Environmental Science and Pollution Research (2020) 27:15337–15349

https://doi.org/10.1007/s11356-020-08046-2

RESEARCH ARTICLE

Advanced landfill leachate biochemical effluent treatment using

Fe-Mn/AC activates O3/Na2S2O8 process: process optimization,
wastewater quality analysis, and activator characterization
Zhanmeng Liu 1 & Liang Pan 1 & Fengping Hu 1 & Yunqi Hu 1

Received: 14 July 2019 / Accepted: 10 February 2020 / Published online: 19 February 2020
# Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
A novel catalyst of Fe-Mn/AC was prepared and used as a heterogeneous catalyst to activate O3/Na2S2O8 for landfill leachate
biochemical effluent treatment. The experimental results indicated that the highest COD (84%) and color (98%) removal was
obtained at Fe-Mn/AC dosage 1.2 g/L, O3 concentration 1.2 g/L, Na2S2O8 dosage 6 g/L, initial pH 10, and reaction time 100 min.
Three-dimensional and excitation emission matrix (3D-EEM) fluorescence spectrometry, Fourier transform infrared spectrosco-
py (FTIR), and gas chromatography mass spectrometry (GC/MS) of wastewater samples before and after treatment demonstrated
that the leachate biochemical effluent contained a large amount of humic and fulvic acid organic compounds. After treatment with
this coupling system, both the pollution level of dissolved organic matter (DOM) and the fluorescence intensity declined. The
micro morphology of Fe-Mn/AC was characterized using scanning X-ray diffraction patterns (XRD), electron microscope
spectra (SEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy. It can be con-
cluded that the microscopic morphology of the catalyst is porous. The main active components are amorphous MnO2 and
multivalent iron oxides. Furthermore, the Fe-Mn/AC catalyst showed great reusability; the removal efficiency of COD was only
reduced from 84% to 79% at the fourth reaction. Moreover, the COD removal efficiency could recover to 81% after catalyst
regeneration.

Keywords Activator characterization . Fe-Mn/AC . Leachate biochemical effluent . Reusability . Sulfate radical oxidation .
Spectrum analysis

Introduction be treated efficiently in order to eliminate the potential for the

pollution of ground water and surface water. In practice, the
Sanitary landfill is widely applied as the most common tech- treatment of landfill leachate continues to be a thorny problem
nique in the management of municipal solid waste due to its (Postacchini et al. 2018). Biological degradation is the most
low cost and simple operation (Calabrò et al. 2015, 2018; prevalent technology used for the treatment of landfill leachate
Renou et al. 2008). However, a major issue associated with due to its low cost (Ahmed and Lan 2012; Chemlal et al.
solid waste landfilling is the generation of leachate (Clarke 2014). However, biological degradation alone cannot treat
et al. 2015). Landfill leachates are high-strength polluted landfill leachate efficiently, and the effluent does not always
wastewaters characterized by high concentrations of toxic meet the national discharge standards (Kumiawan et al. 2006).
and carcinogenic chemicals (Amor et al. 2015; Ma et al. After treatment with a biological process, there are still many
2018; Stefania et al. 2018). Therefore, landfill leachate should residual persistent pollutants in the leachate effluent (Abood
et al. 2014) which require further treatment. The treatment of
Responsible editor: Vítor Pais Vilar leachate biochemical effluent is a significant challenge be-
cause of its residual persistent pollutants.
* Zhanmeng Liu Advanced oxidation processes (AOPs) have been widely
[email protected] applied in the treatment of wastewater containing different
organic compounds that are non-biodegradable or toxic to
1
School of Civil Engineering and Architecture, East China Jiao Tong microorganisms. Typical AOP systems for leachate treatment
University, 808 East Shuanggang Road, Nanchang 330013, China have been widely studied including electro catalytic oxidation
15338 Environ Sci Pollut Res (2020) 27:15337–15349

(Feng and Li 2003), wet air oxidation (Zhou et al. 2018), the reaction system and does not cause secondary pollution to
ozonation (Broséus et al. 2009), Fenton (Tusar et al. 2012), the wastewater (Liu et al. 2017). Among the various hetero-
or Fenton-like oxidation (Bokare and Choi 2014), as well as geneous metal catalysts studied, Fe and Mn have been widely
various combinations of these systems. The use of ozone used due to their easy availability, stable properties, and high
alone for leachate treatment has the disadvantages of low re- catalytic activity (Jo et al. 2014). Saputra and his coworkers
moval efficiency and insufficient oxidizing capacity (Amr (Saputra et al. 2013) have used three different heterogeneous
et al. 2013). However, the use of UV/O3 (Nawrocki and metal catalysts (Mn3O4, Co3O4, and Fe3O4) to catalyze per-
Fijołek 2013), O3/H2O2 (Bourgin et al. 2017), UV/O3/H2O2 sulfate treatment of phenol-containing wastewater. Under the
(Cortez et al. 2010), and other methods combined with ozone optimal reaction conditions, 25 mg/L of phenol could be
treatment of leachate can significantly increase the reaction completely removed after 20 min.
efficiency and oxidative degradation ability. In this study, a novel catalyst of Fe-Mn/AC was prepared
In recent years, persulfate (S2O82−) has drawn increasing and used as a heterogeneous catalyst to activate O3/Na2S2O8
attention as an alternative for the oxidation of contaminants for the generation of SO4−. This was used to oxidize the re-
and is considered promising (Devi et al. 2016). S2O82− itself is sidual pollutants in the leachate biochemical effluent, and the
a strong oxidant with a standard oxidation potential (E°) of related experimental parameters were optimized. The waste-
2.01 V (Matzek and Carter 2016). Furthermore, S2O82− can be water sample, before and after treatment with the Fe-Mn/AC
activated to form a powerful sulfate radical (SO4−, E° = 2.6 V) catalytic O3/Na2S2O8 system, was analyzed using 3D-EEM,
by heat (Miao et al. 2018), transition metals (Gao et al. 2018), FTIR, and GC-MS. The Fe-Mn/AC was characterized by
UV light (An et al. 2015), and so on. It has been demonstrated XRD, SEM, XPS, and FTIR, before and after use. The reuse
by related studies that a broad spectrum of organic pollutants and regeneration of the Fe-Mn/AC catalyst were also
can be rapidly degraded using SO4−· oxidation (Yang and investigated.
Ezyske 2011). The advanced oxidation process based on sul-
fate radicals has strong oxidative capacity and low cost, which
facilitate its potential application in wastewater treatment. Materials and methods
It is well known that the O3/H2O2 advanced oxidation pro-
cess has a wide range of applications in water and wastewater Leachate sampling
treatment (Zhao et al. 2017). Similar to H2O2, there is also a –
O–O– bond in the structure of persulfate. Considering the Leachate samples were obtained from Maiyuan refuse landfill
similar structure of H2O2 and S2O82−, the O3/Na2S2O8 oxida- of Nanchang, China. The samples were put in acid-pre-treated
tion system should have similar oxidation characteristics. polyethylene bottles, transported to the laboratory, and then
Experimental studies (Urs 2003) have shown that when ozone stored at 4 °C. General characteristics of the leachate are
gas is introduced into persulfate solution, S2O82− can be acti- shown in Table 1.
vated to produce SO4−·; at the same time, a large amount of
·OH is produced, which further enhances the degradation of Fe-Mn/AC preparation
organic pollutants (Eqs. 1~6).
Activated carbon pretreatment The activated carbon selected
O3 þ OH− →HO2 − þ O2 ð1Þ
in this study was purchased from Stace Carbon Corporation
O3 þ HO2 − →HO2 − þ O3 − ð2Þ (Nanchang). Before the experiment, the activated carbon was
O3 þ H2 O→  OH þ O2 þ OH −
ð3Þ cleaned by ultrasonic for 1 h and then washed with distilled
water. Finally, the pre-treated activated carbon was dried at
− −
S2 O8 2−
þ OH→HSO4 þ SO4  þ1=2O2 ð4Þ 80 °C and stored in a desiccator.
− −
SO4  þ  OH→HSO4 þ 1=2O2 ð5Þ
Preparation of the Fe-Mn/AC catalyst Briefly, a mixture con-
SO4 −  þOH−→SO4 2− þ OH ð6Þ tains KMnO4 and FeNO3·9H2O, with a molar ratio of Fe3+ to
Fe2+ of 2:1. Then, it was stirred for 1 h at 60 °C in a water bath
In addition, the use of a catalyst can further improve the
thermostat magnetic stirrer (stirring speed was medium).
removal efficiency. Some studies have shown that the appli-
During this process, NaOH solution was added to keep the
cation of heterogeneous metal catalysts to catalyze oxidant for
pH in the range 7~8. This was stirred for 12 h and then filtered.
treatment of wastewater cannot only effectively improve the
Then, the residue was washed several times with distilled
removal of pollutants, but also reduce the dosage of oxidant
water, dried, and ground to obtain iron and manganese oxide.
(Akhtar et al. 2011; Keykavoos et al. 2013; Zhang et al. 2018).
An appropriate amount of the dried and ground iron and man-
Moreover, compared with the homogeneous catalyst, the het-
ganese oxide was added to distilled water along with the
erogeneous metal catalyst can be effectively separated from
pretreated activated carbon. Then, oscillatory impregnation
Environ Sci Pollut Res (2020) 27:15337–15349 15339

Table 1 Main water quality

indicators for wastewater Color/ pH COD/mg/ BOD5 NH3-N/mg/ TS/mg/L
times L L

650–750 5–6 1000–1400 300–400 100–150 260

Cd2+/μ/L As3+/μg/L Hg2+/μg/L Cr3+/μg/L Cr6+/μg/L Pb2+/μg/L
0.05 1.42 0.04 0.39 0.03 0.09

was performed for 8–10 h to make sure the iron and manga- Spectrum analysis of a wastewater sample
nese oxide were fully loaded onto the activated carbon.
Finally, the mixture was dried, placed in muffle furnace, heat- 3D-EEM fluorescence spectra
ed at 3 °C/min to 450 °C, and calcined for 2 h. The calcined
product was Fe-Mn/AC catalyst. The excitation emission matrix (EEM) fluorescence was de-
termined using a fluorescence spectrophotometer (Hitachi
Catalytic oxidation experiment F-2000). Referring to literature (Zhu et al. 2012) and optimiz-
ing experiment many times, scanning parameters were set as
As shown in Fig. 1, the system included an oxygen tank, follows: excitation wavelength: 220–500 nm, scan wave-
bubble stone, ozone generator (HY-001-5A, Guangzhou length intervals: 20 nm, slits: 10 nm; emission wavelength:
Jiahuan Electric), and a reactive column made of 250–600 nm, scan wavelength speed: 1200 nm/min, slits:
Plexiglas, the cover of which could be moved. 10 nm; the voltage of photomultiplier: 700 V, the illuminant
Moreover, the pipes connecting various parts of the reac- of excitation: 150 W xenon arc lamp, response time:
tion column were all of PVC. In addition, ozone gas gen- automatic.
erated by the ozone generator is introduced into the reac-
tion column through the bubble stone at the bottom of the FTIR spectroscope
reactor, and the off-gas produced by the reaction was
absorbed by KI solution. The wastewater samples were analyzed by FTIR spectropho-
The single factor control variable method was used to tometer (Mohamed et al. 2017) (model D/Max-RC). Briefly,
study the influence of each factor to obtain an optimal the wastewater samples before and after treatment were dried
experimental condition. First, using 0.1 mol/L sulfuric and mixed with pre-dried KBr powder, respectively, and then
acid or sodium hydroxide solution to adjust the solution were both sufficiently ground and pressed in a pellet which
pH to the desired values (3, 4, 5, …, 11). Second, the was suitable for FTIR analysis. FTIR spectroscopy was then
wastewater containing a certain concentration of persul- conducted and the spectra were in the range of 4000–
fate (1, 2, 3, …, 8 g/L) leachate was introduced into the 400 cm−1.
reaction column through the peristaltic pump. At the same
time, a certain amount of Fe-Mn/AC catalyst (0.2, 0.4, GC-MS spectrometry
0.6, …, 1.6 g/L) was added. Next, turn on the ozone
generator and adjust the output of ozone (0.2, 0.2, 0.3, Water sample pretreatment To extract as much trace organic
…, 1.6 g/L). Last, a sample was taken from the sampling matter as possible from the leachate, 500 mL of leachate was
port for analysis after the reaction had proceeded for a extracted twice in CH2Cl2 under neutral, basic, and acidic
certain time. conditions. The organic phases extracted under neutral, alka-
line, and acidic conditions were combined and the water in the
extract was absorbed using with anhydrous sodium sulfate. A
rotating evaporator was used to inject 2–3 mL of sample con-
centrate into chromatographic column at 45 °C. First, the non-
polar organic matter was eluted with n-hexane; then, the aro-
matic hydrocarbons were eluted with benzene. Finally, the
remaining organic substances (such as polar phenols) were
eluted with ethanol. These were concentrated separately to
about 1 mL for later use. The landfill leachate was analyzed
using gas chromatography-mass spectrometry (Agilent
7890A-5975C) before and after treatment. The GC oven tem-
perature was kept at 60 °C; then programmed to reach 260 °C
Fig. 1 Schematic diagram of the experimental apparatus at 5 °C/min. The temperature was kept constant at 260 °C for
15340 Environ Sci Pollut Res (2020) 27:15337–15349

40 min. A split/splitless injector was used in splitless mode Results and discussion
and the injector temperature was 250 °C. Mass spectrographs
were taken at 70 eV in EI mode. The mass range was between Treatment of leachate biochemical effluent
m/z 30 and 425 (Zhang et al. 2013). with the Fe-Mn/AC catalytic O3/Na2S2O8 system

Effect of Na2S2O8 dosage on COD and color removal

Microscopic morphological characterization
of Fe-Mn/AC It is seen from Fig. 2 that a higher Na2S2O8 dosage generally
favored COD and color removal. The COD and color removal
XRD patterns efficiency first gradually increased with Na2S2O8 dosage from
1 to 6 g/L. When the Na2S2O8 dosage was 6 g/L, the removal
To determine the crystalline phases, the Fe-Mn/AC was ana- efficiency of COD and color reached 84% and 98%, respec-
lyzed using XRD with an X-ray diffractometer (model tively, which was significantly changed from that of low-dose
D/Max-RC, Japan) and with Cu-Ka radiation in the 2θ range persulfate reaction. The reason for this might be that with the
of 5.00–79.98° at a scan rate of 6°/min. increasing dosage of Na2S2O8, on the one hand, the collision
probability between persulfate and metal ions on activated
carbon increases. This results in a large number of –O–O–
SEM micrograph
cleavage in the S2O82− to generate SO4−· (Lee et al. 2010);
on the other hand, ozone can produce ·OH, and then, ·OH can
The surface morphology of the Fe-Mn/AC was determined
activate S2O82− and cause it to decompose rapidly to generate
using SEM (model S-3400 N II/HORIBAEX-250, Japan).
SO4−· (Eqs. 3 and 5) (Soubh and Mokhtarani 2016; Urs 2003);
The samples were prepared as follows. A small amount of
so, the removal efficiency of COD in the solution increases.
sample was fixed on a sample stub using conductive carbon
However, when the Na2S2O8 dosage was further increased,
glue, then pressed flat, and dried on a heating plate. An ion
the oxidation effect was inhibited and the removal efficiency
sputter apparatus was used to coat the surface of the sample
of COD and color did not improve. There are two main rea-
with platinum to a thickness of 30 A.
sons for this: (1) excessive SO4−· quenches itself (Eq. 7), mak-
ing the S2O82− concentration decrease (Li et al. 2013), and (2)
XPS spectra excessive S2O82− also reacts with SO4−· and consumes SO4−·
reactive groups in solution (Eq. 8) (Dhaka et al. 2017; Salari
XPS spectra were produced using a Kratos AXIS Ultra DLD et al. 2009).
system (Kratos Analytical, Manchester, United Kingdom),
SO4 −  þSO4 −  →S2 O8 2− ð7Þ
equipped with Al Ka radiation (hv = 1486.6 eV). It is conve-
− −
nient to record XPS spectra after cleaning each specimen SO4  þS2 O8 →SO4
2− 2−
þ S2 O8 ð8Þ
using Ar to etch (5 kV, 20 mA) the surface. The analyzer
was fixed perpendicular to the sample surface with a detection
angle of 45° and operated at the constant-pass energy of 20 eV.
In addition, the step size was set at 0.02 eVand each peak was
scanned twice to ensure the acquisition of high-resolution
spectra.

FTIR spectroscopy

The functional groups and structure of the Fe-Mn/AC catalyst

were using a Spectrum OneNTS Fourier transform infrared
spectrometer. Regarding the specific operation method
(Mohamed et al. 2017), at normal temperature, a small amount
of pre-dried catalyst and excess KBr were carefully ground on
an agate mortar. For testing, the powder was pressed for 3–
5 min under a certain pressure to form a sheet; then, the related
spectra were measured and used a Fourier spectrometer. The Fig. 2 Effect of Na2S2O8 dosage on the COD and color removal (Fe-Mn/
data were imported into Origin software for drawing and AC dosage = 1.2 g/L, O3 concentration = 1.2 g/L, pH = 10.0, reaction
analysis. time = 120 min)
Environ Sci Pollut Res (2020) 27:15337–15349 15341

Effect of ozone concentration on COD and color removal

As is seen from Fig. 3, the change in the ozone concentration

has great influence on the oxidation effect. When ozone con-
centration increased from 0.2 to 1.2 g/L, the COD removal
efficiency was significantly improved from 52.6 to 84%. The
main reason might be that as the concentration of ozone in-
creases, more ozone molecules react with the catalyst and
continue to generate ·OH. At the same time, ·OH reacts rap-
idly with organic compounds due to its strong oxidizing and
non-selective properties. On the other hand, ·OH can activate
S2O82− and cause it to decompose rapidly to generate SO4−·.
This strengthens the ability to degrade organic substances, and
the removal efficiency of COD is effectively improved. Fig. 4 Effect of Fe-Mn/AC dosage on the COD and color removal (O3
However, when ozone concentration exceeds 1.2 g/L, the re- concentration = 1.2 g/L, Na2S2O8 dosage = 6 g/L, pH = 10.0, reaction
moval efficiency of COD and color do not improve, because time = 120 min)
ozone and organic matter in the wastewater compete for reac-
tion with the ·OH (Forni et al. 1982); thus, the free radical and color increases gradually. When the catalyst in solution
concentration in the solution is reduced. This has a negative was > 1.2 g/L, the removal efficiency of COD did not change
effect on the degradation of organic matter. clearly and even showed a slight decreasing trend. The reason
for this might be that excessive Fe2+ reacts with ·OH and
Effect of Fe-Mn/AC dosage on COD and color removal SO4−· to reduce the concentration of SO4−· and ·OH, thereby
reducing the capacity for oxidative degradation of organic
A suitable catalytic dosage is necessary for oxidation. Too pollutants. At the same time, too much Mn4+ is oxidized by
high and too low catalytic dosage results in an unfavorable ozone to a higher valence state, after which it consumes dis-
oxidation. The effect of the Fe-Mn/AC dosage on oxidation solved ozone in the water. The high-valence Mn7+ has poor
performance is shown in Fig. 4. It is obvious that, as the ability to oxidize organic matter (Nawaz et al. 2016).
catalyst dosage increased, the removal efficiency of COD
S2 O8 2− þ Mnþ →SO4 −  þSO4 2− þ Mnðnþ1Þþ ð9Þ
and color improved. Transition metal ions from the catalyst
transfer an electron to S2O82− so that the –O–O– in S2O82−
breaks to form SO4−· (Eq. 9). In addition, the catalyst can Effect of reaction time on COD and color removal
promote ozone decomposition to produce ·OH and enhance
the oxidative degradation of organic matter (Legube and The effect of reaction time on the oxidation performance is
Leitner 1999). In this case, the removal efficiency of COD shown in Fig. 5. Both COD and color removal efficiency are

Fig. 3 Effect of O3 concentration

on the COD and color removal
(Fe-Mn/AC dosage = 1.2 g/L,
Na2S2O8 dosage = 6 g/L, pH =
10.0, reaction time = 120 min)
15342 Environ Sci Pollut Res (2020) 27:15337–15349

high (84% and 98%, respectively) when the reaction time is

100 min. The removal efficiency remains stable at longer
times. This is because organic pollutants consume a large
number of ·OH and SO4−·, so the subsequent degradation
ability of this oxidation process is reduced. Moreover, as the
reaction proceeds, most of the easily degradable and partially
un-degradable soluble organic compounds are completely de-
graded, while the proportion of refractory organic compounds
increases. As a result, the removal efficiency of related indi-
cators no longer rises.

Effect of pH on COD and color removal

As shown in Fig. 6, with increase of the pH, the removal Fig. 6 Effect of pH on the COD and color removal (Fe-Mn/AC dosage =
efficiency of COD improved. Under alkaline condition, the 1.2 g/L, Na2S2O8 dosage = 6 g/L, O3 concentration = 1.2 g/L, reaction
removal efficiency of COD is obviously better than in acid time = 120 min)
condition. In alkaline conditions, the self-decomposition reac-
tion of ozone in the solution is accelerated by OH−, the de- after the anaerobic-anoxic-aerobic treatment. The residual cal-
composition of ·OH can react quickly and non-selectively cium ions formed Ca(OH)2 precipitate when the wastewater
with organic pollutants, and ·OH can activate S2O82− at high was alkaline, which affected the catalytic oxidation activity of
pH to produce SO4−·. This is why the removal efficiency of the catalyst. Taking COD and color removal into consider-
COD is only 41.2% when pH = 3, but 84% when pH = 10. ation, it is suggested that pH = 10 would be appropriate for
However, when the wastewater is adjusted to pH 10 and con- the treatment of this wastewater. It is worth noting that the
tinues to increase, the removal efficiency of COD in the efflu- effluent should be neutralized after treatment to prevent sec-
ent water is not significantly improved. This is mainly because ondary pollution to natural water bodies (Stefania et al. 2018).
·OH is the main oxidizing group in the solution. When the pH
of the reaction solution is over 10, the activity of ·OH de- Reuse and regeneration of the Fe-Mn/AC catalyst
creases gradually; thus, the degradation ability of organic mat-
ter in wastewater is reduced. In addition, it was found in the An important index for evaluating catalyst is whether a cata-
experiment that the flocculent precipitate appeared in the lyst can maintain high activity after repeated use. To investi-
wastewater under strongly alkaline condition, because the gate the service life of the Fe-Mn/AC catalyst, uniform exper-
landfill leachate contained a high concentration of calcium imental conditions were set: persulfate dosage 6 g/L, O3 con-
ion and the calcium ions that were not completely removed centration 1.2 g/L, catalyst dosage 1.2 g/L, and reaction time
120 min. Samples from the same batch of catalyst were used
for the tests of catalytic oxidation to determine. Consider the
effect of the number of reuses of the catalyst (Fe-Mn/AC) on
the degradation of organic matter. The Fe-Mn/AC catalyst was
repeatedly washed and dried with deionized water after each
use.
As shown in Fig. 7, the Fe-Mn/AC was used, collected,
rinsed, dried, and recycled for four times. The COD removal
efficiency decreased from 84 to 79% at the fourth catalysis.
The concentration of metal ions in the effluent after each treat-
ment was determined using an atomic absorption spectropho-
tometer. The results showed that only trace iron and manga-
nese ions were eluted after the treatment. The catalyst used
four times was washed with deionized water and calcined at
450 °C in a muffle furnace. After calcination, the catalytic
activity of the catalyst was restored to a certain extent, and
Fig. 5 Effect of reaction time on the COD and color removal (Fe-Mn/AC
the removal efficiency of COD reaches 81% again. It is sug-
dosage = 1.2 g/L, Na2S2O8 dosage = 6 g/L, O3 concentration = 1.2 g/L, gested that the reason for the decrease in the catalytic activity
pH = 10.0) of the Fe-Mn/AC catalyst after repeated use is not the
Environ Sci Pollut Res (2020) 27:15337–15349 15343

Fig. 7 Reuse and regeneration of Fe-Mn/AC catalyst

overflow of active metal ions, but probably the deposition of

small molecules of organic matter or impurities in the activat-
ed carbon in the biochemical effluent of the leachate. This
hinders the catalytic reaction on the surface of the activated
carbon. After calcination, the organic matter was removed and
the surface of the activated carbon was improved to a great
extent, thus allowing the Fe-Mn/AC catalyst to recover some
capacity.

Spectrum analysis of wastewater samples before and

after treatment

For this section, the samples of wastewater used for spectrum

analysis were all treated under the same conditions: Na2S2O8
dosage 6 g/L, Fe-Mn/AC dosage 1.2 g/L, O3 concentration
1.2 g/L, pH 10, and reaction time at 100 min.

The 3D-EEM fluorescence spectral analysis

Characterization of the molecular structure of benzene rings or

Fig. 8 3DEEM of water samples before (a) and after (b) treatment
organic substances with conjugated double bonds is possible
using 3D-EEM fluorescence spectroscopy. In recent years, it
indicate substances in the humic acid-like fluorescent re-
has been extensively used in organic structure and transforma-
gion, and Ex/Em = 270/540 nm indicates a substance in
tion analysis. The biochemical tail water of the landfill leach-
the fulvic acid-like fluorescent region.
ate before and after treatment was subjected to fluorescence
Based on Fig. 8, it can be seen that the fluorescence peaks
tests after 10 times dilution and 0.45-μm filtration. The 3D-
of DOM in the biochemical tail water of the landfill leachate
EEM fluorescence spectrum analysis is illustrated in Fig. 8.
are mainly concentrated in the areas of humic and fulvic acid.
Table 2 shows the changes in the fluorescence index (f450/500).
Moreover, the fluorescence intensity in the fluorescence re-
It is observed from Fig. 8 that the DOM of leachate
gion of humic acid is high, which indicates that there are many
biochemical tail water mainly shows fluorescence charac-
complex and difficult to degrade humic acid substances in the
teristic peaks at Ex/Em = 340/410 nm and Ex/Em = 270/
wastewater.
540 nm. The corresponding fluorescence intensities were
2159 and 509, respectively. After treatment, the fluores-
cence characteristic peaks appear mainly at Ex/Em = 300/ Table 2 Fluorescence index of wastewater before and after treatment
380 nm and Ex/Em = 270/540 nm. The fluorescence in-
Samples Before treatment After treatment
tensities are 165 and 373, respectively. According to re-
search data (Baker 2002; Leenheer and Jean-Philippe f450/500 1.52 3.03
2003), Ex/Em = 340/410 nm and Ex/Em = 300/380 nm
15344 Environ Sci Pollut Res (2020) 27:15337–15349

After advanced treatment with Fe-Mn/AC-catalyzed O3/ organic matter (Liu et al. 2015). After treatment, the bands
Na2S2O8, the leachate biochemical tailings still have fluores- at 1646 cm−1 decrease significantly, indicating that the content
cence peaks in the humic acid-like and fulvic acid-like re- with internal conjugated double bonds (C=C, C=O, etc.) de-
gions, but the fluorescence intensity of the two regions de- creases. After treatment, the height of the water sample peak at
creases to a great extent. The intensity of the humic acid fluo- 1385 cm−1 decreases, indicating that the partially saturated
rescence peak was reduced from 2159 to 168 (degradation hydrocarbon group is cracked by sulfate radicals to form or-
reached 92.2%), which means that the main humic acid sub- ganic compounds with relatively low molecular weight
stances were nearly all completely degraded. The intensity of (Zheng et al. 2007). The stretching vibration peak at around
the fulvic acid fluorescence peak decreased from 509 to 373, 1183 cm−1 attenuates after oxidation by the system, indicating
which indicated that the oxidation system of O3/Na2S2O8 cat- that the system reacts strongly with the organic matter in the
alyzed by Fe-Mn/AC had some degradation effect on the leachate. Similarly, the intensity of the characteristic peak at
fulvic acid compounds in the biochemical tail water of the 620 cm−1 is greatly reduced, indicating that the protein content
leachate. is relatively reduced (Guangxia et al. 2012).
The fluorescence index (f450/500) is the ratio of the intensity
of the fluorescence emission spectrum between 450 and
500 nm at an excitation wavelength of 370 nm. The size of GC-MS analysis
f450/500 has a negative correlation with the aromaticity of fulvic
acid in water. The higher the f450/500 ratio, the greater the In order to investigate the changes of organic matter in the
aromaticity of the fulvic acid in water and the fewer benzene biochemical tail water of the landfill leachate before and after
ring structure systems (Wolfe et al. 2002). As shown in treatment, in this experiment used, GC-MS scanning was used
Table 2, the fluorescence index of the biochemical tail water to detect the type and content of organic matter in the
of the leachate increased from 1.52 to 3.03 after treatment with wastewater.
the Fe-Mn/AC catalytic O3/Na2S2O8 coupling system indicat- It is seen from Fig. 10 that the absorption peak of the
ing that the humic acid in the leachate DOM is weakened, the organic matter has a certain degree of decline, and some ab-
aromatic ring structure is reduced, and the humic acid and sorption peaks even disappear. This was likely due to the
fulvic acids are greatly degraded. complex composition of the biochemical effluent in the land-
fill leachate and to the influence of external conditions such as
FTIR spectroscopy analysis instrument accuracy. Many types of organic matter could not
be determined in the end because of low detection similarity.
The FTIR spectra of wastewater samples before and after Therefore, some organic substances with high degrees of
treatment are shown in Fig. 9. The absorption peak at matching were selected for analysis.
3415 cm−1 decreased and the absorption peak at 2353 cm−1 Using spectrum matching analysis, Table 3 shows some
increased, after treated by Fe-Mn/AC-catalyzed O3/Na2S2O8 organic compounds before and after treatment. The retention
systems. This indicated that this oxidation system reacts times are 17.652 min, 28.564 min, 36.264 min, and
strongly with O–H on organic molecules in the wastewater, 39.055 min, representing alkenes, benzene, amides, and alco-
leading to gradual disintegration of the macromolecular hols, respectively. The results showed that these four organic

Fig. 9 FTIR spectra of wastewater samples before (a) and after (b) Fig. 10 GC-MS spectra of water samples before (a) and after (b)
treatment treatment
Environ Sci Pollut Res (2020) 27:15337–15349 15345

Table 3 GC-MS analysis of

wastewater before and after Number Retention time (min) Name of organics Molecular formula
treatment
Before treatment
1 2.88 Chloroiodomethane CH2ClI
2 16.796 2-ethylhexaldehyde C8H16O
3 17.652 Octamethyltetrasiloxane C6H18O3Si3
4 19.193 3.4.5-trimethyl pyrazole C6H11N3
5 21.512 2-ethoxylethyl ether C8H18O3
6 22.587 m-Phenylenediamine C6H4(NH2)2
7 23.308 Triethyl phosphate C6H15O4P
8 24.584 Decamethylcyclopentasiloxa-ne C10H30O5Si5
9 25.435 4-toluenesulfonyl chloride C7H7ClO2S
10 28.564 (4-methoxy phenyl)-two methylamine C9H13NO
11 29.104 1,3-dimethyl-2-imidazolidinone C5H10N2O
12 30.805 Dodecamethylcyclohexasilo-xane C12H36O6Si6
13 33.561 3-ACETAMIDOPHENOL C8H9NO2
14 36.093 5,6-oxy-3-hydroxy-β-ionone C13H2O3
15 36.264 4-formyl-N-isopropyl benzoamide C11H13NO2
16 39.055 cedrol C15H26O
17 40.192 3-(benzoxazole-2-yl) aniline C13H10N2O
18 40.923 4-phenoxy phenol C12H10O2
19 41.001 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5- C12H15N3O5
Triazine-2,4,6(1H,3H,5H)-trione
20 41.136 Tetramethylsilane derivative
21 41.863 3-methoxy phenylthiophenol CH3OC6H4SH
22 41.94 Dimethyl tetradecyl amine C16H35
23 44.69 phytane C20H43
24 45.37 Methyl cyclosiloxane C9H24Si3
25 48.489 dibutyl phthalate C16H22O4
26 49.158 Tetradecamethylhexasiloxn-e C14H42O5Si6
27 51.944 Tetradecylamine C16H35N
28 52.634 Tetramethylsilane derivative
29 55.867 Sixteen methyl seven silox-ane C16H48O6Si7
30 71.775 9-octadecene amide C18H35
After treatment
1 9.874 3-chloropyridine C5H4ClN
2 17.673 Benzyl chloride C7H7Cl
3 19.198 3,4,5-trimethylpyrazole C4H6N2
4 19.8 5-hexyldihydro-2(3H)-furao-ne C10H18O2
5 21.554 Bromobenzene C6H5Br
6 22.597 4-methyl-1,3-phenylenedia-mine C7H11ClN2
7 24.6 Decamethylcyclopentasiloxa-ne C10H30O5Si5
8 29.202 2-chloro-3-nitropyridine C5H3ClN2O2
9 30.811 Dodecylcyclohexylsiloxane C12H36O6Si6
10 36.103 Pentadecane C15H32
11 36.228 Dodecyltrimethylammoniu-m bromide C15H34NBr
12 39.066 1-(2-fluorophenyl)piperazin-e C10H13FN2
13 41.152 3,4-dihydroxyphenyl glycol C8H10O4
14 41.946 Dimethyltetradecylamine C16H35
15 44.327 Kusal C10H6Cl2N24
16 46.195 Phthalate C8H6O4
17 48.489 Dibutyl phthalate C16H22O4
18 51.949 4-ethylbenzaldehyde C9H10O
19 71.791 9-octadecenamide C18H35

substances were removed to a higher degree after treatment toxic or difficult biodegradable organic pollutants. For
with the Fe-Mn/AC-catalyzed O3/Na2S2O8. example, macromolecules with structurally complex
During treatment, the content of organic substances rings were opened, disconnected, and degraded into
such as alkene olefins, benzenes, amides, and alcohols smaller molecules or intermediates. The absorption peak
was obviously reduced, indicating some of the most analysis with retention time of 20–30 min may be the
15346 Environ Sci Pollut Res (2020) 27:15337–15349

It is thus known that activated carbon has been success-

fully loaded with iron and manganese oxide.
From comparison of the XRD diagram before and after Fe-
Mn loading of the activated carbon, it can be seen that the
diffraction peak of Fe2O3 in the X-ray diffraction pattern is
much smaller than before loading. Moreover, the diffraction
peak of FeO becomes stronger after the loading. The main
reason may be that some metal oxides are decomposed under
high-temperature calcination conditions and then reduced to
lower oxidation states by reaction with the carbon matrix
(Carabineiro et al. 2001). Mn appears as a MnO2 diffraction
peak with low peak strength after loading, but does not appear
before loading. This is due to the amorphous form of the
manganese oxide before loading, and the loaded MnO2 is
dispersed on activated carbon, which is easier to detect (Yan
et al. 2010). In general, after loading, the diffraction peaks of
Fig. 11 XRD patterns of the catalyst the metal in the XRD diagram are obviously weakened. This
also shows that the dispersion of Mn and Fe components
product of degradation of macromolecular organic loaded on activated carbon is greater than that of Mn and Fe
matter. in single-metal supported activated carbon.

Characterization and analysis of Fe-Mn/AC SEM micrograph analysis

XRD pattern analysis SEM micrography is commonly used to characterize the

structure and morphology of reagents (Hu et al. 2017).
The XRD patterns of Fe-Mn/AC are shown in Fig. 11. It The SEM micrographs of nano-Fe3O4 (before and after
can be seen that when Fe-Mn is not loaded, the diffraction reaction) are shown in Fig. 12. Scanning electron micros-
peak (JCPDs39-0238) of Fe 2 O 3 at 2θ = 29.4°(022), copy (SEM) images of the catalysts show that their sur-
39.1°(104), and 48° (113) and that the diffraction peak faces have a large number of pore structures. A large
(JCPDs39-0238) of FeO at 2 θ = 35.7°(111), 42.5°(200), number of snowflake-like objects appear on the surface
and 60.1° (220). These results show that Fe existed in the of the activated carbon, which are Fe3O4, MnO2, or other
form of multivalent states before the activated carbon was substances. This indicates that the metal oxide was suc-
loaded. When the iron-manganese compound was loaded cessfully loaded onto the activated carbon, which is con-
onto the activated carbon, the diffraction peak (JCPDs 07- sistent with the XRD analysis results. Moreover, it can be
0230) of C was found at 2θ = 26.7° (002), MnO2 at 2θ = seen from the figure that a large amount of metal oxide is
50.2° (110), and 68.2° (211) from the XRD diagram. dispersed unevenly on the surface of the activated carbon
Furthermore, there were simultaneous diffraction peaks and inside the activated carbon pores. This phenomenon
of Fe2O3 at 2θ = 29.4°, 39.1°, and 48° (JCPDs 39-0238) is mainly due to the use of impregnation methods of
and FeO at 2θ = 35.7°, 42.5°, and 60.1° (JCPDs 39-0238). preparation.

Fig. 12 SEM of Fe-Mn/AC

catalyst
Environ Sci Pollut Res (2020) 27:15337–15349 15347

Fig. 14 FT-IR spectra of the Fe-Mn/AC catalyst

changes, not only in the elemental composition and chemical state,

but also in the surface structure. The Fe-Mn/AC catalysts were
characterized using XPS, and the binding energy was calibrated
using the C1s signal (284.6 eV) and oxygen (531.6 eV) C1 signals
on the surface of each activated carbon catalyst coating.
In Fig. 13, the XPS characterization diagram for the Fe-
Mn/AC catalyst and the corresponding peaks of Fe-2p and
Mn-2p are obvious. It can be seen that both Fe and Mn have
been successfully loaded on the surface of the activated car-
bon and exist mainly in the form of their metal oxides. Mn2p
XPS spectra have two main binding energy peaks at
641.82 eV and 653.53 eV, corresponding to Mn-2p3/2 and
Mn-2p1/2. The spin-orbit split between the Mn-2p3/2 and
Mn-2p1/2 levels is 11.7 eV, which means that the manganese
oxide supported on the activated carbon is MnO2. This is in
good agreement with the manganese ore characterization re-
sults reported by other scholars (Foord et al. 1984). In
Fig. 13c, it is clear that there are two separate 2p orbital states
at 710.26 eV and 723.76 eV, respectively: Fe-2p3/2 and Fe-
2p1/2. The results of the characterization show that the main
forms of iron ions supported on the activated carbon are Fe3+
and Fe2+, in which results are similar to those reported by
other scholars (Singh et al. 2015).

FTIR spectroscopy analysis

As is seen from Fig. 14, the peaks at 1631 cm −1 and

3417 cm−1 are the absorption peaks of the H–O–H bending
vibration (Krehula et al. 2002). These absorption bands are
Fig. 13 XPS spectrum of the Fe-Mn/AC catalyst usually produced by the presence of moisture (water vapor).
This shows that the prepared Fe-Mn/AC catalyst has a porous
XPS spectrum analysis structure and can absorb water from the environment. The
peak at 2362 cm−1 is caused by carbonyl vibration. The
XPS can detect the elements and atomic valence states on the stretching vibration peak near 472 cm−1 is due to the presence
surface of the material to be characterized over a large energy of MnO2 (Singh et al. 2010). The infrared spectrum of Fe2O3
range at low resolution. It is usually employed to understand exhibits a stretching peak at a wavelength of 560 cm−1 and
15348 Environ Sci Pollut Res (2020) 27:15337–15349

790 cm−1, and the infrared spectrum of FeO shows stretching References
peaks at a wavelength around 670 cm−1. Figure 14 shows
stretching peaks at 562 cm−1, 790 cm−1, and 669 cm−1. The Abood AR, Jianguo B, Jiangkun D, Dan Z, Ye L (2014) Non-
biodegradable landfill leachate treatment by combined process of
results show that the activated carbon has successfully been
agitation, coagulation, SBR and filtration. Waste Manag 34:439–
loaded with iron oxides and manganese oxides. In addition, 447
absorption peaks appear in the infrared spectrum near Ahmed FN, Lan CQ (2012) Treatment of landfill leachate using mem-
1032 cm−1 and 1385 cm−1. According to the study (Gomez- brane bioreactors: a review. Desalination 287:41–54
Serrano et al. 1996), the absorption peaks appearing here were Akhtar J, Amin NS, Aris A (2011) Combined adsorption and catalytic
ozonation for removal of sulfamethoxazole using Fe 2 0 3/Ce0 2
due to the presence of –C–O and C–O, respectively. The main loaded activated carbon. Chem Eng J 170:136–144
reason may be that MnO2 and Fe2O3 react with activated Amor C, Torres-Socías ED, Peres JA, Maldonado MI, Oller I, Malato S,
carbon during the loading process to promote the formation Lucas MS (2015) Mature landfill leachate treatment by coagulation/
of these oxidized functional groups. flocculation combined with Fenton and solar photo-Fenton process-
es. J Hazard Mater 286:261–268
Amr SSA, Hamidi Abdul A, Mohd Nordin A (2013) Optimization of
stabilized leachate treatment using ozone/persulfate in the advanced
Concluding remarks oxidation process. Waste Manag 33:1434–1441
An D, Westerhoff P, Zheng M, Wu M, Yang Y, Chiu CA (2015) UV-
activated persulfate oxidation and regeneration of NOM-saturated
Leachate biochemical effluent was treated using the Fe-Mn/
granular activated carbon. Water Res 73:304–310
AC-catalyzed O3/Na2S2O8 system, with Fe-Mn/AC as a het- Baker A (2002) Fluorescence properties of some farm wastes: implica-
erogeneous catalyst. The experimental results proved that it is tions for water quality monitoring. Water Res 36:189–195
an efficient and promising method for the treatment of leachate Bokare AD, Choi W (2014) Review of iron-free Fenton-like systems for
biochemical effluent. The ·OH produced by O3 and the SO4−· activating H 2 O 2 in advanced oxidation processes. J Hazard Mater
275:121–135
formed by the activation of Na2S2O8 could synergistically ox-
Bourgin M et al (2017) Effect of operational and water quality parameters
idize and degrade the pollutants in the wastewater sample, and on conventional ozonation and the advanced oxidation process O3/
the two had significant synergistic benefits. The COD and color H2O2: kinetics of micropollutant abatement, transformation product
removal efficiency reached 84% and 98%, respectively. After and bromate formation in a surface water. Water Res 122:234
treatment with the coupling system, the fluorescence index of Broséus R, Vincent S, Aboulfadl K, Daneshvar A, Sauvé S, Barbeau B,
Prévost M (2009) Ozone oxidation of pharmaceuticals, endocrine
organic matter (f450/500) increased, the fluorescence intensity of disruptors and pesticides during drinking water treatment. Water Res
organic matter, aromaticity of soluble humic acid decreased, 43:4707–4717
and aromatic ring structure of soluble humic acid are all de- Calabrò PS, Gori M, Lubello C (2015) European trends in greenhouse
creased. Alkane olefins, benzenes, amides, and alcohols were gases emissions from integrated solid waste management. Environ
Technol 36:2125–2137
effectively treated, and reactions such as ring opening and chain
Calabrò PS, Gentili E, Meoni C, Orsi S, Komilis D (2018) Effect of the
structure cleavage occurred during oxidation. recirculation of a reverse osmosis concentrate on leachate genera-
The characterization results of the catalyst indicated that the tion: a case study in an Italian landfill. Waste Manag
microscopic morphology of the catalyst was porous. The main S0956053X18301491
active component of the catalyst consisted of amorphous MnO2 Carabineiro SA, Mckee DW, Silva IF (2001) Uncatalysed and catalysed
CO2 reaction using metal catalysts and binary vanadium mixtures
and multivalent iron oxides, and the main metal ion compo- supported on activated carbon. Carbon 39:451–463
nents were Mn+, Fe2+, and Fe3+. Moreover, the XRD pattern Chemlal R et al (2014) Combination of advanced oxidation and biolog-
showed that the diffraction peaks of the metal in the XRD ical processes for the landfill leachate treatment. Ecol Eng 73:281–
pattern were significantly weakened after Fe and Mn were load- 289
ed. This indicated that the Mn and Fe components loaded on the Clarke BO, Anumol T, Barlaz M, Snyder SA (2015) Investigating landfill
leachate as a source of trace organic pollutants. Chemosphere 127:
activated carbon were more dispersed than the Mn and Fe in the 269–275
single-metal-loaded activated carbon. In addition, the Fe-Mn/ Cortez S, Teixeira P, Oliveira R, Mota M (2010) Ozonation as polishing
AC catalyst exhibited strong recyclability, and the treatment treatment of mature landfill leachate. J Hazard Mater 182:730–734
efficiency was still 79% after being used four times. Devi P, Das U, Dalai AK (2016) In-situ chemical oxidation: principle and
applications of peroxide and persulfate treatments in wastewater
systems. Sci Total Environ 571:643–657
Funding information This work was supported by the National Natural
Sciences Foundation of China (Nos. 51468016 and 61640217) and the Dhaka S, Kumar R, Khan MA, Paeng KJ, Kurade MB, Kim SJ, Jeon BH
Technology Development Research Project of Jiangxi (No. (2017) Aqueous phase degradation of methyl paraben using UV-
200171BBH80008). activated persulfate method. Chem Eng J 321:11–19
Feng YJ, Li XY (2003) Electro-catalytic oxidation of phenol on several
metal-oxide electrodes in aqueous solution. Water Res 37:2399–
Compliance with ethical standards 2407
Foord JS, Jackman RB, Allen GC (1984) An X-ray photoelectron spec-
Conflict of interest The authors declare that they have no conflict of troscopic investigation of the oxidation of manganese. Philos Mag A
interest. 49:657–663
Environ Sci Pollut Res (2020) 27:15337–15349 15349

Forni L, Bahnemann D, Hart EJ (1982) Mechanism of the hydroxide ion- more sustainable chemical alternatives. J Clean Prod 183:1021–
initiated decomposition of ozone in aqueous solution. J Phys Chem 1033
86:255–259 Renou S, Givaudan JG, Poulain S, Dirassouyan F, Moulin P (2008)
Gao F, Li Y, Xiang B (2018) Degradation of bisphenol A through transi- Landfill leachate treatment: review and opportunity. J Hazard
tion metals activating persulfate process. Ecotoxicol Environ Saf Mater 150:468–493
158:239–247 Salari D, Niaei A, Aber S, Rasoulifard MH (2009) The photooxidative
Gomez-Serrano V, Pastor-Villegas J, Perez-Florindo A, Duran-Valle C, destruction of C.I. basic yellow 2 using UV/S2O8(2-) process in a
Valenzuela-Calahorro C (1996) FT-IR study of rockrose and of char rectangular continuous photoreactor. J Hazard Mater 166:61–66
and activated carbon. J Anal Appl Pyrolysis 36:71–80 Saputra E, Muhammad S, Sun H, Ang HM, Tadé MO, Wang S (2013) A
Guangxia QI, Yue D, Nie Y (2012) Characterization of humic substances comparative study of spinel structured Mn3O4, Co3O4 and Fe3O4
in bio-treated municipal solid waste landfill leachate. Front Environ nanoparticles in catalytic oxidation of phenolic contaminants in
Sci Eng 6:711–716 aqueous solutions. J Colloid Interface Sci 407:467–473
Hu L et al (2017) Organic matters removal from landfill leachate by Singh SP, Chakradhar RPS, Rao JL, Karmakar B (2010) EPR, FTIR,
immobilized Phanerochaete chrysosporium loaded with graphitic optical absorption and photoluminescence studies of Fe2O3 and
carbon nitride under visible light irradiation. Chemosphere 184: CeO2 doped ZnO–Bi2O3–B2O3 glasses. J Alloys Compd 493:
1071 256–262
Jo YH, Do S-H, Kong S-H (2014) Persulfate activation by iron oxide-
Singh A, Singh A, Singh S, Tandon P, Yadav BC, Yadav RR (2015)
immobilized MnO2 composite: identification of iron oxide and the
Synthesis, characterization and performance of zinc ferrite nanorods
optimum pH for degradations. Chemosphere 95:550–555
for room temperature sensing applications. J Alloys Compd 618:
Keykavoos R, Mankidy R, Ma H, Jones P, Soltan J (2013) Mineralization
475–483
of bisphenol A by catalytic ozonation over alumina. Sep Purif
Soubh A, Mokhtarani N (2016) The post treatment of composting leach-
Technol 107:310–317
ate with a combination of ozone and persulfate oxidation processes.
Krehula S, Popović S, Musić S (2002) Synthesis of acicular α-FeOOH
RSC Adv 6:76113–76122
particles at a very high pH. Mater Lett 54:108–113
Kumiawan TA, Lo WH, Chan GYS (2006) Radicals-catalyzed oxidation Stefania B, Calabrò PS, Rosa G, Nicola M (2018) Selective removal of
reactions for degradation of recalcitrant compounds from landfill heavy metals from landfill leachate by reactive granular filters. Sci
leachate. Chem Eng J 125:35–57 Total Environ 644:335–341
Lee YC, Lo S-L, Chiueh P-T, Liou Y-H, Chen M-L (2010) Microwave- Tusar NN et al (2012) Manganese functionalized silicate nanoparticles as
hydrothermal decomposition of perfluorooctanoic acid in water by a Fenton-type catalyst for water purification by advanced oxidation
iron-activated persulfate oxidation. 44:0–892 processes (AOP). Adv Funct Mater 22:820–826
Leenheer JA, Jean-Philippe C (2003) Characterizing aquatic dissolved Urs VG (2003) Ozonation of drinking water: part I. Oxidation kinetics
organic matter. Environ Sci Technol 37:18A and product formation. Water Res 37:0–1467
Legube B, Leitner NKV (1999) Catalytic ozonation: a promising ad- Wolfe AP, Kaushal SS, Fulton JR, McKnight DM (2002)
vanced oxidation technology for water treatment. Catal Today 53: Spectrofluorescence of sediment humic substances and historical
61–72 changes of lacustrine organic matter provenance in response to at-
Li B, Li L, Lin K, Zhang W, Lu S, Luo Q (2013) Removal of 1,1,1- mospheric nutrient enrichment. Environ Sci Technol 36:3217–3223
trichloroethane from aqueous solution by a sono-activated persulfate Yan J, Khoo E, Sumboja A, Lee PS (2010) Facile coating of manganese
process. Ultrason Sonochem 20:855–863 oxide on tin oxide nanowires with high-performance capacitive be-
Liu ZP, Wu WH, Shi P, Guo JS, Cheng J (2015) Characterization of havior. ACS Nano 4:4247–4255
dissolved organic matter in landfill leachate during the combined Yang D, Ezyske CM (2011) Sulfate radical-advanced oxidation process
treatment process of air stripping, Fenton, SBR and coagulation. (SR-AOP) for simultaneous removal of refractory organic contam-
Waste Manag 41:111–118 inants and ammonia in landfill leachate. Water Res 45:6189–6194
Liu M, Zhang L, Xi B-d, Yu S, Hou L-a (2017) Degradation of cipro- Zhang QQ, Tian B-H, Zhang X, Ghulam A, Fang C-R (2013) He R
floxacin by TiO2/Fe2O3/zeolite catalyst-activated persulfate under Investigation on characteristics of leachate and concentrated leach-
visible LED light irradiation. RSC Adv 7:51512–51520 ate in three landfill leachate treatment plants. Waste Manag 33:
Ma C, He Z, Jia S, Zhang X, Hou S (2018) Treatment of stabilized landfill 2277–2286
leachate by Fenton-like process using Fe3O4 particles decorated Zr- Zhang Y, Zhang Q, Dong Z, Wu L, Hong J (2018) Structural modified
pillared bentonite. Ecotoxicol Environ Saf 161:489–496 CuFe 2O4/persulfate process for acetaminophen scavenging: high
Matzek LW, Carter KE (2016) Activated persulfate for organic chemical efficiency with low catalyst addition. J Chem Technol Biotechnol 94
degradation: a review. Chemosphere 151:178–188 Zhao Z et al (2017) Advanced oxidation removal of hypophosphite by
Miao D, Peng J, Zhou X, Qian L, Wang M, Zhai L, Gao S (2018) O3/H2O2 combined with sequential Fe(II) catalytic process.
Oxidative degradation of atenolol by heat-activated persulfate: ki- Chemosphere 180:48–56
netics, degradation pathways and distribution of transformation in-
Zheng Z, He P-J, Shao L-M, Lee D-J (2007) Phthalic acid esters in
termediates. Chemosphere 207:174
dissolved fractions of landfill leachates. Water Res 41:4696–4702
Mohamed MA, Jaafar J, Ismail AF, Othman MHD, Rahman MA (2017)
Zhou L, Cao H, Descorme C, He Z, Xie Y (2018) Wet air oxidation of
Fourier transform infrared (FTIR) spectroscop. 45:3–29
indole, benzopyrazole, and benzotriazole: effects of operating con-
Nawaz F, Xie Y, Xiao J, Cao H, Li Y, Zhang D (2016) Insights into the
ditions and reaction mechanisms. Chem Eng J 338:496–503
mechanism of phenolic mixture degradation by catalytic ozonation
with a mesoporous Fe3O4/MnO2 composite. RSC Adv 6:29674– Zhu L, Qi H-y, Lv M-l, Kong Y, Yu Y-w, Xu X-y (2012) Component
29684 analysis of extracellular polymeric substances (EPS) during aerobic
Nawrocki J, Fijołek L (2013) Catalytic ozonation—effect of carbon con- sludge granulation using FTIR and 3D-EEM technologies.
taminants on the process of ozone decomposition. Appl Catal B Bioresour Technol 124:455–459
Environ 142-143:307–314
Postacchini L, Ciarapica FE, Bevilacqua M (2018) Environmental assess- Publisher’s note Springer Nature remains neutral with regard to jurisdic-
ment of a landfill leachate treatment plant: impacts and research for tional claims in published maps and institutional affiliations.