International Journal of

Environmental Research
and Public Health

Article
Study on the Factors Affecting the Start-Up of
Iron-Manganese Co-Oxide Filters for Ammonium
and Manganese Removal from Groundwater
Ya Cheng 1,2 ID
, Tinglin Huang 1,2, *, Lijie Cheng 1,2 and Junbin Wu 1,2
1 Key Laboratory of Northwest Resource, Environment and Ecology, Ministry of Education (MOE),
Xi’an University of Architecture and Technology, Xi’an 710055, China; [email protected] (Y.C.);
[email protected] (L.C.); [email protected] (J.W.)
2 Shaanxi Key Laboratory of Environmental Engineering, Xi’an University of Architecture and Technology,
Xi’an 710055, China
* Correspondence: [email protected]; Tel.: +86-029-822-01038; Fax: +86-029-822-02729




Received: 27 July 2018; Accepted: 21 August 2018; Published: 23 August 2018


Abstract: The high concentration of ammonium (NH4 + -N) and manganese (Mn2+ ) in underground
water poses a major problem for drinking water treatment plants. Effective catalytic oxidative removal
of NH4 + -N and Mn2+ by iron-manganese co-oxide film (MeOx ) filters was first developed by our
group in a previous study. In this study, several identical pilot-scale filters were employed to optimize
the start-up process for simultaneous removal of NH4 + -N and Mn2+ from potable water supplies.
Experiments were conducted to assess the influence of Mn2+ concentration, Fe2+ concentration,
filtration rate and dosing time on the start-up period of the filter. Results demonstrated that the
ability of the filter to remove completely 1.5 mg/L NH4 + -N could be achieved on the sixth day at
the soonest and the removal of Mn2+ could reach 1 mg/L by the 18th day. Filter R3 feeding with
1 mg/L Fe2+ , 2 mg/L Mn2+ and 3.5 mg/L MnO4 − during the start-up period exhibited the optimum
NH4 + -N and Mn2+ removal effect. Short dosing time was not conducive to attaining full NH4 + -N
removal in filters, especially the activity of NO2 − -N conversion to NO3 − -N. The compositional
analysis and element distribution analysis results demonstrated that there was an abundance of C,
O, Mn, Mg, Fe, Ca and Si across the entire area of the surface of the filter media and the elemental
distribution was homogeneous, which was different from the biofilter media. Knowledge-guided
performance optimization of the active iron-manganese co-oxide could pave the way for its future
technological use.

Keywords: iron-manganese co-oxide; filter; start-up; ammonium removal; manganese

1. Introduction
Ammonium (NH4 + -N) and manganese (Mn) contamination of groundwater is one of the problems
faced in water treatment [1]. The presence of Mn in drinking water causes pipes to clog from the
oxidation of Mn2+ , which is precipitated as Mn4+ in the form of manganese oxide (MnO2 ), resulting in
black colored water [2,3]. Importantly, Mn can cause neurotoxicity in humans. Additionally, in water
supply plants, NH4 + -N in raw water needs to be removed before the water is disinfected with chlorine,
as it consumes significant amounts of chlorine and produces chloramines during the disinfection
process [4]. The presence of NH4 + -N in water systems also leads to oxygen depletion, toxicity to fish,
eutrophication of surface waters, human nervous system damage and deterioration in the taste and
odor of water [5]. The treatment of NH4 + -N and Mn2+ to reduce the amount to below maximum
concentration limits is a priority in drinking water treatment plants. Therefore, for some water supply
plants, removal of NH4 + -N and Mn2+ from groundwater is a daily requirement.

Int. J. Environ. Res. Public Health 2018, 15, 1822; doi:10.3390/ijerph15091822 www.mdpi.com/journal/ijerph
Int. J. Environ. Res. Public Health 2018, 15, 1822 2 of 14

In order to solve this problem, various treatment technologies have been used to remove NH4 + -N
and Mn2+ from potable water, including biological and physicochemical methods [6–10]. Biofilters, as
a biological treatment method, have been widely applied, with the advantages of simple processing
technology, strong processing capacity and low investment cost [4,11,12]. However, the start-up
period of the biological filter column usually takes months [13–16]. Hence, considerable effort has
been made to improve designs for the efficient and economic biological removal of NH4 + -N and
Mn2+ [17]. Han et al. systematically investigated the effect of operation factors, such as hydraulic
loading, air-to-water ratio and feed ammonium concentration, on simultaneous removal of NH4 + -N
and Mn2+ using a pilot-scale biological aerated filter. They demonstrated that distribution of ammonia
oxidizing bacteria and manganese oxidizing bacteria could be a main factor affecting the system
performance for simultaneous removal of NH4 + -N and Mn2+ [18]. In order to shorten the start-up
period of the biofilter for the removal of Fe2+ , Mn2+ and NH4 + -N simultaneously, Cai et al. introduced
lab-scale biofilters with three different methods of inoculation. The start-up method that was most
effective involved inoculation with nitrifying sludge first, followed by backwashing sludge obtained
by backwashing the other matured Fe and Mn removal biofilters in the laboratory after complete
NH4 + -N removal. This method required 30 days to achieve complete removal of Mn2+ [19]. In addition,
the sludge used in inoculation is a threat to the safety of drinking water treatment, because the sludge
may contain metals or other potential pollutants [20].
Unlike biofilters, our group has employed physicochemical technology to start up filters which
are used to enhance potable water quality by removing NH4 + -N and Mn2+ [21,22]. Different from the
above traditional biological NH4 + -N and Mn2+ removal filter columns, the removal of NH4 + -N was
achieved by the chemical catalytic oxidation of iron-manganese co-oxide film coated on the filter media
and not by biological degradation. The effective catalytic oxidation of NH4 + -N by iron-manganese
co-oxide film was already verified in our previous study [22]. The mineral structure of oxide film
toward NH4 + -N oxidation was studied systematically and the NH4 + -N removal mechanisms by oxide
film catalytic oxidation have been proposed [23].
The method used to shorten the start-up period is of considerable importance for the further
application of this technology. In order to efficiently and economically remove NH4 + -N and Mn2+ ,
this study attempted to optimize the ripening periods of the removal filters to possibly help reduce the
typically long ripening periods. This paper focuses on how to shorten the start-up period of the filter
for the removal of NH4 + -N and Mn2+ , by starting up the pilot-scale filters with different feedwater.
Pilot experiments were carried out to evaluate the influence of Mn2+ concentration, Fe2+ concentration,
filtration rate and dosing time on the start-up of the filter.

2. Methods

2.1. Experimental Set-Up and Feed Water

A gravity filter made of Plexiglass was adopted for the simultaneous NH4 + -N and Mn2+ removal
process. Each filter had an inner diameter of 100 mm and was filled with quartz sand of size fraction
0.75–1.2 mm, with a height of 1.10 m. Quartz sand was purchased from a local waterworks. Before the
experiment, 1 mol/L HCl was used to soak the quartz sand for 1 day, then was rinsed off. In order
to prevent the leakage of quartz sand, a layer of cobblestone was set below the sand as a supporting
material with a height of 20 cm and a particle size of 8–15mm. The filter column was operated in
down flow mode at a filtration efficiency of 4 m/h and backwashing process consisted of air backwash,
air-water backwash and water backwash. In each step, the intensity of air and water backwash was
13–17 and 3–4 L/(s·m2 ), respectively. Eight sampling points (located at 0, 10, 22, 35, 55, 75, 95 and
115 cm from bottom to top) were attached along the height of the column to allow the sampling of
water. A schematic diagram of the pilot scaled filter system is shown in Figure 1. The feed water of the
filters used in the present study was groundwater obtained from a water source well in Xi’an, China.
Int. J. Environ. Res. Public Health 2018, 15, 1822 3 of 14
Int. J. Environ. Res. Public Health 2018, 15, x 3 of 14

The
wellcompositions of the
in Xi’an, China. Thegroundwater
compositions used in this
of the study are provided
groundwater in Table
used in this study1.are
Iron and manganese
provided in Table
were nearly removed before using the groundwater for the experiment.
1. Iron and manganese were nearly removed before using the groundwater for the experiment.

Figure 1. Schematic
Figure 1. Schematic illustration
illustration of
of the
the pilot-scale
pilot-scale filter
filter system.
system.

Table 1. Chemical
Table 1. Chemical composition
composition of
of the
the feed
feed water.
water.

Parameters
Parameters UnitUnit Value
Value
Cl− mg/L 60–65
Cl− SO42− mg/Lmg/L 60–65
95–110
− 2+
SO4 2Ca mg/L 95–110
mg/L 35–40
2+
Ca Mg2+ mg/L 35–40
mg/L 23–25
Mg2+Temperature mg/L°C 23–25
15–18
Temperature
pH ◦C - 15–18
7.5–7.8
pH Alkalinity (CaCO3) - mg/L 7.5–7.8
200–250
Alkalinity
Fe (CaCO3 ) mg/Lmg/L 200–250
0–0.13
Fe Mn mg/Lmg/L 0–0.08
0–0.13
Mn NH4+-N mg/Lmg/L 0–0.2
0–0.08
NH4 +NO
-N3−-N mg/Lmg/L 0–0.40
0–0.2
−
NO3 NO -N2−-N mg/Lmg/L 0–0.003
0–0.40
−
TOC
NO2 -N mg/Lmg/L 1–3.5
0–0.003
TOC Na+ mg/Lmg/L 80–90
1–3.5
Na+ DO mg/Lmg/L 2.0–4.0
80–90
DO mg/L
TOC: Total organic content; 2.0–4.0
DO: Dissolved oxygen.
TOC: Total organic content; DO: Dissolved oxygen.
2.2. Start-Up Method for Filters
2.2. Start-Up Method for Filters
For starting up the filters, different start-up methods were applied to optimize the start-up
For
procedure. starting
Boosterup pumps
the filters,
and different
tubing werestart-up
usedmethods
to pumpwere feedapplied to optimize
water through the start-up
the system. The
procedure. Booster pumps and tubing were used to pump feed water through
starting principle of the filters was as follows: mixing and dosing potassium permanganate the system. The(MnO
starting
4−),
principle ofchloride
the filters −
manganese (Mnwas as ferric
2+) and follows: mixing
chloride (Fe2+and dosing
) with potassium
peristaltic pump;permanganate
the formed oxides (MnO 4 ),
along
manganese chloride (Mn 2+ ) and ferric chloride (Fe2+ ) with peristaltic pump; the formed oxides along
with the raw water enter into the filter system; the oxides can be retained by the processes of filtration
with
then the raw water
forming a filmenter into the filter
of catalytically system;
active metalthe oxides
oxide can on
coated be the
retained by the processes
filter media, of filtration
after prolonged filter
then forming a film of catalytically active metal oxide coated on the filter
runs. During the start-up period, MnO4 , Mn and Fe were mixed with a mole ratio of complete
− 2+ 2+ media, after prolonged
filter runs. During the start-up − 2+ and Fe2+ were mixed
reaction, shown in Equations (1) period,
and (2), MnO 4 , Mn
to avoid excessive dosage of MnO4−, which with awould
mole damage
ratio of
complete reaction,ofshown in Equations (1) and (2), to avoid period,
excessive −
the development the oxides film. During the operation in dosage
order toofdetect
MnO4NH , which would
4+-N removal

efficiency of the filter in time, NH4Cl was also dosed into the influent and the influent NH4+-N
concentration was kept at 1.5 mg/L:
Int. J. Environ. Res. Public Health 2018, 15, 1822 4 of 14

damage the development of the oxides film. During the operation period, in order to detect NH4 + -N
removal efficiency of the filter in time, NH4 Cl was also dosed into the influent and the influent NH4 + -N
concentration was kept at 1.5 mg/L:

2MnO4 − + 3Mn2+ + 2H2 O → 5MnO2 + 4H+ (1)

MnO4 − + 3Fe2+ + 4H+ → MnO2 + 3Fe3+ + 2H2 O (2)

Several identical pilot-scale gravity filters were adopted in this study. Each filter system was
operated continuously for four weeks. To investigate the effect of Mn2+ and Fe2+ concentration on the
start-up of filter, Mn2+ and Fe2+ were manually dosed into the influent at a certain concentration and
the filtration rate was maintained at 4 m/h. After 14 days’ operation, dosing MnO4 − , Mn2+ and Fe2+
ceased. The ability to remove manganese was evaluated by varying the influent Mn2+ concentration of
the filters on the 8th, 18th and 28th day. In order to study the effect of filtration rate on the start-up of
the filters, the filtration rate increased from 4 to 6 m/h with other parameters kept constant. In addition,
the effect of the dosing time (MnO4 − , Mn2+ and Fe2+ ) on the start-up of the filters was also studied.
Too high a Mn2+ and Fe2+ concentration could lead to too frequent backwashing. Therefore, in this
study, the Fe2+ concentration was 0–2 mg/L, whereas the maximum Mn2+ concentration was set to
4 mg/L. The operating parameters of the filters (named R1, R2, R3, R4, R5, R6 and R7) in this study are
presented in Table 2.

Table 2. The operating parameters of all the filters during operation period (start-up period and normal
operation period).

Start-Up Period Normal Operation Period

Name c(Mn2+ ) c(Fe2+ ) c(MnO4 − ) c(NH4 + -N) v Backwashing T* c(NH4 + -N) v Backwashing
(mg/L) (mg/L) (mg/L) (mg/L) (m/h) Frequency (day) (mg/L) (m/h) Frequency
R1 2 0 2.8 1.5 4 2 days 14 1.5 6 2 days
R2 2 0.5 3.2 1.5 4 2 days 14 1.5 6 2 days
R3 2 1.0 3.5 1.5 4 2 days 14 1.5 6 2 days
R4 2 2.0 4.2 1.5 4 2 days 14 1.5 6 2 days
R5 4 1.0 6.4 1.5 4 1 days 14 1.5 6 2 days
R6 4 1.0 6.4 1.5 6 12 hours 14 1.5 6 2 days
R7 2 1.0 3.5 1.5 4 2 days 4 1.5 6 2 days

T *: The time of dosing MnO4 − , Mn2+ and Fe2+ (Start-up period).

2.3. Analytical Methods

During the experimental runs, effluent samples were collected in polypropylene bottles.
Manganese presented as Mn2+ was analyzed with the 1-(2-pyridylazo)-2-naphthol (PAN) method
at an absorbance of 560 nm using a HACH DR 5000 instrument (Hach Company, Loveland, CO,
USA). The levels of NH4 + -N were determined spectrophotometrically with the Nesslerization method
at an absorbance of 425 nm using the same HACH DR 5000 unit. Nitrate (NO3 − -N) was analyzed
by diazotization method also using the HACH DR 5000 and nitrite (NO2 − -N) was also detected by
spectrophotometry in accordance with standard methods. The dissolved oxygen (DO) and pH were
determined by a portable instrument (HQ30d, Hach Company, Loveland, CO, USA).
A sample of 1.5 g of sand was taken from the top of each filtration column to carry out scanning
electron microscope (SEM), Brunauer-Emmett-Teller (BET) and energy dispersive spectrometer (EDS)
mapping testing. The morphology of the samples was observed using a field emission SEM (FEI
Quanta 600F, Hillsboro, OR, USA). The surface and porous properties of the adsorbent were studied
using nitrogen adsorption experiments realized with autosorb-1 (Quantachrome Instruments, Boynton
Beach, FL, USA) at −196 ◦ C with a heating rate of 10 K/min. The specific BET surface area and pore
size of the adsorbent were evaluated according to the BET method. Multi-elemental EDS mapping
was collected by an INCA IE350 x-ray spectrometer (Oxford Instruments, Abingdon, UK).
Int. J. Environ. Res. Public Health 2018, 15, x 5 of 14

concentrations on the start-up of filter. The influent Fe2+ concentrations were 0 (filter R1), 0.5 (filter
Int. J. Environ. Res. Public Health 2018, 15, 1822 5 of 14
R2), 1 (filter R3) and 2.0 mg/L (filter R4). The experimental results are shown in Figure 2. During the
first two days, the influent and effluent NH4+-N concentration of these four filters remained basically
theResults
3. same, which indicated that the adsorption capacity of virgin sand to NH4+-N could be ignored.
and Discussion
From the third day, NH4+-N removal capacity of the filters increased gradually. At a nearly constant
influent
3.1. EffectNH of Fe 2+ concentration of
4+-N Concentrations on1.5
themg/L,
Start-Up theofeffluent
the FiltersNH4+-N concentration of filters R1, R2, R3 and
R4 could meet the drinking water quality standard in China (<0.5 mg/L) by the eighth, seventh, fourth
3.1.1. The NH +
and fifth day,4 -N Removal Performance
respectively. With prolongingduringthe the Start-Up
running Period
time, the influent NH4+-N could be
eliminated at the 15th,
In this study, 13th, 6thpilot-scale
four identical and 18th day forwere
filters filters
used R1,toR2, R3 and
explore R4,
the respectively.
effect The start-up
of Fe2+ concentrations
period
on for the filters
the start-up was
of filter. much
The faster
influent Fethan
2+ that of the biofilters
concentrations [15]. ItR1),
were 0 (filter should be noted
0.5 (filter R2), that the R3)
1 (filter big
difference among the four filters was that the NH +-N removal efficiency of filters R1, R2 and R4 from
and 2.0 mg/L (filter R4). The experimental results are shown in Figure 2. During the first two days, the
4

day 4 to and
influent 12 increased
effluent NH slower
+ than that of filter R3.
4 -N concentration of these four filters remained basically the same, which
During
indicated thatthe
thefirst 10 days,capacity
adsorption the accumulation
of virgin sand of NO −-N was
to 2NH + accompanied with rapidly increased
4 -N could be ignored. From the third day,
NH ++-N removal capacity. Over time, NO2−-N was negatively correlated with the accumulation peak
NH4 -N removal capacity of the filters increased gradually. At a nearly constant influent NH4 + -N
4

of NO2−-N. The
concentration of accumulation
1.5 mg/L, the time of NO
effluent NH24−-N:
+ -Nfilter R1 (14 days)
concentration > filter
of filters R1,R2R2,(12
R3days)
and R4> filter
couldR4 (10
meet
days) > filter R3 (8 days). The accumulation peak of NO −-N in filter R3 with the shortest accumulation
the drinking water quality standard in China (<0.5 mg/L) by the eighth, seventh, fourth and fifth day,
2

time was 0.8 With

respectively. mg/L.prolonging
The accumulation peaktime,
the running of NO the2−-N in filter
influent NHR14 +with the longest
-N could accumulation
be eliminated time
at the 15th,
was 0.24
13th, mg/L.
6th and 18thJiang
dayetforal. filters
reportedR1,that
R2, the
R3 andaccumulation of NO2 The
R4, respectively. − -N in biofilters
start-up was for
period related to the
the filters
level of DO condition [24]. However, in this study, the influent DO of
was much faster than that of the biofilters [15]. It should be noted that the big difference among theall the filters was almost the
same, which could meet the + oxygen demand of NH +-N removal. So it could be inferred that the
four filters was that the NH4 -N removal efficiency of filters R1, R2 and R4 from day 4 to 12 increased
4

accumulation
slower than that of of
NO 2−-N R3.
filter was due to the lack of NO2−-N catalytic oxidation activity of the filter media.

2.0
R1
1.5
Influent NH+4-N
1.0 Effluent NH+4-N
8d Effluent NO-2-N
0.5
Effluent NO-3-N
2.0
0.0
R2
1.5
N concentration (mg/L)

1.0
7d
0.5

0.0
2.0
R3
1.5

1.0
4d
0.5

0.0
2.0
R4
1.5

1.0
5d
0.5

0.0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Time (days)

Figure 2. The effect of influent Fe2+ concentration on the variation of N (NH4+-N, NO3−-N and NO2−-
Figure 2. The effect of influent Fe2+ concentration on the variation of N (NH4 + -N, NO3 − -N and
N) concentration during the start-up period.
NO2 − -N) concentration during the start-up period.

3.1.2. Mn2+ Removal Performance during the Start-Up Period

During the first 10 days, the accumulation of NO2 − -N was accompanied with rapidly increased
During the start-up period, MnO4−, Mn2+ and Fe2+ reacted completely and Mn2+ and Fe2+ were
NH4 + -N removal capacity. Over time, NO2 − -N was negatively correlated with the accumulation
hardly detectable in the influent water. In order to investigate the variation in manganese removal
peak of NO2 − -N. The accumulation time of NO2 − -N: filter R1 (14 days) > filter R2 (12 days) > filter
capacity of the filters with running time, the experiments were conducted on the 8th, 18th and 28th
R4 (10 days) > filter R3 (8 days). The accumulation peak of NO2 − -N in filter R3 with the shortest
day. The concentration of Mn2+ in the influent was kept at 2 mg/L. The variation of Mn2+ concentration
accumulation time was 0.8 mg/L. The accumulation peak of NO2 − -N in filter R1 with the longest
along the depth of the filters is shown in Figure 3. The removal capacity of the filter column along
accumulation time was 0.24 mg/L. Jiang et al. reported that the accumulation of NO2 − -N in biofilters
the depth of the filter gradually increased.
was related to the level of DO condition [24]. However, in this study, the influent DO of all the filters
was almost the same, which could meet the oxygen demand of NH4 + -N removal. So it could be
Int. J. Environ. Res. Public Health 2018, 15, 1822 6 of 14

inferred that the accumulation of NO2 − -N was due to the lack of NO2 − -N catalytic oxidation activity
of the filter media.

3.1.2. Mn2+ Removal Performance during the Start-Up Period

During the start-up period, MnO4 − , Mn2+ and Fe2+ reacted completely and Mn2+ and Fe2+ were
hardly detectable in the influent water. In order to investigate the variation in manganese removal
capacity of the filters with running time, the experiments were conducted on the 8th, 18th and 28th day.
The concentration of Mn2+ in the influent was kept at 2 mg/L. The variation of Mn2+ concentration
along the depth of the filters is shown in Figure 3. The removal capacity of the filter column along the
depth
Int. of theRes.
J. Environ. filter gradually
Public increased.
Health 2018, 15, x 6 of 14

2.5
2.0
1.5
8d
1.0 R1
18 d
0.5 28 d
2.5
0.0
Mn2+ concentration (mg/L)

2.0
1.5
1.0
R2
0.5
0.0
2.5
2.0
1.5
1.0
R3
0.5
0.0
2.5
2.0
1.5
1.0
R4
0.5
0.0
0 20 40 60 80 100
Depth (cm)

Figure 3. The
Figure 3. effect of
The effect of influent
influent Fe
Fe2+
2+ concentration on the variation of Mn2+
concentration on the variation of Mn concentration
2+
concentration along
along the
the
depth
depth of
of the
the filters
filters at
at different running time.
different running time.

The Mn2+ removal of these four filters is presented in Figure 4. The Mn2+ 2+ removal amount also
The Mn2+ removal of these four filters is presented 2+ in Figure 4. The Mn removal amount also
increased with running time. At the eighth day, the Mn removal amount was nearly the same for
increased with running time. 2+At the eighth day, the Mn2+ removal amount was nearly the same for all
all filters. However, the2+Mn removal capability of the filters became different afterward, which
filters. However, the Mn removal capability of the filters became different afterward, which could be
could be attributed to the different catalytic activities of the filter media.2+The Mn2+ removal capacity
attributed to the different catalytic activities of the filter media. The Mn removal capacity of filters
of filters R3 and R4 was higher than that of the other two filters. Considering the dosing concentration
R3 and R4 was higher than that of the other two filters. Considering the dosing concentration of filter
of filter R3 was lower than that of filter R4, we concluded that a 2+ higher Fe2+ concentration of 1 mg/L
R3 was lower than that of filter R4, we concluded that a higher Fe concentration of 1 mg/L produces
produces better results during the start-up period.
better results during the start-up period.
2.0

R1
Mn2+ removal amount (mg/L)

R2
1.5
R3
R4

1.0

0.5
increased with running time. At the eighth day, the Mn2+ removal amount was nearly the same for
all filters. However, the Mn2+ removal capability of the filters became different afterward, which
could be attributed to the different catalytic activities of the filter media. The Mn2+ removal capacity
of filters R3 and R4 was higher than that of the other two filters. Considering the dosing concentration
of filter R3 was lower than that of filter R4, we concluded that a higher Fe2+ concentration of 1 mg/L
Int. J. Environ. Res. Public Health 2018, 15, 1822 7 of 14
produces better results during the start-up period.

2.0

R1

Mn2+ removal amount (mg/L)

R2
1.5
R3
R4

1.0

0.5

0.0
8d 18 d 28 d
Time

Figure 4.
Figure 4. The
The comparison
comparisonofofthe
theMn
Mn 2+ removal of the filters (R1, R2, R3 and R4) at different running
2+ removal of the filters (R1, R2, R3 and R4) at different running time.
time.

3.1.3. Variation in pH and DO during the Start-up Period

Int. J. Environ. Res. Public Health
3.1.3. Variation in pH and2018,
DO15, x
during
the Start-up Period 7 of 14
Filter R1 was selected to study the variation in pH and DO with the running time during the
Filter R1 wasasselected
operation to study the Theoretically,
variation in pH and DOions
with(H
the running time during the
operation period,
period, as shown
shown in in Figure
Figure 5. hydrogen +) would
5. Theoretically, hydrogen ions (H+ ) would be
be released
released when
when
NH
NH44 +-N
+
-Noxidizes
oxidizestotoNO
NO2 2-N
− oror
− -N NONO3 -N:
− −
3 -N:

NH4++ + 1.5O2 → NO2−− + H2O + 2H++ (3)

NH4 + 1.5O2 → NO2 + H2 O + 2H (3)
NH4 + 2O2 → NO3 + H2O + 2H
+ − + (4)
NH4 + + 2O2 → NO3 − + H2 O + 2H+ (4)
However, compared with the influent pH, the effluent pH did not change much. This was
mainly However, compared
attributed to the with the influent
buffering effect pH, thegroundwater
of the effluent pH did not high
with change much. This
alkalinity was1).
(Table mainly
The
attributed to the buffering effect of the groundwater with high alkalinity (Table
influent DO remained at 5–7 mg/L. The effluent DO decreased gradually along with the running time, 1). The influent DO
remained at 5–7 mg/L. The effluent DO decreased gradually along with the running
which was in accordance with the NH4 -N removal performance (Figure 2). Especially in the first 15
+ time, which
was inthe
days, accordance
effluent NH with the NH4 + -N
4+-N and DO
removal performance
concentration (Figure 2). Especially
decreased synchronously, but it’sinworth
the first 15 days,
noting that
the effluent NH + -N and DO concentration decreased synchronously, but it’s worth noting that the DO
4
the DO consumption (5 mg/L) for NH4 -N (1.5 mg/L) removal was less than the theoretical DO
+

consumption (5 mg/L) for NH + -N (1.5 mg/L) removal was less than the theoretical DO consumption
consumption (6.8 mg/L) according 4 to Equation (4), which should be caused by the atmospheric
(6.8 mg/L) according to Equation
reoxygenation during sampling and testing (4), whichprocess.
should Nonetheless,
be caused bythe theNHatmospheric reoxygenation
4+-N removal capacity of
during sampling and testing process. Nonetheless, the NH + -N removal capacity of the filters during
4
the filters during the start-up period could be evaluated by detecting the change in DO in the influent
the start-up
and effluent.period could be evaluated by detecting the change in DO in the influent and effluent.

8
8
7
7
6
6
5
R1 5

4
DO

4
pH

3
3
Influent DO
2 Effluent DO
2
Influent pH
1 Effluent pH 1

0 0
0 2 4 6 8 10 12 14 16 18
Time (days)

Figure
Figure 5.
5. The
The variation
variation of
of pH
pH and
and dissolved
dissolved oxygen
oxygen (DO)
(DO) in
in filter
filter R1
R1 during
during the
the start-up
start-up period.
period.

3.2. Effect of Mn2+ Concentration on the Start-Up of the Filters

3.2.1. NH4+-N Removal Performance during the Start-Up Period

As known from the above experimental results, the start-up of filter R3 performed the best.
Therefore, in order to further explore the effect of Mn2+ concentration on the start-up of the filters for
NH4+-N and Mn2+ removal, a filter named R5 was initiated. During the start-up period, the influent
2+ +
Int. J. Environ. Res. Public Health 2018, 15, 1822 8 of 14

3.2. Effect of Mn2+ Concentration on the Start-Up of the Filters

3.2.1. NH4 + -N Removal Performance during the Start-Up Period

As known from the above experimental results, the start-up of filter R3 performed the best.
Therefore, in order to further explore the effect of Mn2+ concentration on the start-up of the filters for
NH4 + -N and Mn2+ removal, a filter named R5 was initiated. During the start-up period, the influent
Fe2+ and NH4 + -N concentration of filter R5 was the same as that of R3. The difference was that
the influent Mn2+ concentration increased from 2 to 4 mg/L. The comparison of NH4 + -N removal
performance during the start-up period between filter R3 and R5 is shown in Figure 6. Filter R3 with
low influent Mn concentration (2 mg/L) demonstrated better NH4 + -N removal performance than that
of filter R5 with high influent Mn2+ concentration (4 mg/L). The time at which capacity of NH4 + -N
catalytic oxidation started extended from the first day (filter R3) to the sixth day (filter R5). The effluent
NH4 + -N concentration of filter R3 met the drinking water quality standard in China (<0.5 mg/L) on the
fourth day, but the time for filter R5 to obtain the same level of effluent NH4 + -N concentration required
11 days. Hence, too high a Mn2+ concentration was not beneficial to the formation of NH4 + -N removal
capability of the filters. In addition, we also found that little accumulation of NO2 − -N appeared in
filter R5. This
Int. J. Environ. implied
Res. that2018,
Public Health high15,
Mn x 2+ concentrations were beneficial to the transformation of NO28−of-N.
14

2.0
R3
1.5
Influent NH+4-N
1.0 Effluent NH+4-N
4d Effluent NO-2-N
0.5
Effluent NO-3-N
2.0
0.0
N concentration (mg/L)

R5
1.5

1.0

11 d
0.5

0.0
2.0
R6
1.5

1.0

13 d
0.5

0.0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Time (day)

Figure 6.
Figure 6. The
The effect
effect of
of influent
influent Mn
Mn concentration
concentration and
and filtration
filtration rate
rate on
onthe
thevariation
variationof
ofNN(NH
(NH4++-N,
-N,
4
NO -N
3−− and NO 2−-N)
− concentration during the start-up
NO3 -N and NO2 -N) concentration during the start-up period.period.

3.2.2. Mn
3.2.2. Mn2+
2+ Removal Performance during the Start-Up Period
Removal Performance during the Start-Up Period
The comparison
The comparison of ofthe
theMn
Mn2+2+ removal amount in filters R3 and R5 is shown in Figure 7. The Mn2+
removal amount in filters R3 and R5 is shown in Figure 7. The Mn
2+

removal ability
removal ability of
of filters
filters R3
R3 and
andR5 R5increased
increasedwith withthe
therunning
runningtime.
time.TheTheMnMn2+ removal
2+ removal performance
performance
of filter R3 was much better than that of the filter R5. The Mn
of filter R3 was much better than that of the filter R5. The Mn removal ability of filteron
2+ removal ability of filter R5
2+ R5the
on28th
the
day was even lower than that of filter R3 on the 18th day. During the actual
28th day was even lower than that of filter R3 on the 18th day. During the actual operation of the operation of the filters,
we found
filters, that the
we found frequency
that of backwashing
the frequency may affect
of backwashing may the Mnthe
affect
2+ removal performance
Mn2+ removal of the filters.
performance of the
filters. Backwashing was carried out every day in filter R5, which was more frequent than forR3
Backwashing was carried out every day in filter R5, which was more frequent than for filter (every
filter R3
two days). The higher the Mn 2+ concentration,
2+ the more frequent the
(every two days). The higher the Mn concentration, the more frequent the backwashing. Frequent backwashing. Frequent
backwashing in the filter scoured the oxides coated on the filter media, which resulted in unstable
coating of the oxides. Hence, the ability to remove Mn2+ in filter R5 was weak.

2.0

R3
 The comparison of the Mn removal amount in filters R3 and R5 is shown in Figure 7. The Mn
removal ability of filters R3 and R5 increased with the running time. The Mn2+ removal performance
of filter R3 was much better than that of the filter R5. The Mn2+ removal ability of filter R5 on the 28th
day was even lower than that of filter R3 on the 18th day. During the actual operation of the filters,
we found that the frequency of backwashing may affect the Mn2+ removal performance of the filters.
Int. J. Environ. Res. Public Health 2018, 15, 1822 9 of 14
Backwashing was carried out every day in filter R5, which was more frequent than for filter R3 (every
two days). The higher the Mn2+ concentration, the more frequent the backwashing. Frequent
backwashing
backwashingininthe thefilter
filterscoured
scouredthe theoxides
oxidescoated
coatedon
onthethefilter
filtermedia,
media,which
whichresulted
resultedininunstable
unstable
coating
coatingofofthe theoxides.
oxides.Hence,
Hence,thetheability
abilitytotoremove
removeMnMn inin
2+2+ filter R5R5
filter was weak.
was weak.

2.0

R3
R5

Mn2+ removal amount (mg/L)

1.5 R6

1.0

0.5

0.0
8d 18 d 28 d
Time

Figure
Figure7.7.Comparison
Comparisonof
of the
the Mn
Mn2+ removal
2+ amountof
removal amount ofthe
thefilters
filters (R3,
(R3, R5R5 and
and R6)R6) at different
at different running
running times.
times.
3.3. Effect of Filtration Rate on the Start-Up of the Filters

3.3.1. NH4 + -N Removal Performance during the Start-Up Period

In order to further explore the effect of filtration rate on the start-up of the filters for NH4 + -N
removal, a filter named R6 was adopted. During the start-up period, the influent MnO4 − , Fe2+ , Mn2+
and NH4 + -N concentrations of the R6 filter were the same as that of R3. The only difference was that
filtration rate was changed from 4 m/h to 6 m/h. As shown in Figure 6, the increase of filtration rate
had little effect on the removal capacity of NH4 + -N, but it resulted in the obvious accumulation of
NO2 − -N. The results indicated that the transformation from NO2 − -N to NO3 − -N required longer
reaction time than from NH4 + -N to NO2 − -N.

3.3.2. The Mn2+ Removal Performance during the Start-Up Period

The comparison of Mn2+ removal amount between filter R5 and R6 is shown in Figure 7. The Mn2+
removal ability of filter R5 and R6 gradually increased with the running time and was basically the
same. However, it is worth noting that the Mn2+ removal ability of filters R5 and R6 was significantly
worse than that of filter R3. This phenomenon was closely related to the frequent backwashing as
discussed in Section 3.2.2. During the start-up period, the increase in the filtration rate led to the
increase in the influent loads of the filter, similar to the high influent Mn2+ concentration. Backwashing
was carried out every 12 h in filter R5. Therefore, in this study, the optimal filtration rate was 4 m/h
during the start-up period.

3.4. Effect of Dosing Time on the NH4 + -N Removal Performance

The duration of dosing time determines whether a start-up method is economical. For all filters
dosage of MnO4 − , Fe2+ and Mn2+ was stopped at the 14th day. At this point, the effluent NH4 + -N
concentration of the filters could basically satisfy the limited stated in the drinking water quality
standard in China and the concentration of NO2 − -N was also very low. Therefore, in order to further
shorten the start-up period and reduce the cost, dosing time was optimized.
A filter named R7 was initiated with the same start-up method as filter R3. However, the dosing
time decreased from 14 days to four days. The comparison of NH4 + -N removal performance is shown
in Figure 8.
On the fourth day, the ability of NH4 + -N removal of filter R7 was established. At this time,
dosing MnO4 − , Fe2+ and Mn2+ was stopped. After then, we found that the rate of NH4 + -N removal
 significantly worse than that of filter R3. This phenomenon was closely related to the frequent
backwashing as discussed in Section 3.2.2. During the start-up period, the increase in the filtration
rate led to the increase in the influent loads of the filter, similar to the high influent Mn2+
concentration. Backwashing was carried out every 12 h in filter R5. Therefore, in this study, the
optimal filtration rate was 4 m/h during the start-up period.

Int. J. Environ. Res.

3.4. Public
Effect Health Time
of Dosing 15,the
2018,on 1822
NH4+-N Removal Performance 10 of 14

The duration of dosing time determines whether a start-up method is economical. For all filters
dosage of MnO4−, Fe2+ and Mn2+ was stopped at the 14th day. At this point, the effluent NH4+-N
decreased concentration
in filter R7. The time for NH + -N removal completely extended from day 7 to 11. Meanwhile,
of the filters could 4basically satisfy the limited stated in the drinking water quality
the accumulation − -N became more obvious.
standardof in NO
China2 and the concentration of NO2−-NThe required
was also time
very low. extended
Therefore, fromto8further
in order days to 15 days
shorten the start-up period and reduce the −
cost, dosing time was optimized.
when the effluent was completely free of NO2 -N. Therefore, we concluded that the time when adding
A filter named R7 was initiated with the same start-up method as filter R3. However, the dosing
MnO4 − , Fe2+ and Mn2+ was too short and not conducive to the full formation of the activity of NH4 + -N
time decreased from 14 days to four days. The comparison of NH 4+-N removal performance is shown
removal ininfilters,
Figure 8.
especially the activity of NO2 − -N conversion to NO3 − -N.

1.5

1.0 Effluent NO-2-N

R7 Influent NH+4-N
4 days Effluent NH+4-N
0.5 Effluent NO-3-N
N concentration (mg/L)

0.0

1.5

1.0 R3

14 days
0.5

0.0 x
Int. J. Environ. Res. Public Health 2018, 15, 10 of 14
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Time (day)
On the fourth day, the ability of NH4+-N removal of filter+ R7 was− established. At this time, dosing
Figure 8. The effect of dosing time on the variation of N (NH4 -N, NO3 -N and NO2−-N) concentration
MnO
Figure 8. during
4 The theeffect dosing time on the variation of N (NH4 -N, NO3 − -N and
−, Fe2+ and Mn2+ was stopped. After then, we found that the rate of +
of period.
start-up
NH 4 +-N removal
NO2 − -N)
decreased
in filter R7. The time for NH4+-N removal completely extended from day 7 to 11. Meanwhile, the
concentration during the −start-up period.
accumulation of NO2 -N became more obvious. The required time extended from 8 days to 15 days
when the effluent was completely free of NO2−-N. Therefore, we concluded that the time when adding
3.5. Characterization
MnO4−, Fe2+ and Studies
Mn2+ was too short and not conducive to the full formation of the activity of NH4+-N
removal in filters, especially the activity of NO2−-N conversion to NO3−-N.
3.5.1. Morphological Analysis
3.5. Characterization Studies
The surfaces of the virgin sand and the filter media in filter R3 collected on the 12th day were
3.5.1.by
characterized Morphological
SEM, as shownAnalysis
in Figure 9. From Figure 9a, the surface of the virgin sand was smooth.
After 12 days’ The surfacesthe
running, of the virgin of
surface sand and
the the filter
sand wasmedia
coatedin filter
withR3 collected
many on thewhich
oxides, 12th day wereformed by
were
characterized by SEM, as shown in Figure 9. From Figure 9a, the surface of the virgin sand was
the accumulation of small particles, as shown in Figure 9b. Specific surface areas of these samples were
smooth. After 12 days’ running, the surface of the sand was coated with many oxides, which were
further determined
formed by theusing the BET of
accumulation method. The results
small particles, showed
as shown in Figurethat the specific
9b. Specific surfacesurface
areas of area
these increased
m2 /g were
from 0.106samples (virgin sand) to 3.920 m 2 /g (filter media collected on 12th day). Cao et al. reported
further determined using the BET method. The results showed that the specific surface
area increased
that the increased from 0.106
specific m2/g (virgin
surface sand) to 3.920
area provided m2/g active
more (filter media
sitescollected
for NH on4 +12th
-N day). Cao etoxidation,
catalytic
al. reported that the increased specific surface area provided more active+sites for NH4+-N catalytic
which played a decisive role in the catalytic oxidation process of NH4 -N [25].
oxidation, which played a decisive role in the catalytic oxidation process of NH4 -N [25].
+

(a) (b)

Figure 9. Scanning electronic microscope images of (a) virgin sand and (b) the filter media collected
Figure 9. Scanning electronic
from filter R3 on the 12thmicroscope
day. images of (a) virgin sand and (b) the filter media collected
from filter R3 on the 12th day.
3.5.2. Composition Analysis
The surface element composition of the virgin sand and the filter media collected on the 12th
day was analyzed by EDS. As shown in Table 3, virgin sand mainly contained two elements: silicon
(Si) and oxygen (O). After 12 days’ operation, the oxides formed on the surface of the sand contained
C, Mn, Fe, Mg, Ca, Si and O elements, which was consistent with our previous study [26]. Due to the
minimal change in the total organic content (TOC) along the depth of the filter (data not shown), we
inferred that the C mainly arose from the alkalinity of the water and existed in the form of calcium
Int. J. Environ. Res. Public Health 2018, 15, 1822 11 of 14

3.5.2. Composition Analysis

The surface element composition of the virgin sand and the filter media collected on the 12th
day was analyzed by EDS. As shown in Table 3, virgin sand mainly contained two elements: silicon
(Si) and oxygen (O). After 12 days’ operation, the oxides formed on the surface of the sand contained
C, Mn, Fe, Mg, Ca, Si and O elements, which was consistent with our previous study [26]. Due to
the minimal change in the total organic content (TOC) along the depth of the filter (data not shown),
we inferred that the C mainly arose from the alkalinity of the water and existed in the form of calcium
carbonate and manganese carbonate, which was confirmed in previous studies [27].

Table 3. The elemental composition of the virgin sand and the filter media.

Element. C O Na Mg Si Ca Mn Fe
Virgin sand (%) 65.38 34.62
Filter media (%) 20.74 52.29 0.91 0.70 10.62 1.68 8.46 4.60

3.5.3. Element Distribution Analysis

Int. J. Environ. Res. Public Health 2018, 15, x 11 of 14
Multi-elemental EDS mapping images of the surface of the filter media are shown in Figure 10.
Apparently, 3.5.3.
thereElement
was an abundance
Distribution of O, Mn, Mg, Fe, Ca and Si. And the elemental distribution
Analysis
was homogeneous across theEDS
Multi-elemental entire areaimages
mapping of theofsurface
the surfaceofofthe
the filter media.
filter media According
are shown in Figureto10.the literature,
Apparently,
the characteristic there was
elemental an abundance
distribution onofthe
O, Mn, Mg, Fe,
surface ofCa and media
filter Si. And the elemental
in this studydistribution
was much different
was homogeneous across the entire area of the surface of the filter media. According to the literature,
that of biological filter media. Heterogeneous distribution of Fe, Mn and C was observed on the surface
the characteristic elemental distribution on the surface of filter media in this study was much different
of an “aged”thatbiofilter media
of biological filter[28]. Alain
media. et al. reported
Heterogeneous that
distribution theMn
of Fe, origin
and Cof wasthe coating
observed was a possible
on the
surface of
cause for chemical an “aged” biofilter
heterogeneity in media [28].coatings
surface Alain et al.[29].
reported that the origin of the coating was a
possible cause for chemical heterogeneity in surface coatings [29].

O Mn Mg

Fe Ca Si

Figure 10. Multi-element energy dispersive spectrometry (EDS) mapping images of the filter media
Figure 10. Multi-element energy
collected on the 20th day in dispersive
filter R3. spectrometry (EDS) mapping images of the filter media
collected on the 20th day in filter R3.
3.6. Comparison with Other Studies
Based on our previous research [21], the start-up period of the filter column was further
3.6. Comparison with Other Studies
optimized in this study. The method for oxidation of Mn2+ and Fe2+ by MnO4− during the start-up
Based onperiod
our could guarantee that effluent
[21], NH
+-N would meet the drinking water standard by the fourth
previous research the4 start-up period of the filter column was further optimized
day, when the influent NH4+-N was 1.5 mg/L. On 2+the 18th day,
2+the removal amount of Mn2+ reached
− during
in this study.1 mg/L,
The which
methodwould meet most of the drinking water treatment requirements. A comparison ofstart-up
for oxidation of Mn and Fe by MnO 4 the the period
could guarantee that
start-up effluent
period and theNH + -N
removal would
performance meet
of NH the
+-N drinking
and Mn water
2+ with other standard
studies is by
shown the
in fourth day,
4 4

Table 4. +
Compared with other start-up methods, the method in our study
when the influent NH4 -N was 1.5 mg/L. On the 18th day, the removal amount of Mn reached has obvious advantages. 2+

1 mg/L, which would meet most of the drinking water treatment requirements. A comparison of the
start-up period and the removal performance of NH4 + -N and Mn2+ with other studies is shown in
Table 4. Compared with other start-up methods, the method in our study has obvious advantages.
Int. J. Environ. Res. Public Health 2018, 15, 1822 12 of 14

Table 4. The comparison of the start-up period of NH4 + -N and Mn2+ with other studies.

c(NH4 + -N) (mg/L) c(Mn) (mg/L)

Treatment System Media Types Temperature DO (mg/L) pH Backwashing Period (day) Period (Day) Reference
Influent Effluent Influent Effluent
Pilot-scale filter Quartz sand 15–18 5–7 7.5–7.8 2 day 1.5 <0.1 6 1.0 <0.1 18 This study
Pilot-scale filter Quartz sand 6.6–22 6.5–7.0 7.9–8.1 - 1.39 ± 0.10 0.28 19 0.99 ± 0.12 <0.1 26 [22]
Pilot-scale biofilter Mn Sand 8 8 - 2 day 1.4 <0.1 31 1.2 <0.05 51 [15]
Pilot Mn removal filter Quartz sand 10.5–12.5 8–9.5 7.5–7.9 2 weeks - - 0.1–0.15 0 25 [30]
Bench-scale biofilter Sand - reducing conditions 6.5 - - - 0.1–0.3 <0.05 42 [12]
Lab-scale biofilters Quartz sand 18–22 7.8–8.5 7.5–7.8 - 1.2 <0.1 13 0.8 <0.05 30 [19]
Lab-scale biofilters Sand >20 7.5–8 7.7 weekly - - 0.5 0 90 [2]

DO: Dissolved oxygen.

Int. J. Environ. Res. Public Health 2018, 15, 1822 13 of 14

4. Conclusions
In the present study, an optimization method for the start-up of a NH4 + -N and Mn2+ removal
filter for drinking water treatment was proposed. The chemical oxidation method effectively
shortened the start-up period of the filters. The operational factors of the influent Mn2+ concentration,
Fe2+ concentration, filtration rate and dosing time were optimized. The optimum conditions were
found to be 1.5 mg/L NH4 + -N, 2 mg/L Mn2+ , 1.5 mg/L Fe2+ , a 4 m/h filtration rate and the duration
of dosing time was 14 days. During the start-up period, the specific surface area of the filter media
increased along with prolonging the running time, which provided more active sites for NH4 + -N
catalytic oxidation. During the start-up period, frequent backwashing was not favorable to the
formation of the NH4 + -N and Mn2+ removal ability of the filters. The start-up periods of all filters
in this study were much faster than those of biofilters. This study has shown that the use of an
iron-manganese co-oxide filter could be an effective system for catalytic oxidation to remove NH4 + -N
and Mn2+ from drinking water.

Author Contributions: Y.C., T.H. and J.W. worked together. Specifically, T.H. proposed the idea. Y.C. designed
the study and interpreted the results. Y.C., L.C. and J.W. performed the experiments.
Acknowledgments: This work was supported by the National Key Research and Development Program of China
(No. 2016YFC0400706), the Natural Science Foundation of China (No. 51778521) and the Natural Science Basic
Research Plan in Shaanxi Province of China (No. 2017JQ2014).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Hasan, H.A.; Abdullah, S.R.S.; Kamarudin, S.K.; Kofli, N.T.; Anuar, N. Simultaneous NH4 + -N and Mn2+
removal from drinking water using a biological aerated filter system: Effects of different aeration rates.
Sep. Purif. Technol. 2013, 118, 547–556. [CrossRef]
2. Hoyland, V.W.; Knocke, W.R.; Rd, F.J.; Pruden, A.; Singh, G. Effect of drinking water treatment process
parameters on biological removal of manganese from surface water. Water Res. 2014, 66, 31–39. [CrossRef]
[PubMed]
3. Hasan, H.A.; Abdullah, S.R.S.; Kamarudin, S.K.; Kofli, N.T. On-off control of aeration time in
the simultaneous removal of ammonia and manganese using a biological aerated filter system.
Process Saf. Environ. 2013, 91, 415–422. [CrossRef]
4. Cai, Y.; Li, D.; Liang, Y.; Zeng, H.; Zhang, J. Autotrophic nitrogen removal process in a potable water
treatment biofilter that simultaneously removes Mn and NH4 + -N. Bioresour. Technol. 2014, 172, 226–231.
[CrossRef] [PubMed]
5. Cheng, Y.; Huang, T.; Shi, X.; Wen, G.; Sun, Y. Removal of ammonium ion from water by Na-rich birnessite:
Performance and mechanisms. J. Environ. Sci. 2017, 57, 402–410. [CrossRef] [PubMed]
6. Hasan, H.A.; Abdullah, S.R.S.; Kamarudin, S.K.; Kofli, N.T. Effective curves of completing simultaneous
ammonium and manganese removal in polluted water using a biological aerated filter. J. Ind. Eng. Chem.
2015, 30, 153–159. [CrossRef]
7. Broséus, R.; Cigana, J.; Barbeau, B.; Daines-Martinez, C.; Suty, H. Removal of total dissolved solids, nitrates
and ammonium ions from drinking water using charge-barrier capacitive deionisation. Desalination 2009,
249, 217–223. [CrossRef]
8. Liao, Z.L.; Chen, H.; Zhu, B.R.; Li, H.Z. Combination of powdered activated carbon and powdered zeolite
for enhancing ammonium removal in micro-polluted raw water. Chemosphere 2015, 134, 127–132. [CrossRef]
[PubMed]
9. Charerntanyarak, L. Heavy metals removal by chemical coagulation and precipitation. Water Sci. Technol.
1999, 39, 135–138. [CrossRef]
10. Choo, K.-H.; Lee, H.; Choi, S.-J. Iron and manganese removal and membrane fouling during UF in conjunction
with prechlorination for drinking water treatment. J. Membr. Sci. 2005, 267, 18–26. [CrossRef]
11. Pacini, V.A.; María, I.A.; Sanguinetti, G. Removal of iron and manganese using biological roughing up flow
filtration technology. Water Res. 2005, 39, 4463–4475. [CrossRef] [PubMed]
Int. J. Environ. Res. Public Health 2018, 15, 1822 14 of 14

12. Burger, M.S.; Mercer, S.S.; Shupe, G.D.; Gagnon, G.A. Manganese removal during bench-scale biofiltration.
Water Res. 2008, 42, 4733–4742. [CrossRef] [PubMed]
13. Tekerlekopoulou, A.G.; Pavlou, S.; Vayenas, D.V. Removal of ammonium, iron and manganese from potable
water in biofiltration units: A review. J. Chem. Technol. Biotechnol. 2013, 88, 751–773. [CrossRef]
14. Lytle, D.A.; Sorg, T.J.; Muhlen, C.; Wang, L.; Rahrig, M.; French, K. Biological nitrification in a full-scale and
pilot-scale iron removal drinking water treatment plant. Aqua 2007, 56, 125–136. [CrossRef]
15. Cheng, Q. Competitive mechanism of ammonia, iron and manganese for dissolved oxygen using pilot-scale
biofilter at different dissolved oxygen concentrations. Water Sci. Technol. Water Supply 2016, 16, 766–774.
[CrossRef]
16. Štembal, T.; Markić, M.; RibičIć, N.; BrišKi, F.; Sipos, L. Removal of ammonia, iron and manganese from
groundwaters of northern Croatia—Pilot plant studies. Process Biochem. 2005, 40, 327–335. [CrossRef]
17. Tekerlekopoulou, A.G.; Vayenas, D.V. Simultaneous biological removal of ammonia, iron and manganese
from potable water using a trickling filter. Biochem. Eng. J. 2008, 39, 215–220. [CrossRef]
18. Han, M.; Zhao, Z.W.; Gao, W.; Cui, F.Y. Study on the factors affecting simultaneous removal of ammonia and
manganese by pilot-scale biological aerated filter (BAF) for drinking water pre-treatment. Bioresour. Technol.
2013, 145, 17–24. [CrossRef] [PubMed]
19. Cai, Y.; Li, D.; Liang, Y.; Luo, Y.; Zeng, H.; Zhang, J. Effective start-up biofiltration method for Fe, Mn and
ammonia removal and bacterial community analysis. Bioresour. Technol. 2015, 176, 149–155. [CrossRef]
[PubMed]
20. Puyen, Z.M.; Villagrasa, E.; Maldonado, J.; Diestra, E.; Esteve, I.; Solé, A. Biosorption of lead and copper by
heavy-metal tolerant Micrococcus luteus DE2008. Bioresour. Technol. 2012, 126, 233. [CrossRef] [PubMed]
21. Cheng, Y.; Huang, T.; Sun, Y.; Shi, X. Catalytic oxidation removal of ammonium from groundwater by
manganese oxides filter: Performance and mechanisms. Chem. Eng. J. 2017, 322, 82–89. [CrossRef]
22. Guo, Y.; Huang, T.; Wen, G.; Cao, X. The simultaneous removal of ammonium and manganese from
groundwater by iron-manganese co-oxide filter film: The role of chemical catalytic oxidation for ammonium
removal. Chem. Eng. J. 2017, 308, 322–329. [CrossRef]
23. Cheng, Y.; Li, Y.; Huang, T.; Sun, Y.; Shi, X.; Shao, Y. A comparison study of the start-up of a MnOx filter for
catalytic oxidative removal of ammonium from groundwater and surface water. J. Environ. Sci. 2018, 65,
327–334. [CrossRef] [PubMed]
24. Jiang, H.; Liu, G.-H.; Ma, Y.; Xu, X.; Chen, J.; Yang, Y.; Liu, X.H.; Wang, H.C. A pilot-scale study on start-up
and stable operation of mainstream partial nitrification-anammox biofilter process based on online pH-DO
linkage control. Chem. Eng. J. 2018, 350, 1035–1042. [CrossRef]
25. Huang, T.; Cao, X.; Zhang, Q.; Su, Z.; Zheng, N. Catalytic oxidation of high-concentration ammonia in
groundwater by a naturally formed co-oxide filter film. Desalin. Water Treat. 2014, 52, 1615–1623. [CrossRef]
26. Zhang, R.; Huang, T.; Wen, G.; Chen, Y.; Cao, X.; Zhang, B. Using iron-manganese co-oxide filter film
to remove ammonium from surface water. Inter. J. Enviorn. Res. Public Health 2017, 14, 807. [CrossRef]
[PubMed]
27. Cheng, Y.; Huang, T.; Cheng, L.; Sun, Y.; Zhu, L.; Li, Y. Structural characteristic and ammonium and
manganese catalytic activity of two types of filter media in groundwater treatment. J. Environ. Sci. 2018.
[CrossRef]
28. Sahabi, D.M.; Takeda, M.; Suzuki, I.; Koizumi, J. Removal of Mn2+ from water by “aged” biofilter media:
The role of catalytic oxides layers. J. Biosci. Bioeng. 2009, 107, 151–157. [CrossRef] [PubMed]
29. Manceau, A.; Lanson, M.; Geoffroy, N. Natural speciation of Ni, Zn, Ba and as in ferromanganese coatings
on quartz using X-ray fluorescence, absorption and diffraction. Geochim. Cosmochim. Acta 2007, 71, 95–128.
[CrossRef]
30. Bruins, J.H.; Petrusevski, B.; Slokar, Y.M.; Huysman, K.; Joris, K.; Kruithof, J.C.; Kennefy, M.D. Biological and
physico-chemical formation of Birnessite during the ripening of manganese removal filters. Water Res. 2015,
69, 154–161. [CrossRef] [PubMed]

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