Water Research 242 (2023) 120219

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Fe, Mn and me
Guibai Li
State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin 150090, China

A R T I C L E I N F O A B S T R A C T

Keywords: In over 60 years of research, my team and I have focused on Fe/Mn removal and the application of KMnO4 in
Iron drinking water purification, and we have made several technological innovations during this period. In response
Manganese to the basic need to remove Fe and Mn from groundwater sources in the early days of People’s Republic of China,
Catalytic film
I firstly introduced a catalytic technology involving the application of natural manganese sand produced in China
KMnO4
Compounds of KMnO4 and Chlorine
as one of the simplest, cost-effective techniques. During experiments, many phenomena that were inconsistent
with conventional theories were observed and a new mechanism was proposed, indicating iron/manganese
active films as a catalytic agent instead of MnO2. These films were found to be attached to the surface of natural
manganese sand. Fe/Mn-containing compounds with special structures and catalytic features were identified by
applying various analytical methods.
Drinking water safety was also strengthened by applying KMnO4 as a new cost-effective chemical for source
waters facing environmental pollution in China. Experiments showed that KMnO4 can effectively remove many
pollutants, including trace organic micro-pollutants, by the combined effects of oxidation and adsorption, which
were revealed and confirmed for the first time. Through the application of GC/MS analysis of water samples
before and after KMnO4 treatment of samples from various surface water sources, the oxidation by-products from
KMnO4 were found to be nontoxic. Therefore, KMnO4 is considered to be a safer chemical in comparison with
other conventional oxidants (e.g. HOCl). Previous studies also showed several novel features of KMnO4, such as
enhanced coagulation with chlorine, improved algae removal, and increased removal of organically bound
manganese. In particular, the combined use of KMnO4 and chlorine could achieve the same disinfection effect at
much lower (50%) chlorine dosages.
In addition, there are various chemicals and substances that can be combined with KMnO4 to improve
decontamination performance. Based on extensive experiments, permanganate compounds were found to be
highly efficient in removing heavy metals, e.g., thallium. My research also found that both KMnO4 and powdered
activated carbon were highly effective for removing odors and taste. Therefore, we developed a hybrid combi­
nation of these two technologies and successfully applied them in many water treatment plants, not only for taste
and odor, but also to remove organic micro-pollutants in drinking water.
This paper provides a summary of the aforementioned studies that were conducted by me, in collaboration
with water treatment industry experts in China, and my graduate students. As a consequence of these studies,
several techniques are now widely used in drinking water production in China.

1. The introduction of catalytic technology into the national water quality standards. To remove iron and manganese from
groundwater iron removal process groundwater, a foreign natural oxidation iron removal process,
involving dissolved oxygen assisted by artificial manganese sand was
1.1. Development of a natural manganese sand contact oxidation iron introduced, but that process had the disadvantages of a long process
removal process flow time, large scale equipment, and high investment cost. According to
literature (Zapffe, 1933), artificial manganese sand can catalyze the
During the early days of the establishment of the People’s Republic of oxidation of ferrous iron by utilizing dissolved oxygen in water, but
China, especially in the Northeast of China, the concentration of iron artificial manganese sand in China was expensive at that time and thus
and manganese in groundwater exceeded the limiting values of the was not suitable for application in practice. In view of this, I wondered

E-mail address: liguibai@[Link].

[Link]
Received 3 May 2021; Received in revised form 6 June 2023; Accepted 10 June 2023
Available online 12 June 2023
0043-1354/© 2023 Elsevier Ltd. All rights reserved.
G. Li Water Research 242 (2023) 120219

whether it was possible to use domestic natural manganese sand as a sand, which can be described as an "iron active film". The iron active film
substitute. After investigating, sampling, and performing model tests on can form naturally on the surface of the natural manganese sand media
domestic manganese sand, Weiyuan Yu and I found that natural man­ during the iron removal process, indicating an autocatalytic process.
ganese sand had a strong effect of catalytic oxidation for iron removal When natural manganese sand was used for the treatment of
(Li and Yu, 1963, 1965; Li, 1973a, 1980), and was also available at a groundwater with high iron concentration, the media became coated by
very low cost. Subsequently, I proposed and developed a novel tech­ iron-containing materials, and specifically globular iron-containing de­
nique for iron removal using natural manganese sand (Li, 1973b, 1973a, posits were observed. These deposits had an excellent catalytic activity
1975, 1977; Liu, 1978, 1983; Li, 1994), which only needed a simple and iron removal efficiency, which confirmed that the catalyst of this
aeration of the iron-bearing groundwater and then direct filtration process was not the manganese dioxide in the manganese sand, but
through a natural manganese sand filter. As a consequence of the actually the iron active film.
introduced catalytic effect, the highly-simplified removal process
significantly reduced the construction cost compared to the natural 1.3. Production of artificial rust sand
oxidation process, and was quickly promoted and applied through-out
China, thereby benefitting ~ 100 million people by this technique. The discovery of the iron active film revealed that the natural
manganese sand was only the carrier of the active film, and suggested
that other cheap filter materials, such as quartz sand, could be used
1.2. Discovery of catalysis by the iron active filter film instead of manganese sand. To demonstrate this, experiments were
performed by applying quartz sand as filter media for the treatment of
Previous studies (Zapffe, 1933; Li and Yu, 1963; Li, 1973a) have groundwater with an iron content of 5‒20 mg/L. A natural formation of
reported that the manganese dioxide in natural manganese sand was the an iron active film was observed on the sand surface within 7‒10 days,
catalyst to remove iron, but many abnormal phenomena were also resulting in a higher efficiency of iron removal. However, for ground­
observed by Cansheng Liu and me in our experiments and applications water with a low iron content, the iron active film may take a long time
of water production (Li, 1974, 1977; Liu, 1981; Liu et al., 1987). For to develop, which may exceed up to 20‒30 days; during this period
example, when the surface of manganese sand was covered with some before active film formation, the iron content in the filtered water was
yellow iron-containing precipitate, reduced catalytic activity of man­ not below the national water quality standard value. In order to reduce
ganese sand should be observed, as the iron-containing precipitate de­ the period of substandard water (‘filter maturation time’), I proposed a
posits covered the manganese sand. In contrast, the catalytic activity of method employing artificial quartz sand filter material, denoted as
the old manganese sand was found to be stronger than that of the new “artificial rust sand”, with the catalytic property to enhance the removal
manganese sand. efficiency of iron. In practice, aerated water with a high concentration of
Moreover, backwashing of the manganese sand filter was also Fe was filtered through the sand layer to accelerate the formation of the
applied when clogged by iron deposition, to increase the iron removal active film on the surface of the quartz sand. Following this, the artificial
efficiency. After washing the filter layer in accordance with the catalytic filter media was applied directly for water treatment, and a highly
theory of manganese dioxide, some interesting, unexpected, and con­ effective iron removal was achieved rapidly, normally within 10 min.
tradictory results were obtained. Fig. 1 shows the effect of backwashing In 1966, Yongzhen Peng and I started some experiments at a water
time on Fe removal by the manganese sand filter at a backwashing water treatment plant (Li, 1978, 1981) to investigate why it was experiencing
flow rate of 30 L/ (m2⋅s). When the backwashing time was 5‒8 min (data elevated Fe in the treated water. Our investigation was unsuccessful for
#1), the iron concentration in the effluent from the filter column more than ten days, and then suddenly one day we noticed that the iron
declined to less than 0.3 mg/L within 10‒15 min. Subsequent tests concentration from one particular filter unit had decreased to below the
involving prolonged backwashing times (up to 40 min) were conducted national standard. Apparently, owing to an operational error the water
to fully investigate the recovery performance of sand filtration. How­ level in the filter unit dropped to below the surface of the filter media,
ever, with much longer backwash times of 20 min (data #2) and 40 min thereby causing the influent iron-containing water to fall directly on to
(data #3), the filtered water quality greatly deteriorated in terms of Fe the filter layer. The effect of this was that ferrous iron was oxidized by
concentration. dissolved oxygen available on the sand surface, which greatly increased
This phenomenon showed that the catalyst in this process was not the formation of the active film.
manganese dioxide, but an iron film covering the surface of manganese
1.4. The catalytic activity and chemical structure of the iron active film

Cansheng Liu and I (Li, 1977, 1981; Li and Liu, 1989) conducted
experiments using long-term iron removal filter materials, and some key
results are shown in Fig. 2. Curve #1 represents the Fe removal per­
formance with continuous operation of the filter column, showing a
sustained and high iron removal efficiency. Curve #2 shows the iron
removal efficiency of the filter media after the filter column had been
shut down for 4 days. The iron removal efficiency of the filter material
was greatly reduced at the re-start of operation, and then gradually
recovered. Curve #3 shows the corresponding iron removal efficiency of
the filter material after the filter column had been shut down for 12 days.
In this case, it can be seen that the iron removal efficiency of the filter
material decreased to a greater extent after re-starting, and the recovery
of treatment performance was much longer. This indicated that the iron
film on the surface of the filter material gradually reduced its catalytic
Fig. 1. Effect of backwashing time on iron removal capacity of natural man­ activity as a function of downtime. In other words, the catalytic effect of
ganese sand. Filter material grain size: 0.6‒2.0 mm, filter layer thickness: 0.8 the iron film can only be achieved by a continuous iron removal process.
m, iron concentration within groundwater: 3.4 mg/L, filtration rate: 30 m/h Thus, the original iron active film on the surface of the filter material is
(backwashing times: 5‒8 min (data #1); 20 min (data #2); 40 min (data #3)); continuously covered with new films, which keeps the films fresh and
this figure is cited and reprinted from our previous work (Li and Liu, 1989). their catalytic effect active. The chemical composition of the fresh film

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G. Li Water Research 242 (2023) 120219

cannot be rapidly oxidized by dissolved oxygen in water under natural

pH conditions (pH 6‒7.5) because of the limitations in kinetics (Rosso
and Morgan, 2002). Additionally, the removal of manganese by strong
oxidants in the early days of our country (PR China) was very expensive,
and nearly impossible to apply. In 1958, a water treatment plant was
built in the Pingfang District of Harbin City incorporating a natural
oxidation process (aeration-reactive precipitation-sand filtration) for
iron and manganese removal. After the complete commissioning of the
water treatment plant, an effective removal was observed for iron but
not manganese. In cooperation with Maogong Fan and Yuchao Liu (Li,
1979; Peng et al., 1985; Li and Liu, 1989), I investigated the treated
water of this water plant again a year later and found an excellent
manganese removal efficiency. I also found that the quartz sand in the
filter units of the water plant had turned black, and the sand surface was
covered with a layer of manganese film, which had a catalytic effect on
the oxidation of divalent manganese in water by dissolved oxygen. This
Fig. 2. Experimental aging curve of iron activated film with iron concentration film was mainly composed of manganese, but also contained iron, sili­
in groundwater: 16‒18 mg/L; dissolved oxygen: 7‒8 mg/L. pH=6.0, water con, calcium, magnesium, and other elements. We termed this layer as a,
temperature: 6 ◦ C, filtration rate: 10 m/h (data #1-Rusty sand in continuous "manganese active film", and proposed a possible mechanism of man­
operation mode; data #2-Rusty sand after 4 d not operating; 3-Rusty sand after ganese removal by contact oxidation with the manganese active film
12 d not operating); this figure is cited and reprinted from our previous work (Liu et al., 1982; Peng et al., 1985; Li and Liu, 1989; Zhang et al., 2012;
(Li and Liu, 1989).
Chen, 2014; Xiong et al., 2014).
The above phenomenon was reproduced during another experiment,
was investigated, and it was found that trivalent iron accounted for 70‒ but the natural generation of a manganese active film was found to be
90%, and the divalent iron accounted for 2‒30%. In addition, quantities very slow, and it took several months under normal conditions. The filter
of Si, Ca, Mg, and Mn were also observed in the fresh film. Thermal and media that generates a manganese active film and reduces the manga­
weight loss analysis were used to explore the activity of the fresh film, as nese concentration in the treated water to 0.1 mg/L, was referred to as
summarized in Fig. 3. It was found that the Fe-chemical composition of ‘mature’ manganese filter media. Before the maturation stage of the
the fresh film can be calculated by the formula [m Fe(OH)3 + (1-m) Fe filter media was reached, the manganese concentration in the treated
(OH)2⋅2H2O], where m is the proportion of trivalent iron. It can be water was unable to meet the national water standards. In addition, if
considered that the active film was an iron compound with a special this water was discharged without further treatment, it may cause
chemical structure. environmental pollution.
At the time of this period of research, it was assumed by practitioners In collaboration with Haiyang Yang and others, I used Energy-
and researchers around the world that the iron removal through dispersive X-ray spectroscopy (EDS) to analyze the manganese active
oxidation was due to the presence of iron bacteria, which are abundantly film on the surface of the mature filter media. As shown in Fig. 4a, Mn in
available in nature, and their biological enzymes can catalyze the the film accounted for 45.44%, followed by Fe, Ca, Si, Al, O, C and other
oxidation of divalent iron. I cooperated with Cansheng Liu to sterilize minor elements. Fig. 4b shows the Raman spectrum, indicating the
the iron filter layer and found that the iron removal efficiency by the presence of manganese oxide in the manganese active film, similar to
filter did not decrease. These results further confirmed that the removal Birnessibe-MnOx. The MnOx crystalline structure of the manganese
of iron by iron active film contact oxidation is mainly due to chemical active film was evident from its XRD pattern (Fig. 4c). Fig. 5a shows the
catalytic oxidation, rather than the biological action of iron bacteria XPS full scan spectrum with the principal elements contained on the
under most natural water conditions (pH=6.0‒8.0). manganese active film, while Fig. 5b shows the XPS fine scan spectrum
and the Mn element peaks. Similarly, Fig. 5c shows the XPS full scan
2. Introducing catalytic technology into manganese removal spectrum and the O element peak of the manganese active film. In
from groundwater summary, the above analyses revealed that the manganese active film
contained manganese oxide crystals with a particular structure and
2.1. Discovery of catalysis of manganese active film which had a specific catalytic effect.
In order to remove manganese by contact oxidation with manganese
Owing to the high redox potential of manganese, divalent manganese active film, the manganese containing water is first aerated and then

Fig. 3. Differential thermal curve (a) and thermal weight loss curve (b) of fresh film; this figure is cited and reprinted from our previous work (Li, 1977).

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Fig. 4. (a) EDS analysis showing the elemental composition of the film on the surface of mature filter media; (b) Raman spectra suggesting the presence of Birnessite-
MnOx on the surface of mature filter media; (c) XRD spectra showing the MnOx crystal structure of manganese filter film on the surface of mature filter media; this
figure is cited and reprinted from our previous work (Yang et al., 2020; Yang, 2022; Yang, 2022).

directly filtered through the mature manganese filter with an active sand and Mashan manganese sand, respectively from Leping county and
layer to remove manganese. It uses dissolved oxygen as an oxidant Mashan city in China, had a strong adsorption capacity for divalent
without the addition of chemical agents, which is practically quite manganese in water, and reduced the manganese concentration in the
convenient, and more economical and efficient than chemical oxidation treated water to below 0.1 mg/L. While removing manganese, the sur­
for manganese removal. However, the period of maturation of the quartz face of the manganese sand also began to form a manganese active film,
sand filter was found to be too long, representing a critical limitation of indicating the media’s ability to remove manganese by a combination of
this technology that needed to be overcome. adsorption and contact oxidation. Thus, it was evident that after satu­
ration of the adsorption capacity, the manganese concentration in the
2.2. Technology for removing manganese by natural manganese sands treated water gradually increased. With increasing time during opera­
tion, the removal of the manganese by the manganese sand media with
In the 1970s, inspired by the high iron removal efficiency of natural its active film gradually increased and exceeded the decreasing
manganese sand, Chao Liu and I (Guangxi Comprehensive Design adsorption rate, so that the manganese concentration in the treated
Institute iron and Manganese Removal Test Group, 1981; Liu et al., water began to decrease; these varying effects were reflected by a peak
1982; Shen and Du, 1982; Li and Liu, 1989) conducted experiments in the manganese concentration in the treated water. Finally, the man­
using natural manganese sand to remove manganese, and obtained ganese concentration in the filtered water reduced to below 0.1 mg/L,
excellent results. Fig. 6 shows the results of manganese removal exper­ indicating maturation of the manganese sand filter layer.
iments with alternative filter media, including natural manganese sand It can be seen from Fig. 6 that the maturation period of Leping and
and quartz sand. The experimental feed water was groundwater with an Mashan manganese sand was 36 and 51 days, respectively. Quartz sand
ultra-high concentration of iron (14 mg/L) and manganese (6‒8 mg/L). and Jinxi manganese sand (excluding high-valence manganese) had a
Because of the high manganese and iron concentration, a two-stage weak adsorption capacity for divalent manganese, and a maturation
filtration process was applied: a first stage filtration for iron removal period of 96 days was observed. For groundwater with a typical man­
and a second stage filtration for manganese removal. The second-stage ganese concentration <1.5 mg/L, highly effective manganese removal
filter column was tested with alternative filter media including natural was observed using high-quality manganese sand, with adsorption
manganese sand and quartz sand, and the manganese-containing water occurring over a long period of operation. For the case where the filter
was filtered at a filtration rate of 7.5 m/h. The results summarized in layer was mature before the adsorption capacity of the manganese sand
Fig. 6 clearly demonstrated the rapid maturation by the natural man­ was exhausted, the filter was able to produce manganese-free water
ganese sand media. from the beginning. This combined process of manganese removal by
High-quality natural manganese sands, such as Leping manganese adsorption in the initial period of operation, and contact oxidation with

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G. Li Water Research 242 (2023) 120219

Fig. 5. (a) Full XPS scan showing the principal elements of the manganese film the surface of mature filter media; fine XPS scans showing the Mn (b) and O (c)
elemental peaks of the manganese film on the surface of mature filter media; this figure is cited and reprinted from our previous work (Yang et al., 2021; H. Yang,
2022, 2022).

maturation period associated with quartz sand filter material, and the
system was quite simple to operate, highly economical and effective, and
thus has been widely promoted and applied in China.

2.3. Mechanism of removing manganese ions by natural manganese sand

In Fig. 6, the high-quality natural manganese sand removes manga­

nese mainly through adsorption in the early stages of the treatment
process. During the removal period of manganese by adsorption, the
manganese concentration in the effluent was reduced to below 0.1 mg/
L. Meanwhile, the manganese active film also developed gradually on
the surface of manganese sand. When the adsorption begins to decay and
becomes saturated, the manganese sand mainly relies on the manganese
active film to catalyze and remove manganese until the filter material
Fig. 6. The maturation process of Mn removal using alternative filter material; matures and the manganese concentration in the treated water reduces
this figure is cited and reprinted from our previous work (Li and Liu, 1989). again to below 0.1 mg/L. In comparison, the quartz sand has a weak
adsorption capacity for divalent manganese in water, resulting in an
the active film in the later period of operation, was referred to as the insignificant reduction of manganese concentration in the treated water
technology of manganese removal by natural manganese sand (Li and as compared with the raw water in the initial period of operation.
Liu, 1989; Ma et al., 1992; Li et al., 1994; Shao et al., 1996, 2014). In Subsequently, the catalytic oxidation of the manganese active film
1978, a manganese removal water plant was built in Harbin according to formed in the later stages becomes the main factor for manganese
the aforementioned principle. The water treatment plant has produced removal until the maturation of the filter media. This maturation process
iron and manganese free water continuously since it was put into was found to be much slower than that of high-quality manganese sand.
operation. The natural manganese sand removal technology combines In 1973, we used the aged sand from the manganese removal filter to
the adsorption and catalytic oxidation processes, with the latter using test the manganese removal (Li, 1979). Firstly, aged sand was stored
dissolved oxygen as the oxidant. After aeration, manganese-containing outdoors for one year, and the manganese film on the surface of the
water only needs to be filtered with manganese sand to remove man­ quartz sand had already been air-dried, and its composition was found to
ganese rapidly. This technology overcomes the limitation of the long be mainly MnO2 after analysis. In this work, raw water with a

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manganese concentration of 1.0‒1.4 mg/L was pre-aerated and then In that particular experimental study, the mature filter media was
filtered through the aged sand. Consequently, when the pH was 7.0‒7.1, loaded into 4 filter columns, and a certain volume of oxygen-free iron-
the adsorption and removal period of the filter layer was 10 d, and the containing water was circulated for 24 h. The concentrations of ferrous
Mn concentration was found to be greater than 0.1 mg/L. Theoretically, iron in the column (influent) water from No. 1 to No. 4 were 0, 5, 10 and
if the pH is raised to 7.4‒7.6, the adsorption capacity of MnO2 should 20 mg/L, respectively. After draining out the iron-containing solution,
roughly double. Therefore, it was expected that the adsorption period the filter column was washed and filtered with manganese-containing
for manganese removal should also be doubled, corresponding to about raw water for 130 days. The concentration of divalent manganese in
20 days. However, experimental results showed that the manganese the water was about 1.43 mg/L and the pH was about 7.5. Fig. 7 shows
adsorption and removal period of the aged sand filter layer was pro­ the change of manganese in the effluent of the four filter columns.
longed to 106 days, suggesting the combined effects of adsorption and It can be seen from Fig. 7 that since No. 1 did not contain ferrous iron,
catalytic oxidation. Similar results were obtained for the experiments the manganese concentration in the effluent from the filter column was
with high-quality manganese sand. The MnO2 on the surface of always lower than 0.1 mg/L over the period of 130 days. However,
high-quality and aged sand was not a catalytic substance in the process column No. 2 was affected by the previous exposure to 5 mg/L of ferrous
of manganese removal, but it can oxidize divalent manganese and iron, and a highly reduced catalytic activity of the manganese film was
generate a catalytic manganese film. Therefore, I concluded that man­ observed. The manganese concentration in the effluent water began to
ganese oxide can produce a manganese active film. KMnO4 and ozone rise by more than 0.1 mg/L on the 50th day, and then decreased after
can also generate a manganese active film by oxidizing divalent man­ reaching a peak value. After the 90th day, the manganese concentration
ganese (Zhong et al., 2011; Wang et al., 2014; Gong, 2015; Jia, 2015; in the effluent water was found lower than 0.1 mg/L again. Conse­
Guo, 2017; Liu et al., 2019; Sun, 2019), which further confirmed my quently, the concentration of manganese was found to have exceeded
proposed mechanism. The removal of manganese by the manganese the national standard for a continuous period of 40 days. Similarly, No. 3
active film through contact oxidation is an autocatalytic process: the and No. 4 columns with previous exposure to 10 mg/L and 20 mg/L of
MnO2 on the surface of the manganese sand oxidizes the divalent ferrous iron, respectively, displayed manganese concentrations that
manganese and generates a manganese active film, which then further exceeded the standard value for periods of 62 d and 80 d, showing a
improves the removal of manganese. This greatly accelerates the long-term and serious impact (Liu et al., 1990; Chen, 2014; Li, 2015;
maturation rate of the manganese sand, and the maturation period is Wang et al., 2015; Yang et al., 2017, 2018). These findings suggested
significantly shorter than that of the quartz sand. that there needs to be an awareness of the contamination of manganese
The concept of removing manganese by biological methods was active films by ferrous iron, while designing the water treatment
introduced and studied by researchers a long time ago, and in different process.
parts of the world. In 1990, investigations in China observed the exis­ The test also detected the number of iron bacteria in the filter col­
tence of a large number of iron and manganese bacteria in the manga­ umn. During the 130-day operation, the manganese concentration in the
nese removal filter. Therefore, scientists put forward the idea of effluent of the filter column fluctuated greatly due to the influence of
biological manganese removal (Liu et al., 1990; Li et al., 2016, 2019), ferrous iron, but the number of iron bacteria was not affected and did not
and this has been widely considered in China for the last 30 years. In change much. This indicated that the catalytic activity of the manganese
cooperation with my students, I started research on the manganese film was not closely related to the number of iron bacteria, so that the
removal mechanism of manganese active films in 2012 (Yang et al., manganese active film mainly removed manganese by chemical cata­
2020; Jiang et al., 2023). In the initial stage of manganese removal by lytic oxidation, and the biological effect, although present, was not the
manganese sand there are few iron bacteria, and manganese is removed main factor.
mainly through chemical catalytic oxidation. However, in the initial
stage of manganese removal by quartz sand, the quartz sand matures
slowly, probably assisted by iron bacteria. In contrast, the phenomenon
of DO-based oxidation of divalent manganese and formation of a man­
ganese active film was observed on the surface of aseptic quartz sand.
After sterilizing the mature filter media, the manganese removal effi­
ciency of the filter layer was not weakened. Therefore, in the initial stage
of manganese removal from quartz sand, both biological effects and
chemical catalytic oxidation contribute to the development of a man­
ganese active film. As the autocatalytic oxidation of the manganese
active film progresses, the chemical catalytic oxidation becomes stron­
ger, while the biological action becomes weaker until it becomes a
secondary factor.

2.4. The effect of ferrous iron in water on the catalytic activity of

manganese active film

The redox potential of iron is lower than that of manganese, and thus
divalent iron acts as a reducing agent for the high multivalent manga­
nese in the manganese active film. My graduate student (Zhong, 2019)
immersed the manganese film in a solution of ferrous iron, and observed
that the high multivalent manganese was reduced to divalent manga­
nese and dissolved in water. Thus, the high-valence manganese in the
manganese film was reduced and solubilized, resulting in the loss of the
film’s catalytic structure and activity, and the substantial deterioration
of the manganese removal efficiency. For a long time, the water industry
did not understand the impact of ferrous iron, which caused poor Fig. 7. The change of manganese content in the effluent water of the filter
manganese removal in many water treatment plants, or even their fail­ column treated with different concentrations of ferrous ions for 24 h; this figure
ure sometimes. is cited and reprinted from our previous work (Zhong, 2019).

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3. Use KMnO4 in the drinking water purification process to manganese-containing water, resulting in an improved removal effi­
ciency of trace organic matter. Hence, in addition to oxidation, KMnO4
3.1. Removal of trace organic pollutants from drinking water by KMnO4 can also be utilized for the adsorption of trace organic pollutants.
for the first time in china This mechanism was further confirmed in subsequent studies. For
example, in 1989, Jun Ma and I, together with other team members
In the 1970s, it was discovered that chlorine disinfection of drinking (Ma, 1990), performed experiments using samples of Songhua River
water can produce chlorinated disinfection by-products, such as chlo­ water. The samples (CODMn 9‒11 mg/L, turbidity 30 NTU, pH 7.2‒7.3,
roform, that are potentially harmful to human health. Later, a variety of water temperature ~0 ºC) were taken from the lower reaches of the
trace organic pollutants also of human health concern were discovered Harbin section of the Songhua River in winter. After natural precipita­
in drinking water. The combined application of ozone and activated tion of the raw water sample, 4 mg/L of KMnO4 was added, and the
carbon with conventional treatment processes has been promoted as a water temperature was adjusted to 10 ◦ C. After stirring and a reaction
universal technology, not only for the effective removal of trace organic period of 2 h, the remaining KMnO4 was reduced by addition of ferrous
pollutants in water, but also for the decreased generation of chlorinated sulfate, and then 5 mg/L aluminum sulfate was added. After further
disinfection by-products. At that time in the 1970s, China had just stirring and filtration, the types and content of trace organic matter in
entered the period of reforms and opening up. Although there was also the water were evaluated using GC/MS, and around 100 different kinds
serious water pollution, the social economy was still underdeveloped of organic substances were identified in each sample, as shown in Fig. 8.
and it was quite difficult to promote and apply this more advanced The types and concentration of organic matter in the raw and treated
technology in practice. I wondered whether it was possible to find a water are listed in Table 1. It can be seen that the olefinic trace organic
more economical and effective technology for removing trace organic substances were easily oxidized by KMnO4, and were completely
pollutants from drinking water. In my previous research, KMnO4 was removed from the water. In comparison, alkane substances were found
used to oxidize and remove iron and manganese from surface water, and to be difficult to oxidize by KMnO4 due to their saturation. However, the
also to deodorize the drinking water. Undesirable odor and taste are application of KMnO4 showed a high removal rate regardless of their
mainly caused by particular trace organic substances in the water, and it chain length, which proved that the removal of organic matter was
was speculated that KMnO4 could effectively remove these trace organic mainly ascribed to the adsorption of manganese dioxide produced by the
pollutants. In the 1980s, my graduate student and I used KMnO4 to reaction. Many similar results can be found in Table 1.
purify surface water, and we found that it had a significant removal
efficiency for trace organic matter and heavy metals (e.g., iron and 3.3. Study of the by-products of KMnO4 oxidation
manganese) in water. This technology only needs a small dose of KMnO4
(about 1 mg/L) to the water, and can obtain satisfactory results, which It is well-known that KMnO4 has been widely been used all over the
makes it economical, effective, and simple, and thus it has been applied world for water treatment. However, very little knowledge was available
widely since the 1980s in water treatment plants. prior to 2000 about the formation of KMnO4 oxidation by-products that
had the potential to be toxic to the human body. Li Cong and I did some
3.2. Discovery of a new mechanism for removing micro-pollutants by research on this in the early 2000s (Li, 1975; Cong, 2002; Li et al., 2004).
KMnO4 Samples of the raw water in Beijing were taken from the Heishanhu
section of the Jingmi diversion canal which consisted of the following
In 1988, I collaborated with Jiuhui Qu and other water treatment typical characteristics: turbidity 3.0 NTU, pH 8.08, and DOC 2.66 mg/L.
experts to investigate a contaminated well in Shenyang, China (Li et al., Tests were conducted in which 3.0 mg/L FeCl3•6H2O and 1.0 mg/L
1989; Li and Ma, 1989; Li and Qu, 1989; Ma, 1990; Ma and Li, 1990; Li KMnO4 were added simultaneously to the raw water samples, and GC/
and Ma, 1991 G. 1992, 1992; Ma and Li, 1994; Ma and Graham, 1996; MS was used to analyze and identify the organic content in the water
Ma and Li, 1996; Ma et al., 1997b, 1998; Ma et al., 1999b; Zhang et al., samples after treatment.
2002c; Li and Zhang, 2003; Y. Yang et al., 2003; Cai, 2004; Cai and Li, The Songhua River water was sampled from three different locations,
2004; Liu, 2005; Liu et al., 2005a, 2005b, 2005c; Li et al., 2006; Zhang with No. 1 and No. 2 taken from the upper Songhua River of Harbin,
et al., 2006; Chen et al., 2007; He, 2007; Tian et al., 2007; He et al., China. The water samples were taken on two occasions during the
2008; Liu, 2008; Liang et al., 2012). Jiuhui Qu was my first graduate freezing period and dry season in winter, with many days separating the
student to conduct research on the removal of trace organic matter by two sampling events. The turbidity, TOC, and pH of the source No. 1
KMnO4 (Qu, 1988; Qu and Li, 1990, 1991, 1992). In addition to a large (comparative value for No. 2) was 10 NTU (12 NTU), 8.5 mg/L (9.4 mg/
amount of trace organic pollutants, the well water also contained a L), 7.2‒7.3 (7.2‒7.3), and the temperature was close to 0 ◦ C, respec­
relatively high concentration of divalent manganese. Considering that tively. The raw water samples were also subjected to simulated con­
divalent manganese can consume KMnO4 and significantly affect the ventional treatment, after which 5 mg/L Al2(SO4)3 and 4 mg/L KMnO4
removal of micro-pollutants, we arranged a set of comparative experi­ were added simultaneously. In contrast, the No. 3 raw water sample was
ments to observe the effect of divalent manganese on pollutant removal. taken from the lower Songhua River in Harbin, which was not in the
One of the experiments was to remove manganese from the raw water same year as No. 1 and No. 2. The turbidity of the raw water was about
first and then treat the manganese-free water to remove the trace 20 NTU, the average CODMn was 10 mg/L, the pH was 7.2‒7.3, and the
organic pollutants. A second approach was to directly use the raw water water temperature was close to 0 ◦ C. The raw water sample was also
to remove trace organic matter, to understand the effect of Mn (II). subjected to simulated conventional treatment, and subsequently 5 mg/
However, the results were exactly the opposite of what was expected. It L Al2(SO4)3 and 4 mg/L KMnO4 were added.
was observed that the removal of trace organic pollutants by adding The organic content of the Jingmi Canal’s raw water and the treated
KMnO4 to manganese-containing raw water was better than that of water was evaluated using GC/MS analysis. The raw water had 125
manganese-free water. Through GC–MS analysis, we found that KMnO4 types of organic compounds with a total peak area of 32,128,231, while
could not only remove some trace organic matter through oxidation, but the treated water had 75 types with a total peak area of 17,034,439 after
also remove trace organic matter that cannot be oxidized. This was treatment with FeCl3 and KMnO4, with a reduction of 40% in type and
attributed to the adsorption of trace organic pollutants by insoluble 47% in concentration. Among the detected compounds, two were among
MnO2 generated during the oxidation by KMnO4. The adsorption by the USEPA raw water regulations but completely disappeared after
MnO2 formed through the reaction of KMnO4 on trace organic matter KMnO4 treatment. The effluent water had 18 new types of organic
was further confirmed in subsequent experiments. These studies addi­ matter (Table 2), but no toxic and harmful substances were found ac­
tionally confirmed the generation of enhanced MnO2 by adding KMnO4 cording to the USEPA regulations.

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G. Li Water Research 242 (2023) 120219

Fig. 8. GC/MS analysis of trace organic matter in the raw water from Songhua River (a), and the water after coagulation with potassium permanganate and
aluminum sulfate (b), finished on the 24th January 1990; this figure is cited and reprinted from our previous work (Ma and Li, 1990).

Table 1
The effect of KMnO4 in removing trace organic matter in water.
Organic matter category Raw water Treated water

Peak Number Chromatographic peak area Peak Number Chromatographic peak area

Acid 13 2,224,099 6 126,801

Alcohol 9 679,844 2 648
Aldehyde 6 639,736 4 11,039
Alkanes 19 1,063,184 13 112,780
Benzene 2 33,616 0 0
Ester 12 1,457,971 6 174,137
Halogenated hydrocarbons 0 0 0 0
Heterocyclic compound 12 1,531,754 2 1167
Ketone 12 2,311,520 7 33,695
Nitrobenzene 3 198,042 1 3360
Olefin 4 28,811 0 0
Phenol 6 1,373,172 2 13,555
Polycyclic aromatic hydrocarbons 1 21,504 0 0
Other 1 44,864 0 0

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G. Li Water Research 242 (2023) 120219

Table 2 considered to be a safe and efficient oxidant for water treatment in

The newly generated products of organic matter from Jingmi water diversion comparison with other oxidants.
canal in Beijing, China.
Serial Organic name Serial Organic name 3.4. Discovery of KMnO4 as a coagulation aid
number number

1 2–2 Methyl-1, 3-butadiene 10 3 • Methyldecane Many new functionalities of KMnO4 have been discovered in the field
2 2-methylhorane 11 1. 10-Dioxydecane of drinking water purification through research studies since 1980.
3 4, 5-Dihydro-2-methyl-1, 12 Stearyl Phosphate
3-oxazone
In 1990, Jun Ma and I (Ma and Li, 1990; Ma et al., 1992; Ma, 1993;
4 Oxymethyl-9- 13 Hexadecane Ma and Li, 1993, 1994; Ma et al., 1997a; Ma and Li, 1997; Chen et al.,
chloroundecanoic acid 2000a; Ma et al., 2001; Liu, 2002; Zhang et al., 2006; Liu et al., 2009)
5 1-octanol 14 2, 3, 4, 5-tetrahydrogen worked together and used KMnO4 for the water treatment of an indus­
6 Methyl hexadecanoate 15 1-Hydroheptacontane
trial sector in Daqing that abstracts water from a heavily polluted lake
7 6-Twelve Huan 16 3-(Australian methyl)-
heptane source. The raw water of the water plant was found to be seriously
8 1- Non-block 17 Tetradecane polluted by domestic sewage and industrial wastewater, resulting in a
9 3-methylethanol 18 Nonaconane much lower coagulation efficiency than would normally be expected.
More than 10 mg/L of chlorine was required to be added to the water
during treatment process, which resulted in not only an unsatisfactory
Similarly, a total of 172 kinds of trace organic matter was detected in
treatment performance, but also serious equipment corrosion. In view of
the Songhua River (No. 1 point) with 10 types also found in the USEPA
this, we replaced the chlorine with a small dose of KMnO4, and found
regulations list. KMnO4 treatment reduced the variety and concentration
that KMnO4 acted as a strong coagulation aid. This was the first direct
of organic matter in the raw water by 48% and 77%, respectively, with 4
application of KMnO4 in drinking water production at any large-scale
USEPA-listed organic substances completely removed and 6 partially
level.
removed (total removal rate of 79%). 6 new types of organic matter were
The following experiment also confirmed the coagulation-assisting
observed (Table 3), but none were regulated by USEPA. Raw water from
effect of KMnO4. The turbidity, temperature and pH of the raw water
sample No. 1 was treated with Al2(SO4)3 alone as a control. This treat­
were 220 NTU, 10 ◦ C, and 6.5, respectively. When 5 mg/L of poly­
ment without KMnO4 caused a 7.6% reduction in the types of trace
aluminum chloride was added alone, the turbidity of the water dropped
organic matter and removed 13.3% of the total amount, indicating a
to 22 NTU after coagulation and precipitation. However, by combining
much lower degree of treatment as compared to that with KMnO4.
5 mg/L of polyaluminum chloride and 0.5 mg/L of KMnO4, the turbidity
No. 2 sample contained 187 trace organic compounds, with 13 listed
of the water after coagulation and precipitation was found to be 14.1
as potentially toxic by USEPA. KMnO4 treatment reduced the types of
NTU, which indicated that the addition of KMnO4 reduced the turbidity
organic matter in the raw water by 47.06% and the total concentration
by an additional 35.6%. Moreover, the addition of 5 mg/L poly­
up to 43.2%. 13 USEPA-listed compounds were all removed, 10
aluminum chloride and 0.5 mg/L permanganate compounding agent,
completely and 3 partially, with an average concentration removal rate
further reduced the turbidity of the water after coagulation and filtration
of 80.7% by GC/MS analysis. 9 new organic compounds were generated
to 12.1 NTU, with a 45% increase in removal, as shown in Fig. 9.
during treatment, none of which were considered toxic or harmful ac­
Since 2000, Ruiping Liu and I have worked together and widely
cording to USEPA regulations.
applied the KMnO4 in many of the water treatment plants between the
Lastly, 100 trace organic compounds were detected in No. 3 water
northeast and southwest of the China, and KMnO4 was found to be a
sample, with 5 listed as potentially toxic by USEPA. KMnO4 treatment
highly efficient coagulation aid. The multifunctional coagulation-
reduced the types and concentration of organic matter by 53% and 90%,
assisting mechanisms of KMnO4 mainly involved oxidation of DOM,
respectively. 4 USEPA-listed compounds were completely removed, 1
co-precipitation induced by coagulant and DOM, and adsorption of
partially, with a total concentration removal rate of 99.7%. However, 13
newly-formed manganese dioxide.
new organic compounds (Table 3) were generated during treatment,
none of which were considered toxic or harmful according to USEPA
regulations. 3.5. Engineered application of a hypermanganate compound
In summary, KMnO4 has not been extensively studied in recent years
in terms of oxidative by-products generation, but the results obtained so In 1989, Guoren Xu and I collaborated together to study the per­
far have not revealed any compounds which are potentially toxic to formance of combining the addition of KMnO4 and chlorine at the
human health at the concentrations found. Therefore, KMnO4 can be above-mentioned water treatment plant. This combination was a more
effective coagulant aid, and as a result we proposed the concept of a

Table 3
Novel by-products detected in Songhua River water.
Raw water Serial number Organic name Serial number Organic name

No. 1 1 Methyl benzoate 4 2-methyl-1,3-cyclodione

2 Oxalic acid phthalate 5 3,7,11-trimethyl-6,10-dodecen-1-ol
3 Methyl 2-quinolinate 6 Dodecanoic acid
No. 2 1 2,5-Dimethyl-3–2 alkyne 2,5-dione 6 4-decanone
2 Diethyl Amyl Phosphate 7 4-amino-3-penten-2-one
3 2-ethylheptanoic acid 8 6-aminocaproic acid
4 2,2-Diethyl-3-methyl-3-butenoic acid 9 2,3-Dihydro-1,1-dimethyl-4‑hydroxy acid
5 Cis-acetate-3-hexenyl ester
No. 3 1 2,2,4-Trimethyl-1,3-pentanediol 8 4-methylphenol
2 Caprylic acid 9 Tetradecanoic acid
3 1,2,3-propanetriol ester 10 1,2-methyl propyl butyl phthalate
4 1-Butyl-1-methylethylpropylcyclopropane 11 (Z,Z)− 9,12-octadecadienoic acid
5 N,N-bis(2-hydroxyethyl)dodecanoic acid 12 (Z)− 9-octadecanoic acid-2,3-dihydroxypropyl ester
6 Ethyl 2,4‑diethyl-3-furanhydroxy acid 13 3,3,5-Trimethylcyclohexanol
7 2-bromobenzyl-1H-6-amine bleaching

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G. Li Water Research 242 (2023) 120219

treatment of organic manganese in heavily polluted water from a water

plant in Guangzhou by applying KMnO4 and chlorine; this combination
proved to effective in achieving a high removal efficiency for manga­
nese. We found that many other agents can also be combined with
KMnO4 to form permanganate compounds, where the permanganate
was the main agent and the auxiliary agent provided further enhance­
ment to the water purification. A highly effective removal of trace heavy
metals such as lead, cadmium, chromium, mercury, and etc. was
observed in drinking water treatment upon applying permanganate
compounds, as reported by researchers (Ma et al., 2000b; Gao and Liu,
2002; Yang, 2007; Sun et al., 2009; Yu et al., 2009b; Yang et al., 2010,
2015; Du et al., 2017).
In 2010, the presence of thallium contamination was observed in the
Beijiang river (Guangdong, China), causing concern about risks to
human health. At that time, scientists had no effective technology to
remove trace amounts of thallium from drinking water. In collaboration
with Jun Ma, Zhonglin Chen, Heng Liang, and others, I carried out
thallium removal experiments using the permanganate compounds.
After extensive investigations, we finally succeeded in removing thal­
lium by electrostatic adsorption by use of permanganate compounds,
which contained large amounts of δ-MnO2 and showed a negative sur­
face charge under neutral conditions. The overall degree of removal of
Fig. 9. The effect of Potassium Permanganate Compound (PPC) and KMnO4 thallium reached up to 70%. This technology was subsequently applied
enhanced coagulation on sedimentation effluent turbidity removal; this figure is
to water plants in more than 30 cities, covering 6 million people, setting
cited and reprinted from our previous work (Chen, 1997).
an example of the large-scale application of permanganate compounds
for thallium removal.
compounding agent. The results shown in Fig. 9 demonstrate the supe­
rior performance of the permanganate compound as a coagulation aid 3.6. Combined use of KMnO4 and powdered activated carbon to remove
than that of KMnO4, as reported by numerous scientists (Xu et al., 1995; taste, odor and trace organic pollutants
Chen, 1997, 1998; Ma et al., 1999a; Xu, 1999; Xu and Li, 1999; Xu et al.,
1999a, b; Chen et al., 2001c; Xu and Li, 2001; Zhang et al., 2001, 2002; Polluted source water often has an unpleasant odor, especially when
Zhang et al., 2002b; Fan et al., 2004, 2004b; Zhang, 2004; Zhang et al., algal blooms occur in lakes and reservoirs, resulting in a deterioration of
2004d; Chen et al., 2005a; Li et al., 2005f; Liang et al., 2005b, 2005c; the water quality. Conventionally, powdered activated carbon is utilized
Yang et al., 2005a). for taste and odor removal, however, sometimes the effect is not so
In 1994, Wei Chen and I used KMnO4 and calcium hypochlorite to obvious. Through a series of experiments, Zhonglin Chen and I found
treat the high algae-laden water of Taihu Lake, and found excellent re­ that integration of KMnO4 with powdered activated carbon was highly
sults (Ma et al., 2000a; Shi et al., 2000; Zhang et al., 2000; Chen, 2001; effective in taste and odor removal, that is, whenever the deodorizing
Chen et al., 2001a, 2001b; Zhang et al., 2004a; Chen et al., 2005b; Liang effect of powdered activated carbon was not satisfactory, KMnO4
et al., 2005a). showed a significant effect, and vice versa. Nowadays, the combined
In 2003, Yanling Yang and I used KMnO4 and chlorine to inactivate application of KMnO4 and powdered activated carbon for taste and odor
bacteria. We found that even by reducing the amount of chlorine by half, removal has become a very common technology in our country and has
the same inactivation efficiency can be achieved due to the presence of been widely used by various researchers (Chen et al., 1998; Fan, 1998;
KMnO4, as shown in Fig. 10. This provided an important benefit in terms Fan et al., 1999; Chen et al., 2000b; Jiang, 2000; Jiang et al., 2000b, a;
of significantly reducing the generation of chlorinated disinfection by- Jiang et al., 2001; Zhang, 2001; Zhang and Li, 2001; Zhang et al., 2002a,
products in the water (Yang, 2003; Liu et al., 2004; Yang et al., 2004; 2004a, 2004c).
Li et al., 2005a, 2005b, 2005c; Li et al., 2005d, 2005e, 2005 g; Yang In 2003, excessive algae developed in the Miyun Reservoir in Beijing,
et al., 2005b). which resulted in the raw water from the water treatment plant having
In 2009, Wenzheng Yu and I worked together to evaluate the an unpleasant odor. Ruiping Liu and I, together with the cooperation of
water plant staff, conducted various experiments and discovered that
permanganate compounds combined with activated carbon had the best
odor removal efficiency (Liu et al., 2013). Subsequently, the technology
was permanently adopted by the treatment plant to solve the issue of the
odor problem in tap water. In view of the major scale of water produced
by treatment plant in Beijing, the application of this technology provides
an important example of its value for large-scale water plants
(million-ton/day).
The combined use of KMnO4 and powdered activated carbon also
showed a high removal efficiency for trace organic pollutants. The
Nanjiao Water Plant in Dongying City, Shandong Province, uses the
reservoir water in the lower Yellow River as its water source. Due to the
discharge of sewage and wastewater along the Yellow River, the water
quality has been found significantly polluted. In 2009, I cooperated with
Xing Li, Heng Liang, etc., in testing the application of permanganate
Fig. 10. The effect of chlorine in combination with KMnO4 and chlorine alone compounds and powdered activated carbon to the raw water. After their
on the total coliform removal; this figure is cited and reprinted from our pre­ addition, conventional coagulation, and sand filtration followed by ul­
vious work (Yang, 2003). trafiltration, was suggested to improve the water quality. The

10
G. Li Water Research 242 (2023) 120219

renovation project of the water plant was completed and put into pro­ Chen, W., 2001. Research on the Enhanced Coagulation of Manganate Complex to
Removal of Pollutants such As Cyanobacteria in Taihu Lake. Harbin Institute of
duction in December 2009. A total of 106 quality parameters of the final
Technology. PhD thesis.
water from the water treatment plant were found to be below the limits Chen, W., Chen, Z., Tian, J., Yu, L., Chen, W., Li, G., 2007. Potassium permanganate
of the Chinese national water quality standards, and overall a highly compound pre-oxidation treatment of micro-polluted water. Ind. Water Treat. 27
effective decontamination of the pollutants was observed. Among the (05), 48–50.
Chen, W., Li, G., Wu, H., Wu, P., 2005b. Study on the effectiveness of PPC to remove
purification processes used in water treatment plants, conventional cyanobacteria from Taihu Lake and its influencing factors. Water Supply Drain. J. 01
coagulation followed by ultrafiltration is not effective in removing trace (31).
organic pollutants. Therefore, the integration of these conventional Chen, W., Li, G., Zou, H., 2001a. Indoor experimental study on removal of cyanobacteria
from Taihu Lake water with potassium permanganate compound. J. Harbin Jianzhu
processes with the addition permanganate compounds and powdered Univ. 34 (03), 72–74.
activated carbon, has played a vital role in improving the removal ef­ Chen, W., Li, G., Zou, H., Wu, P., 2001b. Experimental study on the removal of chroma in
ficiency of trace pollutants (Yu et al., 2009a; Wu et al., 2012; Wang et al., Taihu Lake water by potassium permanganate compound. J. Harbin Jianzhu Univ.
34 (06), 67–69.
2016). The Nanjiao Water Plant, having a capacity of 100,000 m3/day, Chen, Z., 1997. Research on Enhanced Coagulation, Turbidity and Deodorization with
was successfully operated by applying the permanganate compounds Permanganate Compound. Harbin University of Architecture and Construction. PhD
and powdered activated carbon before the ultrafiltration process, at an thesis.
Chen, Z., Fan, J., Ma, J., Tian, H., Zhang, Y., Li, G., 1998. Combination of potassium
unprecedented large-scale for the first time in China. permanganate and powder activated carbon to remove and control mutagenic
substances in micropolluted surface water. China Water Supply Wastewater 14 (04),
4. Conclusions 5–7+10+12.
Chen, Z., Fan, J., Yang, R., Ma, J., Li, G., 2000a. Development of by-products of drinking
water chlorination disinfection and its control technology. J. Harbin Univ. Civ. Eng.
I have been engaged in the research of drinking water purification Archit. 33 (06), 35–39.
technology for more than 60 years. The goals of my work have been to: Chen, Z., Niu, W., Ma, J., Wang, D., Li, G., Jiao, M., 2001c. Permanganate compound
enhanced coagulation treatment of surface water with high organic content. Ind.
(1) combine the societal needs and economic development relating to
Water Treat. 21 (5), 15–16+26.
water supply, (2) conduct research to solve the main, contemporary Chen, Z., Wang, D., Li, G., Lv, Q., Luo, J., Yang, C., 2000b. Experiment on removing algae
problems in drinking water treatment, (3) lead the scientific and tech­ and odor with potassium permanganate compound agent. China Water Wastewater
nological development in the water treatment industry and solve 16 (11), 58–60.
Cong, L., 2002. Research on Water Purification Effect of New Ecological Manganese
problems through novel innovation, and (4) promote the application of Dioxide. Harbin Institute of Technology.
lab-scale innovations in the real world, in order to protect the general Du, X., Liu, G., Qu, F., Li, K., Shao, S., Li, G., Liang, H., 2017. Removal of iron, manganese
public from water-borne diseases. and ammonia from groundwater using a PAC-MBR system: the anti-pollution ability,
microbial population and membrane fouling. Desalination 403, 97–106.
In general, iron and manganese removal techniques require contin­ Fan, J., 1998. Research on the Combined Technology of Permanganate Compound and
uous monitoring, since the existence of these metals in natural waters is Activated Carbon to Remove Organic Matter in Water. Harbin University of
a potential threat to human health. In the future, there are some Architecture and Engineering. PhD thesis.
Fan, J., Li, G., Chen, Z., 1999. Study on the combined use of potassium permanganate
outstanding problems to be solved. In particular, the effects of seasonal compound agent and granular activated carbon to remove organic pollutants in
variation of surface water on drinking water exceedances in iron or water. China Water Wastewater 15 (01), 7-10+12.
manganese should be studied. Also, KMnO4 alternatives for iron/man­ Fan, J., Ma, J., Chen, Z., Li, G., 2004. Research on controlling drinking water
chlorination disinfection by-products. Water Purif. Technol. 23 (01), 7–9+36.
ganese removal need to be developed, since KMnO4 is strictly managed Gao, B., Liu, Y., 2002. Adding potassium permanganate and chlorine to remove iron and
for pharmaceutical production. manganese from water. China Water Wastewater 18 (12), 87–88.
Gong, X., 2015. Experimental Study on the Removal of iron, manganese, Ammonia and
Nitrogen from Groundwater in Small Villages and Towns in Northeast China.
Declaration of Competing Interest Changchun: Jilin University, pp. 35–36. Master thesis.
Guangxi Comprehensive Design Institute iron and Manganese Removal Test Group,
1981. The application of Mashan manganese sand in iron and manganese removal.
The authors declare that they have no known competing financial
Build. Technol. Commun. Water Supply Drain. (06), 42–44.
interests or personal relationships that could have appeared to influence Guo, Y., 2017. Study on the Simultaneous Removal of Ammonia Nitrogen and
the work reported in this paper. Manganese by Iron-Manganese Oxide Film Catalytic Oxidation in Groundwater.
Xi’an University of Architecture and Technology ,. PhD thesis.
He, L., 2007. Efficacy of Potassium Permanganate Compound in Treatment of Micro-
Data availability pollution of Source Water in Dongguan Section of the Dongjiang River. Qingdao
Technological University.
Data will be made available on request. He, L., Guibai, L., Lv, M., Yu, L., 2008. Study on the treatment of source water from
Zhongtang Water Plant by potassium permanganate compound. J. Qingdao Technol.
Univ. 29 (1), 63–67.
Jia, H., 2015. Experimental Study on Removal of Manganese from Groundwater by
Acknowledgments Modified River Sand Filter Media. Jilin University, Changchun.
Jiang, C., 2000. Research on the Pollution Removal Efficiency of Combined
Permanganate Compound and Powdered Activated Carbon. Harbin Jianzhu
I want to thank a lot of people here for their help to finish this review University Engineering. PhD thesis.
paper. Xing Du at Guangdong University of Technology; Haiyang Yang Jiang, C., Ma, J., Li, G., 2000a. Combination of potassium permanganate and powdered
activated carbon to remove trace organic pollutants in water. J. Harbin Jianzhu
and Langming Bai at Harbin Institute of Technology; Bingqian Yang, Univ. 33 (06), 45–49.
Zhaoyang Su, Muhammad Saboor Siddique, Mengjie Liu and Jinjin Zhao Jiang, C., Ma, J., Li, G., 2000b. Potassium permanganate strengthen the adsorption
at Research Center for Eco-Environmental Sciences, Chinese Academy of performance of powdered activated carbon. J. Harbin Jianzhu Univ. 33 (06), 40–44.
Jiang, C., Ma, J., Wang, Z., Zhang, H., Li, G., 2001. Combination of potassium
Sciences; Professor Nigel J.D. Graham at Imperial College London. permanganate and powdered activated carbon to treat micro-polluted source water.
China Water Wastewater 17 (03), 12–15.
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