Chemosphere 215 (2019) 1e7

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Chemosphere
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Removal of micropollutants and cyanobacteria from drinking water

using KMnO4 pre-oxidation coupled with bioaugmentation
Zhiyu Jian a, Yaohui Bai a, *, Yangyang Chang b, Jinsong Liang a, Jiuhui Qu a
a
Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085,
China
b
School of Environmental Science and Technology, Dalian University of Technology, Dalian, 116024, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Treatment of micropollutants and

cyanobacteria - laden water was
investigated.

KMnO4 pre-oxidation coupled with
bioaugmented sand filtration is
proposed.

KMnO4 oxidation is efficient but re-
leases Mn2þ and cyanobacterial
toxins.

Mn2þ can be oxidized to Mn oxide,
which exhibits oxidation/adsorption
of pollutants.

a r t i c l e i n f o a b s t r a c t

Article history: Increasing micropollutant and cyanobacterial contamination of drinking water threatens human health
Received 17 July 2018 worldwide. However, these contaminates are not efficiently removed by common drinking water
Received in revised form treatment processes, and thus additional treatments are frequently required. Recent investigations have
30 September 2018
demonstrated that KMnO4 pre-oxidation can efficiently remove some micropollutants and cyanobacteria
Accepted 4 October 2018
Available online 4 October 2018
but the release of cyanobacterial toxins and Mn2þ limit its use. To overcome these problems, we pro-
posed a KMnO4 pre-oxidation coupled with bioaugmentation (e.g., sand filtration) method to treat
Handling Editor: Xiangru Zhang micropollutant- and cyanobacteria-laden water. We used 2-hydroxy-4-methoxybenzophenone-5-
sulfonic acid (BP-4, a common micropollutant in drinking water sources) and Microcystis aeruginosa (a
Keywords: widely distributed cyanobacterial species) as model pollutants to verify the feasibility of the proposed
Drinking water treatment method. Results revealed that KMnO4 pre-oxidation efficiently removed existing natural organic matter
Micropollutants and Microcystis aeruginosa but failed to remove BP-4 and released Mn2þ and microcystin-LR (MC-LR)
Cyanobacteria during treatment. Following the addition of a manganese-oxidizing bacterial strain (Pseudomonas sp.
KMnO4 pre-oxidation
QJX-1) to the KMnO4-treated solution, we found that the bacteria could transform Mn2þ to Mn(III&IV)
Bioaugmented sand filtration
oxides, with the formed Mn oxides then able to remove BP-4 and MC-LR. Overall, the proposed method
exhibited advantages in the removal of natural organic matter (i.e., decreasing disinfection byproduct
formation), micropollutants, and cyanobacteria as well as preventing the release of Mn2þ, and thus may
be considered a good alternative for treating polluted drinking water.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction

* Corresponding author. The escalating worldwide contamination of drinking water

E-mail address: yhbai@rcees.ac.cn (Y. Bai).

https://doi.org/10.1016/j.chemosphere.2018.10.013
0045-6535/© 2018 Elsevier Ltd. All rights reserved.
2 Z. Jian et al. / Chemosphere 215 (2019) 1e7
sources with thousands of man-made compounds is a critical
environmental problem (Schwarzenbach et al., 2006). Although
some organic contaminants are found at very low concentrations in
water, they can react with chlorine to generate disinfection
byproducts (DBPs) during drinking water disinfection processes
(Kemper et al., 2010). Epidemiological studies have suggested that
consumption of chlorinated tap water containing halogenated DBPs
is somewhat related to bladder cancer, colorectal cancer, increased
spontaneous abortions, stillbirth, and birth defects (Jiang et al.,
2017; Li and Mitch, 2018). Many studies have examined synthetic
organics as important precursors of DBPs, including pesticides (Le
Roux et al., 2011; Matsushita et al., 2018), antibiotics (Dodd et al.,
2005; Navalon et al., 2008), and UV sunscreen (Nakajima et al.,
2009; Chang et al., 2016). Therefore, controlling the precursors of
DBPs is a critical factor in drinking water treatment.
Increased nutrient (i.e., N and P) concentrations can lead to
eutrophication in drinking water sources such as surface water.
These conditions can result in algal blooms. However, Algal cells are
not easily removed by common treatment processes due to their
electronegativity during coagulation/sedimentation (Tang et al.,
2017), which can cause algal cells to grow in the sand filter and
enter successive treatment systems or even the distribution
network (Joh et al., 2011; Shekhar et al., 2017). Algal growth in
subsequent processes and pipelines not only reduces water puri-
fication efficiency and increases pipeline corrosion, but also re-
duces the concentration of residual chlorine in the distribution
network, thereby creating conditions for the breeding of patho-
genic microorganisms (Setareh and Javaherdashti, 2006; Wei et al.,
2014). In addition, when algae especially cyanobacteria grow, they
can release toxic substances (e.g., microcystins and odorants),
which are not easily removed during drinking water treatment
(Himberg et al., 1989; Fang et al., 2010).
As a conventional chemical for pre-oxidation, KMnO4 is effective
in removing trace organic pollutants, mutagenic substances, and
chloroform precursors in drinking water. KMnO4 is also significant
for enhanced coagulation and algae removal. For example (Chen
et al., 2009), reported a 10%e30% increase in the algae removal
rate with 0e40 mg/L of aluminum salt coagulant and pre-oxidation
with 1.7 mg/L of KMnO4. However, studies have found that when
KMnO4 oxidizes cyanobacteria or organic matter in water, carci-
nogenic microcystins (Ou et al., 2012) and/or genotoxic Mn2þ
(Chang et al., 2016) can be generated. To address this issue, we
proposed an alternative KMnO4 pre-oxidation coupled with bio-
augmentation method. We used 2-hydroxy-4-
methoxybenzophenone-5-sulfonic acid (BP-4, a common micro-
pollutant in drinking water sources) and Microcystis aeruginosa (a
widely distributed cyanobacterial species) as model pollutants to
explore the removal of micropollutants/cyanobacteria and whether
conversion of Mn2þ to biogenic manganese oxide (BMO) would
further purify water quality (e.g., remove cyanobacterial toxins).
Our study aimed to develop a feasible method to treat complex
pollution (e.g., micropollutants and cyanobacteria) in drinking
water sources.
2. Materials and methods
2.1. Selection of micropollutants and cyanobacteria
We selected BP-4, an organic UV-filter compound, as the model
micropollutant as it is a common precursor of DBPs (Chang et al.,
2016) and is frequently detected in wastewater and/or algal
blooms (Rodil et al., 2008; Fent et al., 2010). We purchased BP-4
from Sigma-Aldrich (MO, USA).
The cyanobacterial species used in this study was Microcystis
aeruginosa, which was selected due to its prevalence in algal
blooms and impact on water quality deterioration (e.g., release of
toxins and odor substances into water) and treatment (Sano et al.,
2011). We purchased the cyanobacterial species from the Wuhan
Institute of Hydrobiology, Chinese Academy of Sciences, after
which it was cultured in BG-11 medium (Rippka et al., 1979). Details
on cyanobacterial growth conditions are described in the Sup-
porting Information (Text S1). Microcystis aeruginosa cultures were
harvested at the exponential growth phase and diluted to cell
densities of 1.5  106 cells/mL and 3.0  106 cells/mL for all
experiments.
2.2. Manganese-oxidizing bacterial strain and culture medium
Manganese-oxidizing bacterial strain Pseudomonas sp. (Bai et al.,
2016b) was used to explore the role of biogenic manganese oxide
on the removals of micropollutant and cyanobacteria. The strain
(Text S2) was obtained from the Research Center for Eco-
Environment Science, Chinese Academy of Sciences. Pseudomonas
sp. QJX-1 was enriched in several 500-mL flasks containing 200 mL
of PYG medium (Bai et al., 2016b), and then incubated at 30  C and
170 rpm in a rotary shaker until the bacteria reached the logarith-
mic growth phase (~48 h). The bacterial cells were harvested by
centrifugation at 3000 g for 5 min at room temperature. The cells
were washed three times with 50 mL of sterile deionized water. The
bacterial deposit was resuspended with 500 mL of sterile deionized
water. The bacterial suspension was employed immediately as the
experimental inoculum.
2.3. Preparation of micropollutant-laden and cyanobacteria-laden
water
The micropollutant-loaded water was composed of 176 mg/L of
tyrosine (Tyr, a typical NOM that supplies C and N for bacteria)
(Chang et al., 2016) and 1 mg/L of BP-4. Cyanobacteria -laden water
A contained 176 mg/L of Tyr and 1.5  106 cells/mL of Microcystis
aeruginosa. Cyanobacteria-laden water B contained 176 mg/L of Tyr
and 3.0  106 cells/mL of Microcystis aeruginosa. The Tyr was pur-
chased from J&K China Chemical Ltd.
2.4. KMnO4 pre-oxidation
We transferred 200 mL of micropollutant-loaded water to a
series of 500-mL Erlenmeyer flasks. We then added KMnO4 to the
simulated pollution water at [KMnO4]0:[Tyr]0 ratios of 2:1, 1:1, and
1:5, respectively, followed by stirring in the dark. Under different
experimental times, the KMnO4 and residual concentrations of
Mn2þ, Tyr, and BP-4 were measured.
Cyanobacteria-laden waters A and B (200 mL) were transferred
to a series of 500-mL Erlenmeyer flasks, after which KMnO4 was
added at 5 mg/L, 25 mg/L, 50 mg/L, 100 mg/L, 150 mg/L, respec-
tively, followed by stirring in the dark. After 30 min of pre-
oxidation, the residual concentrations of Mn2þ and cyanobacterial
cell integrity were measured.
2.5. Biogenic manganese oxidation
After collecting 200 mL of KMnO4-treated residual
micropollutant-loaded water, we added 10 mM N-2-
hydroxyethylpiperazine-N0 -2-ethanesulfonic acid (HEPES) (pH
7.2) to maintain the pH at 7.0e7.5. For each test, 0.5 g/L
MgSO4$7H2O, 60 mg/L CaCl2$2H2O, and 5 mg/L KHPO4$3H2O were
added to the pre-oxidation residual as trace elements required for
bacterial growth. We then filtered 200 mL of the above-mentioned
pre-oxidation residual using 0.22-mm membrane filters into 500-
 Z. Jian et al. / Chemosphere 215 (2019) 1e7
mL sterile flasks. Pure manganese-oxidizing bacterium Pseudo-
monas sp. QJX-1 was then added as the inoculant to investigate
whether the bacteria could oxidize Mn2þ in the KMnO4-treated
water. The Pseudomonas sp. QJX-1 solution (3 mL) was inoculated
into a series of flasks containing 200 mL of KMnO4-treated solution.
All flasks were sealed with seal-film and incubated at 30  C and
170 rpm. Under different incubation times, the optical density at
600 nm (OD600) and residual concentrations of Mn2þ, BP-4, and Tyr
were measured, respectively.
To understand the role of biogenic manganese oxidation in
KMnO4-treated cyanobacteria-laden water, we first investigated
whether the release of cyanobacterial toxins inhibited the growth
and Mn2þ oxidation of Pseudomonas sp. QJX-1. We added 3.5 ng/mL
of microcystin-LR (MC-LR) purchased from Shanghai Solarbio
Bioscience & Technology Co., Ltd, into 200 mL of PYG medium
(commonly used for the growth of Mn2þ-oxidizing bacteria) (Liang
et al., 2015, 2016) containing 0 mg/L, 4.3 mg/L, or 46.0 mg/L Mn2þ,
respectively. Except for the controls, we inoculated 3 mL of Pseu-
domonas sp. QJX-1 into each flask, which were then sealed with
seal-film and incubated at 30  C and 170 rpm. Under different in-
cubation times, the OD600 and residual concentrations of Mn2þ and
MC-LR were measured, respectively. After confirming the impacts
of MC-LR on bacterial growth and Mn oxidation, we performed the
biogenic manganese oxidation test for the KMnO4-treated water.
The pre-oxidation residuals of cyanobacteria-laden waters A
and B with the addition of 50 mg/L of KMnO4 ([KMnO4]0:[-
Tyr]0 ¼ 1:5) were selected as the media for the biogenic manganese
oxidation tests. We added 10 mM HEPES (pH 7.2) to maintain the
pH of the pre-oxidation residuals at 7.0e7.5, for maximizing bac-
terial growth. Subsequently, the trace elements mentioned above
were added. The pre-oxidation residuals (200 mL) were then
filtered using 0.22-mm membrane filters (removing residual cya-
nobacterial cells) into 500-mL sterile flasks. We then used Pseu-
domonas sp. QJX-1 as the inoculant to investigate whether the
bacteria could oxidize Mn2þ in the pre-oxidation residuals of the
cyanobacteria-laden water. We inoculated 3 mL of the Pseudomonas
sp. QJX-1 solution into a series of flasks containing 200 mL of
KMnO4-treated residual. All flasks were sealed with seal-film and
incubated at 30  C and 170 rpm. Under different incubation times,
the OD600 and residual concentrations of Mn2þ and MC-LR were
measured, respectively.
All flask experiments were run in triplicate.
2.6. Removal of MC-LR by freeze-dried BMO
To determine the removal of BMO on MC-LR, we enriched BMO
by centrifuging 72 h-incubated culture (2 L). Washing three times
with sterile ultrapure water to remove the bacteria culture me-
dium. To avoid the possible oxidation of MC-LR by superoxide
produced from living bacteria (Chang et al., 2018), the collected
precipitates were freeze-dried for the oxidation and adsorption
experiments with BMO. The freeze-dried BMO was incubated with
3.5 ng/L of MC-LR in 60 mL of Milli-Q water at 30  C with shaking.
Under different experiment times, the MC-LR concentrations were
determined using a Microcystin BX Plate Kit (Beacon Analytical
Systems Inc, ME, USA) according to the manufacturer's instructions.
2.7. Chemical analysis
KMnO4 was measured at an absorbance of 525 nm using a U-
3100 spectrophotometer (Hitachi Co., Japan). Concentrations of
Mn2þ were measured using inductively coupled plasma/optical
emission spectrometry (ICP-OES, Agilent, USA). The Tyr concen-
tration was analyzed using an Agilent 1290 ultraperformance liquid
chromatograph (UPLC) equipped with a Waters Acquity UPLC HSS
3
T3 column (2.1 mm  100 mm  1.8 mm) and identified with an
Agilent 6460 triple quadrupole mass spectrometer (USA) (Chang
et al., 2018). BP-4 was determined by a Waters high performance
liquid chromatograph equipped with a Waters C18 column
(2.1 mm  100 mm  1.8 mm) and identified by tandem mass
spectrometry (HPLC-MS, Waters, USA) (Rodil et al., 2008).
2.8. Biological analysis and MC-LR determination
We measured the OD680 of the cyanobacterial suspension for
calculating the cyanobacterial cell density (Fig. S1) and OD600 of the
suspension for bacterial density using a U-3100 spectrophotometer
(Hitachi Co., Japan). Cyanobacterial cell integrity was determined
using a flow cytometer (FACSCalibur 4CLR, BD Biosciences, San Jose,
USA) equipped with an argon ion laser emitting at a fixed wave-
length of 488 nm for fluorescence measurement. SYTOX green
nucleic acid stain (Invitrogen, USA) was used to determine cell
integrity according to Qi et al. (2016). The MC-LR concentration of
the filtered water samples was measured using the Microcystin BX
Plate Kit (Beacon Analytical Systems Inc, ME, USA) according to the
manufacturer's instructions.
3. Results and discussion
3.1. KMnO4 pre-oxidation of micropollution water
To investigate the treatment effect of KMnO4 on micropollutant-
loaded water, we measured the concentration of micropollutant
(BP-4)-loaded water during the pre-oxidation process. Results
(Fig. 1) showed that the concentration of BP-4 did not significantly
decrease during KMnO4 pre-oxidation, demonstrating that KMnO4
did not oxidize BP-4. However, we observed the appearance of a tan
colloid in the solution during the initial period. This suggested that
KMnO4 oxidized Tyr and produced MnO2 colloid and Mn2þ
(Navalon et al., 2008; Malik et al., 2010). Because the reaction be-
tween KMnO4 and Tyr was too rapid to quantify Tyr variation, we
used real-time spectrophotometry to determine the continuous
concentration changes in KMnO4 to verify the reaction. As shown in
Fig. 1, the KMnO4 concentration declined sharply, indicating that
KMnO4 exerted rapid oxidation of Tyr. We verified that the colloids
produced were mainly MnO2 using the leucoberbelin blue (LBB)
method (Krumbein and Altmann, 1973) (data not shown).
Concurrently, we showed that the colloidal particle size gradually
decreased with time, and a stable colloidal particle size of 50 nm
was finally formed (Fig. S2). To investigate whether the MnO2
colloids could oxidize Tyr, we further examined the variation of
Mn2þ during oxidation (Fig. 1, bottom subfigure). Results revealed
that Mn2þ was released quickly. After 30 min, Mn2þ decreased and
finally attained a stable level probably due to the adsorption of
MnO2 on Mn2þ (Zhang et al., 2007). In general, the greater the
KMnO4 dosage used, the better was the oxidation effect. However,
higher concentrations of KMnO4 also produced more Mn2þ.
3.2. Bioaugmentation of KMnO4-treated micropollution water
As KMnO4 had no significant effect on BP-4 removal and also
caused leakage of Mn2þ when oxidizing Tyr, we attempted to
convert Mn2þ to BMO using Mn2þ-oxidizing bacteria, with the
formed BMO able to oxidize/adsorb BP-4. Here, we used Mn2þ-
oxidizing strain Pseudomonas sp. QJX-1 to construct a biological
system to verify the above concept.
According to our previous research, QJX-1 cannot utilize BP-4 as
a carbon source for growth (Chang et al., 2018). Hence, we first
explored whether QJX-1 could survive in KMnO4-treated water and
use Tyr or Tyr transformation products as C/N sources for growth.
4 Z. Jian et al. / Chemosphere 215 (2019) 1e7

Fig. 2. Biogenic Mn2þ oxidation in the KMnO4-treated micropollutant-loaded water.

Fig. 1. KMnO4 oxidation for micropollutant (BP-4)-loaded water. The micropollutant- Data are means ± standard deviations for triplicate assays. pH ¼ 7.2, T ¼ 30 ± 0.2  C.
loaded water contained 176 mg/L of Tyr and 1 mg/L BP-4. Data are means ± standard
deviations for triplicate assays. Pre-oxidation conditions: t ¼ 60 min, pH ¼ 6.0 and
T ¼ 25 ± 0.2  C. 3.3. KMnO4 pre-oxidation of cyanobacteria-laden water

To understand the ability of KMnO4 to oxidize the cyanobacteria

As shown in Fig. 2, we observed that the bacteria could use Tyr as a
(Microcystis aeruginosa)-laden water, we used 5 mg/L, 25 mg/L,
nutrient source (reflected in the KMnO4:Tyr ¼ 1:1 and 1:5 ratios of
50 mg/L, 100 mg/L, and 150 mg/L of KMnO4 as oxidants to treat
the upper two subfigures), as well as Tyr transformation products
simulated cyanobacteria-laden water A (containing 1.5  106 cells/
(reflected in the KMnO4:Tyr ¼ 2:1 ratio). Subsequently, we further
mL cyanobacteria) and cyanobacteria-laden water B (containing
investigated whether QJX-1 could oxidize Mn2þ during growth. As
3.0  106 cells/mL cyanobacteria). Results demonstrated that the
seen in Fig. 2, Mn2þ decreased from 3.5 mg/L to 0 mg/L within 120 h
proportion of damaged cyanobacterial cells in the cyanobacteria-
only when KMnO4:Tyr ¼ 1:5, suggesting the formation of BMO.
laden water gradually increased with the increase in KMnO4
However, in the other two systems (KMnO4:Tyr ¼ 2:1 and 1:1), the
dosage (Fig. 3). This confirms previous findings that KMnO4 can
Mn2þ concentration remained unchanged, which was probably due
damage and destroy the integrity of algal cells (Fan et al., 2013; Ma
to a shortage of usable energy (Tyr) for Mn2þ biotransformation.
et al., 2018). However, the release of Mn2þ by KMnO4 reduction and
The structure of the formed BMO is similar with hexagonal bir-
occasional release of intracellular toxins from cyanobacteria are the
nessite (d-MnO2) (Bai et al., 2016b). Several studies have demon-
main disadvantages of its use (Rodríguez et al., 2008; Ou et al.,
strated that BMO can oxidize and adsorb organic pollutants and
2012). To investigate if these negative effects occurred during
metalloids (Chen et al., 2010; Forrez et al., 2010). Combined the
KMnO4 pre-oxidation, we further measured the Mn2þ concentra-
results from this study (Fig. 2) and an our previous study (Chang
tion. We observed whether KMnO4 oxidation would produce
et al., 2018), it was proved that BMO could oxidize/adsorb BP-4 in
increased Mn2þ with the increase in KMnO4 dose. Hence, soluble
the water. Furthermore, the fluctuation in the BP-4 concentration
Mn2þ became a potential risk factor for water quality safety. To
might be due to the adsorption capacity of BMO constantly
investigate the effect of KMnO4 pre-oxidation on MC-LR, we
changing and aging (Webb, 2005), which caused the desorption of
measured MC-LR concentrations under different test times. We
BP-4.
observed that before KMnO4 pre-oxidation, the MC-LR background
 Z. Jian et al. / Chemosphere 215 (2019) 1e7 5

Fig. 3. KMnO4 oxidation for the cyanobacteria (Microcystis aeruginosa)-laden water.

Data are means ± standard deviations for triplicate assays. Pre-oxidation conditions:
t ¼ 30 min, pH ¼ 6.0 and T ¼ 25 ± 0.2  C.

values of cyanobacteria-laden waters A and B were 2.22 mg/L and

Fig. 4. The interaction between MC-LR and BMO formed in situ. Data are means ±
2.79 mg/L, respectively, but when the cyanobacteria-laden waters standard deviations for triplicate assays. pH ¼ 7.2, T ¼ 30 ± 0.2  C.
were oxidized with 50 mg/L of KMnO4, the MC-LR concentrations
increased to 3.27 mg/L and 3.44 mg/L, respectively. Based on previ-
ous research (Ou et al., 2012), we deduced that KMnO4 pre-
oxidation could damage Microcystis aeruginosa and release MC-LR.

3.4. Bioaugmentation of KMnO4-treated cyanobacteria-laden water

The Microcystis aeruginosa used in this study likely generated

MC-LR during growth (Zhang et al., 2017). Considering the toxic
effects of MC-LR, we first tested the impact of MC-LR on the growth
of QJX-1 and subsequent biogenic manganese oxidation (Fig. 4).
According to the variation in bacteria density (OD600), QJX-1
exhibited identical growth trends in the three groups (0, 4.3 mg/L,
and 46 mg/L Mn2þ). This demonstrated that MC-LR (3.5 ng/mL,
much higher than the Chinese drinking water standard which is
1.0 mg/L) did not have a significant toxic effect on the growth of QJX-
1. Subsequently, we analyzed the Mn2þ concentration and found
that MC-LR did not affect the biogenic manganese oxidation of QJX-
1. To investigate whether BMO from in situ could remove MC-LR, we
measured MC-LR concentrations. Results showed a significant
Fig. 5. MC-LR removal by freeze-dried BMO. The medium contained 3.5 ng/mL of MC-
fluctuation in MC-LR levels during the formation of BMO, indicating LR and 70 mg/L BMO. Data are means ± standard deviations for triplicate assays.
the occurrence of adsorption-desorption. Due to the low amounts pH ¼ 6, T ¼ 25 ± 0.2  C.
of formed BMO, the removal of MC-LR was not clear. Thus, we
freeze dried and concentrated BMO and mixed it with MC-LR. As pre-oxidation could transform BMO by QJX-1 and whether BMO
shown in Fig. 5, BMO could remove 56% MC-LR within 5 min. Af- could effectively remove MC-LR. We inoculated QJX-1 in the re-
terward, the weak adsorption-desorption process was observed. sidual solution of KMnO4-treated cyanobacteria-laden water. As
Furthermore, we explored whether Mn2þ released from KMnO4 shown in Fig. 6, QJX-1 oxidized Mn2þ in the pre-oxidation residues
6 Z. Jian et al. / Chemosphere 215 (2019) 1e7
Fig. 6. Biogenic Mn2þ oxidation in KMnO4-treated cyanobacteria-laden water. Data are
means ± standard deviations for triplicate assays. pH ¼ 7.2, T ¼ 30 ± 0.2  C.
of cyanobacteria-laden waters A and B, suggesting that the
manganese-oxidizing bacteria survived in the KMnO4-treated wa-
ter and utilized the limited nutrients for growth. In addition, we
observed that the MC-LR concentration did not show a clearly
decreasing trend with time due to the low amounts of generated
BMO.
3.5. Potential application of KMnO4 pre-oxidation coupled with
bioaugmented sand filtration
KMnO4 pre-oxidation can cause leakage of Mn2þ and increasing
MC-LR concentrations. The remaining pollutants will enter subse-
quent water treatment processes, with previous research also
indicating that Mn2þ and MC-LR are difficult to remove during
coagulation (Li et al., 2014; Tobiason et al., 2016). Hence, it would be
better to eliminate Mn2þ and MC-LR during sand filtration. Some
studies have attempted to inoculate a single strain into the sand
filter to increase its decontamination efficiency (Mcdowall et al.,
2009; Bai et al., 2016a). Extensive studies have also suggested
that the manganese-oxidizing microbes that exist in the sand filter
can oxidize Mn2þ to Mn4þ and some microorganisms in the sand
filter can degrade MC-LR (Vandenabeele et al., 1992; Ho et al., 2007;
Bai et al., 2016a). In addition, BMO formed by manganese-oxidizing
bacteria can oxidize and adsorb contaminants and thus further
purify water (Meng et al., 2009; Chen et al., 2010). Hence, we can
introduce manganese-oxidizing bacteria (QJX1) into the sand filter
to increase its manganese oxidation potential. Although we did not
see significant removal of in situ-formed BMO on BP-4 and MC-LR
due to its low production, in the actual sand filter, the BMO
would accumulate on the surface of the sand owing to the
continuous inflows of source water containing Mn2þ. Hence,
KMnO4 pre-oxidation coupled with bioaugmented sand filtration
not only removed micropollutants and cyanobacteria but also
prevented the release of Mn2þ and further purified source water.
4. Conclusions
Micropollutants and cyanobacterial blooms are critical world-
wide environmental issues, especially regarding water pollution.
However, common drinking water treatment processes are ineffi-
cient in their removal We thus proposed a KMnO4 pre-oxidation
coupled with bioaugmentation approach to treat water contain-
ing micropollutants and cyanobacteria. We used BP-4 as a model
micropollutant and Microcystis aeruginosa as a model cyanobacte-
rial species to verify the feasibility of the proposed method. The
main outcomes of this study were: (i) KMnO4 pre-oxidation
effectively oxidized Tyr but not BP-4, with Mn2þ released during
oxidation; (ii) If Mn2þ oxidizing bacteria existed (often present in
the sand filter), the released Mn2þ was further oxidized into BMO,
which could remove/decrease BP-4; (iii) For cyanobacteria, KMnO4
pre-oxidation effectively removed the Microcystis aeruginosa cells
in water, but caused the release of cyanobacterial intracellular
substances (MC-LR increase) and Mn2þ. Using Mn2þ oxidizing
bacteria, Mn2þ was oxidized into BMO, which, in turn, decreased
MC-LR when at sufficient amounts.
Overall, our study proposed and verified that KMnO4 pre-
oxidation coupled with bioaugmentation is a suitable alternative
for the treatment of drinking water containing micropollutants
and/or cyanobacteria.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Funding No. 51578537 and 51778603), Chi-
nese Academy of Sciences (QYZDY-SSW-DQC004), and National
Water Pollution Control and Treatment Science and Technology
Major Project (2015ZX07406006).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2018.10.013.
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