (reactions 3 and 4); these ions may partici-
pate in several reactions that result in the forma- 100
tion of precipitates (Komnitsas et al., 2007). pH
in the system, apart from an initial increase did 80
not follow a certain trend and fluctuated be-
Mn (mg/L)

tween 5.7 and 6.7. 60

Fe0 + 2H2O → Fe2+ + H2 + 2OH- (3) 40

Fe0 + 2H+ → Fe2+ + H2

Zeolite
(4) 20
0 50 100 150 200
Eh values (data not shown) are in accordance
Time (h)
with pH values in all batch systems. Eh of the
0.5 1 5 10 20
solution varies between -75 and 35 mV when
0.5 and 20 g/L AC dosage is used respectively. Figure 4: Manganese concentration vs time (initial Mn
Regarding zeolite, Eh values decreased gradu- concentration 100 mg/L, zeolite dosage 0.5-20 g/L).
ally and at the end of the run varied between -50 100
and 15 mV, slightly lower than in the case of ZVI
AC. In the zero valent iron system Eh values 80

vary between -10 and 56 mV making thus the

Mn (mg/L)

60
progress of the following reaction 5, which ac-
celerates iron corrosion, extremely slow. 40

2Fe3+ + Fe0 → 3Fe2+ (5) 20

0
Conductivity values (data not shown) are in 0 50 100 150 200
line with pH and Eh measurements. It is men- Time (h)
tioned that conductivity in the AC and zeolite 0.5 1 5 10 20
solutions varies between 330 and 430 μS/cm, Figure 5: Manganese concentration vs time (initial Mn
while in the ZVI solution is just above concentration 100 mg/L, ZVI dosage 0.5-20 g/L).
3rd AMIREG International Conference (2009): Assessing the Footprint of 27
Resource Utilization and Hazardous Waste Management, Athens, Greece

At a dosage of 20 mg/L the maximum re- 1

moval rate recorded over the first 24 h was

3.47 mg/g, while for the next 4 days it dropped 1
1
to 1.42 mg/g. The main removal mechanism in 2 2 3 3
1
3
1

this case, due to favorable solution pH, is ad-

sorption on active sites of activated carbon.
Zeolite is less efficient in removing manga-
5 10 20 30 40 50 60 70

nese due to its lower surface area compared to
AC and the lower solution pH. Removal per-
centages at the end of the test do not exceed
60 % and 40 % when dosages of 20 and 10 g/L
are used respectively. When lower dosages are
used manganese removal does not exceed 22 %
after 7 days.
The main mechanism for manganese removal
in this case is ion exchange. This is confirmed
by the presence of K, Ca and Mg ions in the so-
lution, up to 10 mg/L.
When a dosage of 20 g/L is used, ZVI re-
moves almost 70 % of Mn after 7 days; at dos-
ages ≤5 g/L removal percentage does not exceed
15 %. It is underlined that limited Mn removal
is anticipated in case solution pH values do not
exceed 6.5-6.7 over the entire leaching period.
The concentration of total dissolved iron
(data not shown) increased at the beginning of
the tests and reached 135 mg/L after 6 hours
when a 20 g/L dosage was used. After 24 hours
it dropped rapidly and varied until the end of the
tests between 15 and 40 mg/L. ZVI removes
2? scale
Figure 6: XRD analysis of reactive iron particles (1:
maghemite, 2: lepidocrocite, 3: Fe-hydroxides).
probable under the specific solution conditions:
4Fe0 + 3O2 +2H2O → 4δ-FeOOH (9)
Fe2+ + CO 32− /OH- → Ferrous precipitates (10)
4Fe3+ + 3O2+12e− → 2Fe2O3 (11)
Fe3+ + 3H2O → Fe(OH)3 + 3H+ (12)
It is believed that part of Mn removed from
solution is co-precipitated with and/or adsorbed
on these iron oxides and hydroxides.
Figures 7 and 8 show the Langmuir iso-
therms in cases AC and zeolite are used as reac-
tive materials. Based on the R2 values it is seen
that adsorption can be best described by the
0.25 y = 0.4599x + 0.0583
0.20
R2 = 0.9039
0.15
M/Y

also 67 % of sulfate ions (data not shown) pre- 0.10

sent in solution (initial SO4 concentration
180 mg/L). The reduction of sulfates by ZVI 0.05

can be described by the following reactions; it is 0.00

known that the presence of sulfates enhances 0 0.1 0.2 0.3 0.4
ZVI corrosion (Bartzas et al., 2006b). 1/Ce
Activated carbon Linear (Activated carbon)
4Fe0 + SO42- + 9H+ → 4Fe2+ + HS- + 4H2O (6)
Figure 7: Langmuir isotherm (initial Mn concentration
SO42- + 4H2 → HS- + 3H2O + OH- (7) 100 mg/L, AC dosage 0.5-20 g/L).

4Fe2+ + HS- + 7OH- → FeS(am) + 0.40

0.35
y = 21.558x - 0.1843
R2 = 0.9434
3Fe(OH)2(am) + H2O (8) 0.30
0.25
XRD analysis (Siemens D500 diffractometer
M/Y

0.20
using a Cu tube and a scanning range from 3° to 0.15
70° 2-theta, with a step 0.03° and 4 sec/step 0.10

measuring time) of the iron particles at the end 0.05

0.00
of the tests revealed the presence of maghemite 0.01 0.01 0.02 0.02 0.03 0.03
(γ-Fe2O3), lepidocrocite (γ-FeOOH) and Fe- 1/Ce
hydroxides (δ-FeOOH) (Fig. 6).
ZL Linear (ZL)
These phases may form through the follow-
ing reactions; reactions (9) and (10) are more Figure 8: Langmuir isotherm (initial Mn concentration
100 mg/L, zeolite dosage 0.5-20 g/L).
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
Langmuir model.
3.2 Column tests
Figure 9 presents the evolution of manganese
concentration in solution vs. time for each reac-
tive medium used, namely coarse/fine limestone
and goat manure.
It is seen from this figure that the efficiency
of coarse and fine limestone increases slowly
with time; after 30 days fine limestone removes
70 % of manganese while when coarse lime-
stone is used the removal percentage exceeds
40 % after 47 days. This is due to the slow pro-
vision of alkalinity in the system and the respec-
tive slow increase of pH from 5.5 to 7.2 after 46
days.
On the other hand when goat manure is used,
Mn removal is complete the first 10 days,
whereas the efficiency of the system drops
gradually and after 47 days reaches 45 %. Goat
manure acts as electron donor in the dissimila-
tory reduction of sulphate to sulphide, generat-
ing thus alkalinity (reaction 13) and promoting
metal precipitation as sulphide (reaction 14)
(Pagnanelli et al., 2009):
SO 2-4 + 2CH2O + 2H+ → H2S + 2H2CO3
Me2+ + H2S → MeS↓ + 2H+
It is believed that the efficiency of goat ma-
nure would have been much better over a longer
period if a bigger quantity was used in the col-
umn or two columns were used in series to in-
crease retention time.
As mentioned earlier the initial pH of the
feed solution in column tests was 5.5. When the
pH of the feed solution was decreased to 3 by
the addition of sulfuric acid, manganese re-
100
90
80
70
Mn (mg/L)
60
50
40
30
20
10
0 Argun, M.E., 2008. Use of clinoptilolite for the removal
0 10 20 30
Time (days)
Coarce limestone Fine limestone
Figure 9: Manganese concentration vs time (initial Mn
concentration 100 mg/L, flow rate 80 mL/h).
28
moval dropped dramatically in all systems over
a period of 45 days. No system managed to raise
pH to values higher than 7; it is mentioned that
the behavior of goat manure which as organic
material is not effective in low pHs was antici-
pated.
4. CONCLUSIONS
Manganese removal from leachates was studied
in batch and column tests. Among the three re-
active media tested in batch tests (activated car-
bon, zeolite and zero valent iron), activated car-
bon was the most efficient; manganese removal
reached almost 99 % after 5 days, when the ini-
tial Mn concentration was 100 mg/L. At a dos-
age of 20 g/L the maximum removal rate re-
corded over the first 24 h was 3.47 mg/g, while
for the next 4 days it dropped to 1.42 mg/g.
Main removal mechanisms are adsorption for
activated carbon, ion exchange for zeolite and
co-precipitation and/or adsorption on Fe oxy-
hydroxides formed in the system containing
zero valent iron.
Column tests showed that goat manure ex-
hibits for a short period (10 days) remarkable
(13) manganese removal efficiency due to adsorption
(14) of manganese on organic material/precipitation
as sulphide; longer retention time would have
led to a better efficiency of this system. On the
other hand limestone (either coarse or fine) ex-
hibited due to slow solubilisation and therefore
limited pH buffering effect, low removal rates
over the period tested. When the pH of the feed
solution was decreased to 3, manganese removal
dropped dramatically in all systems.
ACKNOWLEDGEMENTS
The financial support of the Research Commit-
tee of the Technical University of Crete (TUC)
in the frame of the basic research programme
2007-2008 is greatly acknowledged.
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