http://pubs.acs.

org/journal/acsodf Article

Effect of Different Modification Methods on the Adsorption of

Manganese by Biochar from Rice Straw, Coconut Shell, and Bamboo
Guoliang Chen,* Khamphouvanh Viengvilay, Weijian Yu, Teng Mao, Zhihui Qu, Bixin Liang,
Zhang Chen, and Zhixian Li

Cite This: ACS Omega 2023, 8, 28467−28474 Read Online

ACCESS
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Metrics & More Article Recommendations

ABSTRACT: The adsorption capacity of pristine biochar without

modification is usually low. In this experiment, we comprehen-
Downloaded via 152.52.34.131 on October 14, 2024 at 04:23:28 (UTC).

sively evaluated the adsorption of Mn(II) by biochar with different

modification methods from different biomass. The biochar from
rice straw, coconut shell, and bamboo was produced by pyrolysis at
600 °C under nitrogen and then modified with HNO3, NaOH, and
Na2S, respectively. The results showed that the adsorption
capacities of these modified biochar samples were in the order
Biochar-NaOH > Biochar-Na2S > Biochar-HNO3. Among the
three modification methods, biochar modified with NaOH is the
optimum for the adsorption of Mn(II). However, the same method
of modification has different effects on different biomass
feedstocks. Rice straw: R-C > R-NaOH-C > R-Na2S-C > R-HNO3-C; coconut shell: C-NaOH-C > C-Na2S-C > C-HNO3-C >
C-C; bamboo: B-NaOH-C > B-Na2S-C > B-C > B-HNO3-C. At the pH of 5 and 30 °C, R-C, C-NaOH-C, and B-NaOH-C showed
the highest maximum adsorption capacity for Mn(II). Equilibrium data were evaluated by Langmuir, Freundlich, and Temkin
isotherm models, and the results suggested that the Langmuir model is the most suitable to expound the adsorption behavior of
Mn(II) on R-C, C-NaOH-C, and B-NaOH-C. Overall, the results from this work suggest that the key for preparing biochar
adsorbents with high capacity is to choose the appropriate biomass feedstock and modification method.

1. INTRODUCTION groups), S-containing groups (e.g., sulfonic groups), and other

Manganese (Mn) is an essential element for living organisms.1 functional groups.5,8 The results of previous studies indicated
However, excess manganese in the environment is very that the feedstock or biochar modified by acids, bases, or metal
harmful. It can cause humans headache and memory loss salts can enhance the adsorption capacity of pristine biochar by
and stress on the growth of plants.2,3 The World Health introducing additional functional groups onto their surfa-
Organization suggested that the Mn concentration in drinking ces.9−11
water should be less than 0.05 mg/L. With the rapid Therefore, this study was to comprehensively evaluate the
development of the manganese mining and industry, the mechanism of chemical modification methods (HNO3, NaOH,
concentration of Mn in water is increasing. It has preoccupied and Na2S) on enhancement of the adsorption capacity of
a growing number of scientists in recent years.4 biochar adsorbents for Mn(II) removal and find out the
Biochar has been widely used as adsorbents for removing promising modification method. This experiment was based on
pollutants from water and wastewater due to its special surface low-cost, wide-ranging rice straw, coconut shell, and bamboo
structure.5 Numerous factors including feedstocks and feedstock. This work will provide support for the preparation
operation parameters of the pyrolysis process (temperature,
of biochar with high adsorption capacity and solving the
duration, heating rate, and pressure) affect the yield and quality
of biochar. However, the adsorption capacity of pristine problems caused by agricultural and forestry waste.
biochar without modification is usually very low.6,7 Mod-
ification typically changes the properties of biochar and Received: April 21, 2023
increases the adsorption capacity to numerous pollutants. Accepted: July 18, 2023
Functional groups on biochar surfaces can be classified into Published: July 26, 2023
several groups: O-containing groups (e.g., carboxylic groups,
phenolic groups, and lactonic groups), N-containing groups
(e.g., amine-N groups, pyrrolic-N groups, and graphitic-N
© 2023 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsomega.3c02685
28467 ACS Omega 2023, 8, 28467−28474
ACS Omega http://pubs.acs.org/journal/acsodf Article

2. MATERIALS AND METHODS flask. The mixtures were shaken in a thermostatic shaker at 25
2.1. Preparation of Biochar and Modified Biochar. °C for 3 h and then filtered. The concentration of Mn2+ in the
Rice straw, coconut shell, and bamboo branch feedstocks were supernatant was measured by an atomic absorption spec-
collected from Xiangtan, Hunan Province, China. All the trophotometer (Agilent 240FS, USA). The removal rate (E)
biomass feedstocks were washed with distilled deionized water and adsorption capacity (Q) were calculated by eqs 3 and 4:5
several times and dried at 60 °C for 48 h. The dried biomass
was filled into the crucible and compacted and placed in a box-
(3)
type atmosphere furnace (JQF1100-3, Shanghai Jiugong
Electric Co., Ltd., China) for pyrolysis at 600 °C under the
protection of nitrogen for 2 h. The obtained biochar was (4)
ground into powder (<0.154 mm) and stored in a sealed bag 2+
before use.12,13 The rice straw biochar was recorded as R-C, C0 (mg/L) is the Mn concentration in solution; Ct (mg/L) is
the coconut shell biochar was recorded as C-C, and the the Mn2+ concentration in solution at time t; W (g) is the mass
bamboo biochar was recorded as B-C. of the adsorbent; V (L) is the volume of solution; Q (mg/g) is
To prepare modified biochar, 20 g of obtained biochar was the adsorption capacity. The biochar that had the maximal
placed in three 500 mL beakers, and 200 mL of 10% HNO3, 3 adsorption capacity was selected for the subsequent experi-
mol/L NaOH, and 1.5 mol/L of Na2 S were added, ments.
respectively. The mixtures were stirred continuously with a 2.3.2. Biochar Dosage, pH, and Temperature. To
speed of 150 rpm for 180 min at 25 °C and then separated by investigate the influence of the biochar dosage on the
filtration. The samples were repeatedly washed with deionized adsorption of Mn2+, 10, 50, 100, 150, 200, 250, 300, 350,
water until the pH of the filtrate was nearly neutral and then and 400 mg of biochar were added to 50 mL of 50 mg/L
were oven-dried again at 60 °C for 24 h. The nitric acid- MnCl2 solution, respectively. The influence of pH and
modified rice straw biochar was recorded as R-HNO3-C, the temperature experiments were carried out by mixing 50 mg
sodium hydroxide-modified rice straw biochar was recorded as of biochar and 50 mL of MnCl2 solution with a series of
R-NaOH-C, and the sodium sulfide-modified rice straw different pH (2, 3, 4, 5, 6, and 7, adjusted with 1 mol/L NaOH
biochar was recorded as R-Na2S-C. The nitric acid-modified or HCl) and at different temperatures (20, 25, 30, 35, and 40
coconut shell biochar was recorded as C-HNO3-C, the sodium °C), respectively.
hydroxide-modified coconut shell biochar was recorded as C- All the mixtures were shaken in a thermostatic shaker for 3 h
NaOH-C, and the sodium sulfide-modified coconut shell to achieve equilibrium and then filtered. The concentration of
biochar was recorded as C-Na2S-C. The nitric acid-modified Mn2+ in the supernatants was measured by an atomic
bamboo biochar was recorded as B-HNO3-C, sodium absorption spectrophotometer.
hydroxide-modified bamboo biochar was recorded as B- 2.3.3. Adsorption Kinetics and Isotherms. For adsorption
NaOH-C, and sodium sulfide-modified bamboo biochar was kinetics, 50 mg of biochar and 50 mL of 50 mg/L MnCl2
recorded as B-Na2S-C. solution were added into a 250 mL conical flask. The pH of the
2.2. Properties of Biochar. 2.2.1. Biochar Yield. The mixture was adjusted to around 5, shaken at 25 °C, and
mass of the crucible was M0; the crucible was filled and sampled at 10, 20, 30, 60, 120, 180, 300, 480, 720, 1080, and
compacted with biomass, and the mass was M1. It was 1680 min. The adsorption isotherm experiment was carried out
subjected to pyrolysis in a box-type atmosphere furnace under by mixing 50 mg of biochar and 50 mL of different
a N2 atmosphere, and the mass was M2 after natural cooling. concentrations of MnCl2 solution (10, 20, 30, 40, 50, 75,
The biochar yield (Wbiochar) was calculated following eq 1: 100, 150, and 200 mg/L) at 25 °C for 3 h. All samples were
measured immediately after separation.
2.3.4. Statistical Analysis. Each experimental treatment was
(1) conducted in triplicate to reproduce conditions, and the results
were presented as the means of each treatment. Graphical work
2.2.2. Biochar Ash and pH. The ash content of biochar was was carried out using Origin 8.0 (OriginLab Corporation,
measured by referencing to “Experimental Methods for Northampton, MA, USA).
Charcoal and Charcoal” (GB/T177664-1999). We weighed
about 400 ± 0.1 g of the biochar sample and recorded it as M0. 3. RESULTS AND DISCUSSION
We placed it into the bottom of the crucible and then weighed
3.1. Properties of Biochar. The yield, ash, and pH data of
the mass M1. We opened and placed it in a high-temperature
different biochar samples are displayed in Table 1.
electric furnace, kept at 800 °C for 4 h, and naturally cooled it
As shown in Table 1, the biochar yields of rice straw,
to give a mass M2. The calculation formula for the ash content
coconut shell, and bamboo are 33.86, 34.69, and 27.88%,
(Wash) of biochar is shown in eq 2:
respectively. The major nonash content of biomass feedstock is
lost during pyrolysis. The adsorption capacity of biochar is
(2)
usually related with the surface area, functional groups, and
components of biochar.15,16 Chemical modification has been
The pH of biochar was measured with a pH meter according reported to enhance its performance as an amendment or
to the method of Chen et al.14 absorbent by introducing additional functional groups onto its
2.3. Batch Adsorption Experiments. 2.3.1. Adsorption surfaces.17,18 After modification by HNO3, NaOH, and Na2S,
of Pristine Biochar and Modified Biochar. Fifty and 100 mg there were significant differences among the pH and ash
of pristine biochar and modified biochar were added to 50 mL content of obtained biochar. It may be caused by the change of
of 10, 50, and 100 mg/L MnCl2 solution with a pH of 5 the surface area, functional groups, and components during the
(adjusted with 1 mol/L NaOH or HCl) in a 150 mL conical modification process, and the surface area, functional groups,
28468 https://doi.org/10.1021/acsomega.3c02685
ACS Omega 2023, 8, 28467−28474
ACS Omega http://pubs.acs.org/journal/acsodf Article

Table 1. Biochar Yield, Ash, and pH beneficial for adsorption. For coconut shell and bamboo, C-
NaOH-C and B-NaOH-C had the maximum adsorption
biocharcoal yield (%) ash content (%) pH value
capacity. However, for rice straw, the results of modification
R-C 33.86 32.78 10.12 were not ideal. The adsorption capacities of R-NaOH-C, R-
R-HNO3-C 25.43 3.24
Na2S-C, and R-HNO3-C at different manganese ion concen-
R-NaOH-C 15.07 8.50
trations were lower than that of R-C without modification.
R-Na2S-C 16.75 8.65
Modification with alkali led to the micropore volume of
C-C 34.69 6.75 9.70
C-HNO3-C 2.75 4.20
biochar to be decreased and thus resulted in a smaller
C-NaOH-C 3.42 8.43
surface.25−27 This is disadvantageous for adsorption. The
C-Na2S-C 3.95 8.92 results indicated that the same method of modification had
B-C 27.88 7.93 9.49 different effects on different biomass feedstocks. The physical
B-HNO3-C 4.32 3.14 and surface chemical properties of biochar or biomass
B-NaOH-C 3.97 7.99 feedstock should be carefully considered in the selection of
B-Na2S-C 4.70 8.21 pretreatment methods.
Therefore, the unmodified biochar R-C, B-NaOH-C, and C-
NaOH-C were selected for the subsequent experiments.
and components of obtained biochar are associated with 3.3. Effect of the Adsorbent Dosage. It is very necessary
modifying reagents. This was in agreement with other research to find the appropriate dosage of biochar for manganese ion
results.19−22 removal. The results of R-C, C-NaOH-C, and B-NaOH-C are
3.2. Comparison of Different Modification Methods. shown in Figure 1.
In general, it is recognized that surface areas and functional Figure 1 indicates that the removal rate of manganese ions
groups of biochar increased during the chemical modification increased with the increase of the biochar dosage. When the
process, which is important for enhancing its contaminant dosage of R-C was above 200 mg, C-NaOH-C was above 350
sorption ability.23,24 The results of adsorption experiments by
mg, and B-NaOH-C was above 400 mg, the adsorbent and
R-C, R-HNO3-C, R-NaOH-C, and R-Na2S-C on different
adsorbate in the solution achieved equilibrium26,28 and the
concentrations of manganese ion solution are displayed in
Table 2. removal rate no longer increased and approached fixed values:
As seen from Table 2, with the increase of Mn2+ in solution, 97.2, 94.9, and 92.75%, respectively. A higher adsorbent dosage
the adsorption capacity of manganese ions by the unmodified in the solution can provide more adsorptive sites.29 However,
biochar and modified biochar increased. The order of Mn2+ the adsorption capacity of R-C, C-NaOH-C, and B-NaOH-C
adsorption capacities by this biochar was as follows: rice straw, increased first and then decreased with the increase of the
R-C > R-NaOH-C > R-Na2S-C > R-HNO3-C; coconut shell, dosage. When the concentrations of biochar in the solution
C-NaOH-C > C-Na2S-C > C-HNO3-C > C-C; bamboo, B- reached a certain value, the chance of biochar particles
NaOH-C > B-Na2S-C > B-C > B-HNO3-C. Among the three colliding with each other is greatly increased and formed
modification methods, biochar modified with NaOH was the agglomerated particles, which led to a decrease in the
optimum for manganese ion removal. It may be due to ash, adsorption of Mn2+. The maximum adsorption capacity of R-
condensed organic matter of biochar dissolved, and the surface C, C-NaOH-C, and B-NaOH-C for manganese ions was 21.44,
basicity increase during modification with NaOH, which is 9.51, and 7.04 mg/g, respectively.

Table 2. Adsorption Experiments of Unmodified and Modified Biochara

adsorption capacity of Mn2+ (mg/L)
biomass biochar dosage (mg) Mn2+ concentration in solution (mg/L) biochar Biochar-HNO3 Biochar-NaOH Biochar-Na2S
rice straw 50 10 10.00 ± 0.37 1.53 ± 0.04 2.36 ± 0.06 1.98 ± 0.04
50 20.29 ± 0.50 4.49 ± 0.12 5.80 ± 0.10 5.30 ± 0.23
100 22.82 ± 1.10 5.02 ± 0.04 6.43 ± 0.30 6.05 ± 0.11
100 10 10.00 ± 0.26 1.97 ± 0.06 3.53 ± 0.12 2.77 ± 0.23
50 22.04 ± 0.63 4.68 ± 0.17 8.17 ± 0.32 6.83 ± 0.16
100 23.18 ± 0.83 5.60 ± 0.07 8.54 ± 0.25 7.39 ± 0.07
coconut shell 50 10 1.07 ± 0.04 1.62 ± 0.08 3.44 ± 0.04 2.03 ± 0.11
50 2.18 ± 0.05 2.96 ± 0.15 8.27 ± 0.10 4.83 ± 0.07
100 2.85 ± 0.07 3.97 ± 0.04 8.99 ± 0.20 5.77 ± 0.17
100 10 1.43 ± 0.04 2.13 ± 0.05 4.33 ± 0.20 3.79 ± 0.09
50 3.63 ± 0.04 5.14 ± 0.13 8.46 ± 0.18 5.76 ± 0.13
100 4.55 ± 0.15 6.44 ± 0.29 9.76 ± 0.29 7.05 ± 0.09
bamboo 50 10 1.86 ± 0.06 1.52 ± 0.08 3.89 ± 0.09 2.53 ± 0.08
50 2.93 ± 0.03 2.53 ± 0.05 6.23 ± 0.12 3.98 ± 0.09
100 3.43 ± 0.09 3.00 ± 0.10 7.00 ± 0.11 4.93 ± 0.24
100 10 2.03 ± 0.06 1.59 ± 0.08 4.09 ± 0.06 2.27 ± 0.07
50 4.46 ± 0.12 3.86 ± 0.08 6.88 ± 0.22 5.97 ± 0.29
100 5.29 ± 0.23 4.49 ± 0.19 7.48 ± 0.23 6.53 ± 0.13

a
Mean ± standard of error (n = 3).

28469 https://doi.org/10.1021/acsomega.3c02685
ACS Omega 2023, 8, 28467−28474
ACS Omega http://pubs.acs.org/journal/acsodf Article

more and more surface-active sites. In addition, when the pH

was low, a large amount of H+ existed in the aqueous solution;
H+ had a higher migration conversion rate than metal ions and
competed with metal ions for adsorption sites. Therefore, the
competition gradually decreased as the pH increase, and the
adsorption of manganese ions by biochar increased. The results
of Chen et al.14 also showed that as the pH increased, metal
ions were more likely to replace protons on the surface of the
adsorbent. When the pH was above 5, the adsorption capacity
of manganese ions by R-C, C-NaOH-C, and B-NaOH-C
decreased. It may be that when the pH was above a certain
value, the negatively charged ions in the solution increased and
the manganese ions might be surrounded by the anions in the
solution, which were difficult to combine with the negatively
charged adsorption sites of biochar. Therefore, the adsorption
capacity of Mn2+ by biochar increased first and then decreased.
When the pH of solution is above 7, the manganese ions easily
transform to hydroxide precipitation.30
3.5. Effect of Temperature. In the process of adsorption,
Figure 1. Effect of biochar dosage on adsorption of Mn2+ by R-C, C- it is often associated with the variation of the energy, and the
NaOH-C, and B-NaOH-C. effect of temperature on the reaction rate is significant. The
results of different temperatures (at 20, 25, 30, 35, and 40 °C)
From the adsorption capacity of manganese ions by three on the manganese ion adsorption by three biochar samples are
kinds of biochar, when the dosage of biochar exceeded 50 mg, shown in Figure 3.
the increase of adsorption capacity was not obvious.
Considering the removal efficiency, the appropriate R-C, C-
NaOH-C, and B-NaOH-C dosage is 50 mg when the
concentration of Mn2+ in solution is 50 mg/L.
3.4. Effect of pH. In the process of adsorption, solution pH
is the most important factor. It not only affects the surface
properties of the adsorbent but also affects the ion exchange
process. The effects of pH on the adsorption of Mn2+ by three
biochar samples are displayed in Figure 2.

Figure 3. Effect of temperature on adsorption of Mn2+ by R-C, C-

NaOH, and B-NaOH-C.

Figure 3 indicates that the adsorption capacity of manganese

ions by three biochar samples increased first and then
decreased with the increase of temperature. The adsorption
Figure 2. Effect of initial pH on adsorption of Mn2+ by R-C, C- capacities of obtained biochar are influenced by temperature.
NaOH, and B-NaOH-C. At 30 °C, the adsorption capacities of Mn2+ by R-C, C-NaOH,
and B-NaOH-C were the maximum, and the maximum
adsorption capacities were 24.68, 9.75, and 6.88 mg/g,
From Figure 2, the adsorption capacity of manganese ions respectively. In the process of adsorption, chemisorption is
by R-C, C-NaOH-C, and B-NaOH-C increased and then an endothermic reaction, the temperature rise is favorable for
decreased with the increase of pH. When the pH was 5, the adsorption, physical adsorption is an exothermic reaction, and
adsorption capacities of manganese ions by R-C, C-NaOH-C, the temperature rise is unfavorable for adsorption. From the
and B-NaOH-C were the maximum, 22.11, 8.93, and 7.04 mg/ data of temperature on adsorption, it can be inferred that the
g, respectively. At pH from 1 to 5, the adsorption of manganese adsorption processes of manganese ions by R-C, C-NaOH-C,
ions by the three biochar samples increased rapidly. It may be and B-NaOH-C are accompanied by chemical adsorption and
due to an increase in the pH, and the degree of ionization of physical adsorption. The temperature of the environment plays
the surface of the biochar increased, which exposes biochar to an important role in the process of absorbing. Under the
28470 https://doi.org/10.1021/acsomega.3c02685
ACS Omega 2023, 8, 28467−28474
ACS Omega http://pubs.acs.org/journal/acsodf Article

combined action, 30 °C is the optimum for the adsorption by The quasi-second-order kinetic model assumes that
biochar. chemisorption is the main rate-adjusting step in the adsorption
3.6. Adsorption Kinetics. To explore the mechanism of process; this involves the process of generating valence forces
Mn2+ removal, adsorption equilibrium experiments with R-C, when electrons are exchanged and shared between the
C-NaOH-C, and B-NaOH-C were carried out. The isotherm adsorbent and the adsorbate. The equation of the quasi-
curves by fitting the data with three adsorption models (quasi- second-order kinetic model can be expressed as follows (eq 6):
first-order, quasi-second-order, and intraparticle diffusion
models) are displayed in Figure 4; the corresponding
parameters are calculated and summarized in Table 3. (6)
qe (mg/g) is the equilibrium adsorption capacity of metal ions,
qt (mg/g) is the capacity of metal ions adsorbed at any time,
and K2 (mg/(g·min)) is the rate constant during the
adsorption process.
The intraparticle diffusion model can be used to investigate
the diffusion of metal ions inside the adsorbent after they
migrate from the liquid phase to the solid particle in the
process of adsorption. The equation of the intraparticle
diffusion model can be expressed as eq 7:

(7)
qt (mg/g) is the adsorption capacity of metal ions at any time,
Kp (mg/(g·min1/2)) is the rate constant of the internal
diffusion model, and C (mg/g) is a constant related to the
boundary.
Fitting the adsorption process of manganese ions by R-C, C-
NaOH-C, and B-NaOH-C, three kinds of biochar with quasi-
Figure 4. R-C, C-NaOH-C, and B-NaOH-C adsorption kinetic first-order, quasi-second-order, and intraparticle diffusion
curves. models, respectively, and the parameters obtained are shown
in Table 3.
Table 3 indicates that the quasi-first-order kinetic model is
more suitable for the adsorption of manganese ions by R-C,
Figure 4 indicates that the initial adsorption rate of the correlation coefficient R2 is 0.989, and the obtained
manganese ions by the three biochar samples is very rapid equilibrium adsorption capacity qe is closer to the actual qe
and achieved the adsorption equilibrium at about 180 min. At value. For adsorption of manganese ions by C-NaOH-C and B-
the stage of rapid adsorption, there are enough active binding NaOH-C, the quasi-second-order kinetic model is more
sites on the surface of biochar. suitable, the correlation coefficient R2 is 0.953 and 0.997,
The quasi-first-order reaction kinetic model, pseudo-second- respectively, and the equilibrium adsorption qe is also closer to
order kinetic model, and intraparticle diffusion model are the the actual qe value. The correlation coefficient R2 of quasi-first-
most commonly used kinetic models to investigate the order and quasi-second-order kinetics indicated that physical
adsorption process of metal ions by adsorbents. In the quasi- adsorption and chemisorption were simultaneously present in
first-order reaction kinetic equation, it is suggested that for the the adsorption of Mn2+ by three biochar samples. The results
process of ions from the liquid phase to absorbents, the rate at of fitting with the intraparticle diffusion model were the worst.
which metal ions occupy the surface-active sites of the 3.7. Adsorption Isotherms. The isotherm adsorption
adsorbent is proportional to the number of adsorbed sites on curves of manganese ions by three biochar samples are
the adsorbent that are not occupied. The equation of the quasi- displayed in Figure 5.
first-order reaction kinetic model can be expressed as follows From Figure 5, the adsorption capacity of manganese ions
(eq 5): by three biochar samples increased with the increase of
manganese ion concentration. The trend of the adsorption
(5)
capacity increased rapidly and then stabilized.
qe (mg/g) is the equilibrium adsorption capacity of metal ions, The Langmuir model, Freundlich model, and Temkin model
qt (mg/g) is the capacity of metal ions adsorbed at any time, are the most commonly used isothermal adsorption models for
and K1 (1/min) is the rate constant during the adsorption describing the equilibrium constants of adsorption processes
process. and investigating the relationship between the adsorbate and

Table 3. Quasi-First-Order, Quasi-Second-Order, and Intraparticle Diffusion Model Parameters

quasi-first-order quasi-second-order intraparticle diffusion

biocharcoal qe (mg/g) K1 (1/min) R2 qe (mg/g) K2 (mg/(g·min)) R2 Kp (mg/(g·min)) C (mg/g) R2
R-C 19.855 0.253 0.989 19.700 1.017 0.983 0.026 19.261 0.105
C-NaOH-C 8.260 0.032 0.911 8.754 0.006 0.953 0.121 4.956 0.531
B-NaOH-C 6.673 0.049 0.979 7.012 0.011 0.997 0.078 4.600 0.497

28471 https://doi.org/10.1021/acsomega.3c02685
ACS Omega 2023, 8, 28467−28474
ACS Omega http://pubs.acs.org/journal/acsodf Article

adsorption energy, and KT (L/mg) is the equilibrium constant

associated with the maximum binding energy.
The adsorption processes of manganese ions by R-C, C-
NaOH-C, and B-NaOH-C were fitted with the Langmuir
isotherm adsorption model, Freundlich isotherm adsorption
model, and Temkin isotherm adsorption model, and the
parameters obtained are shown in Table 4.
The correlation coefficients R2 of the Langmuir isotherm
adsorption model, Freundlich isotherm adsorption model, and
Temkin isotherm adsorption model are 0.970, 0.964, and
0.958, respectively. It indicated that the Langmuir isotherm
adsorption model was best suitable for the adsorption of
manganese ions by R-C, C-NaOH-C, and B-NaOH-C. The
maximum adsorption capacities of R-C, C-NaOH-C, and B-
NaOH-C for manganese ions are 25.67, 10.45, and 7.89 mg/g,
respectively. The KF of the Freundlich equation reveals the
relative adsorption capacity of the adsorbent, and the relative
adsorption capacity of the three biochar samples can be seen
Figure 5. Adsorption isotherms. from the table: R-C > C-NaOH-C > B-NaOH-C.
The parameter KL in the Langmuir equation and the
parameter n of the Freundlich equation can both indicate the
strength of the adsorption. When n is less than 1, it indicates
adsorbent in the process of adsorption at a certain temper- that the adsorption is difficult to react, and when n is more
ature.22 The equation of the Langmuir model can be expressed than 2, the adsorption by adsorbents is easy. From Table 3, the
as follows (eq 8): parameters n of the Freundlich equation for the adsorption of
manganese ions by R-C, C-NaOH-C, and B-NaOH-C are
more than 2, indicating that the adsorption of manganese ions
(8) by the three kinds of biochar is easy to carry out. The order of
qe (mg/g) and qm (mg/g) are the equilibrium adsorption parameter KL values in the Langmuir equation for the
capacity and maximum adsorption capacity of metal ions, adsorption of manganese ions was B-NaOH-C > R-C > C-
respectively. Ce (mg/L) is the concentration of metal ions in NaOH-C, indicating that the adsorption strength to
solution during adsorption equilibrium, KL is the equilibrium manganese ions is B-NaOH-C > R-C > C-NaOH-C.
constant related to temperature and the properties of
adsorbents and adsorbates. The greater the KL value, the 4. CONCLUSIONS
stronger the adsorption capacity of the adsorbent. In conclusion, among the three modification methods, biochar
The Freundlich model is based on the empirical adsorption modified with NaOH is the optimum for the adsorption of
equilibrium model established by the adsorption of the Mn2+. However, the same method of modification has different
adsorbate on multiphase surfaces. The equation of the effects on different biomass materials. For rice straw, R-C
Freundlich model can be expressed as follows (eq 9): without modification has the maximum capacity. For coconut
shell and fresh bamboo, biochar samples modified by NaOH
(9)
are the optimum. There are significant differences among the
qe (mg/g) is the equilibrium adsorption capacity of metal ions, adsorption capacity of these biochar adsorbents from different
and KF is the characteristic constant of the Freundlich biomass feedstocks. The physical and surface chemical
equation, which can indicate the relative adsorption capacity properties of biochar or biomass feedstock should be carefully
of the adsorbent. 1/n can indicate the adsorption strength. considered in the selection of pretreatment methods. In the
The Temkin model is used to evaluate the adsorption case of a manganese ion concentration of 50 mg/L in an
potential of the adsorbate on the adsorbent. The equation of aqueous solution, the optimum dosage for adsorption of
the Temkin model can be expressed in the following (eq 10): manganese ions by three biochar samples is 50 mg; pH and
temperature play an important role in the process of
adsorption. The optimum pH of solution for the adsorption
(10)
of manganese is 5, and the optimum temperature is 30 °C. The
Qe (mg/g) is the equilibrium adsorption capacity of metal ions, adsorption processes of Mn2+ by these biochar samples are
R (8.314 J/(mol·K)) is the constant, T (K) is the absolute fitted better with the Langmuir isothermal adsorption model.
temperature, b (J/mol) is the constant associated with the The kinetic model indicated that physical adsorption and

Table 4. Isothermal Adsorption Model Parameters of Langmuir, Freundlich, and Temkin

Langmuir Freundlich Temkin

biocharcoal qm (m/g) KL R2 KF n R2 B KT R2
R-C 25.674 0.073 0.970 6.900 3.986 0.772 503.921 0.967 0.885
C-NaOH-C 10.453 0.053 0.964 2.204 3.431 0.813 1179.616 0.620 0.913
B-NaOH-C 7.888 0.076 0.958 2.151 4.015 0.780 1653.699 0.976 0.887

28472 https://doi.org/10.1021/acsomega.3c02685
ACS Omega 2023, 8, 28467−28474
ACS Omega http://pubs.acs.org/journal/acsodf Article

chemisorption are simultaneously present in the adsorption

process of the three biochar samples to manganese ions.
■ REFERENCES
(1) Jiang, F.; Ren, B.; Hursthouse, A.; Zhou, Y. Trace metal
Overall, the results obtained from this study suggest that the pollution in topsoil surrounding the Xiangtan manganese mine area
key of using biochar as adsorbents is to find the appropriate (South-Central China), source identification, spatial distribution and
biomass feedstock. assessment of potential ecological risks. Int. J. Environ. Res. Public
Health 2018, 15, 2412.

■ AUTHOR INFORMATION
Corresponding Author
(2) Li, Y.; Xu, Z.; Ma, H.; Hursthouse, A. S. Removal of
manganese(II) from acid mine wastewater, a review of the challenges
and opportunities with special emphasis on Mn-oxidizing bacteria and
microalgae. Water 2019, 11, 2493.
Guoliang Chen − School of Resource & Environment and (3) Luo, X.; Ren, B.; Hursthouse, A. S.; Thacker, J. R. M.; Wang, Z.
Safety Engineering and Hunan Province Key Laboratory of Soil from an abandoned manganese mining area (Hunan, China),
Coal Resources Clean-Utilization and Mine Environment significance of health risk from potentially toxic element pollution and
Protection, Hunan University of Science and Technology, its spatial context. Int. J. Environ. Res. Public Health 2020, 17, 6554.
Xiangtan 411201, China; orcid.org/0009-0004-5685- (4) Xie, Q.; Ren, B.; Hursthouse, A.; Shi, X. Effects of mining
1522; Email: [email protected] activities on the distribution, controlling factors, and sources of metals
in soils from the Xikuangshan south mine, Hunan Province. Integr.
Authors Environ. Assess. Manage. 2022, 18, 748−756.
Khamphouvanh Viengvilay − School of Resource & (5) Chen, Z.; Liu, T.; Tang, J.; Zheng, Z.; Wang, H.; Shao, Q.; Chen,
G.; Li, Z.; Chen, Y.; Zhu, J.; Feng, T. Characteristics and mechanisms
Environment and Safety Engineering, Hunan University of of cadmium adsorption from aqueous solution using lotus seedpod-
Science and Technology, Xiangtan 411201, China derived biochar at two pyrolytic temperatures. Environ. Sci. Pollut. Res.
Weijian Yu − School of Resource & Environment and Safety 2018, 25, 11854−11866.
Engineering and Hunan Province Key Laboratory of Coal (6) Liu, L.; Liu, J.; Zhao, L.; Yang, Z.; Lv, C.; Xue, J.; Tang, A.
Resources Clean-Utilization and Mine Environment Synthesis and characterization of magnetic Fe3O4@CaSiO3 compo-
Protection, Hunan University of Science and Technology, sites and evaluation of their adsorption characteristics for heavy metal
Xiangtan 411201, China ions. Environ. Sci. Pollut. Res. 2019, 26, 8721−8736.
Teng Mao − School of Resource & Environment and Safety (7) Zhang, J.; Deng, R.-J.; Ren, B.-Z.; Hou, B.; Hursthouse, A.
Engineering, Hunan University of Science and Technology, Preparation of a novel Fe3O4/HCO composite adsorbent and the
Xiangtan 411201, China mechanism for the removal of antimony (III) from aqueous solution.
Sci. Rep. 2019, 9, 13021.
Zhihui Qu − School of Resource & Environment and Safety (8) Luo, X.; Ren, B.; Hursthouse, A. S.; Jiang, F.; Deng, R.-j.
Engineering, Hunan University of Science and Technology, Potentially toxic elements (PTEs) in crops, soil, and water near
Xiangtan 411201, China Xiangtan manganese mine, China, potential risk to health in the
Bixin Liang − School of Resource & Environment and Safety foodchain. Environ. Geochem. Health 2020, 42, 1965−1976.
Engineering, Hunan University of Science and Technology, (9) Chen, C.; Peng, Z.; Gu, J. Y.; Peng, Y.; Wu, L. Exploring
Xiangtan 411201, China environmentally friendly biopolymer material effect on soil tensile and
Zhang Chen − School of Resource & Environment and Safety compressive behavior. Int. J. Environ. Res. Public Health 2020, 17,
Engineering and Hunan Province Key Laboratory of Coal 9032.
Resources Clean-Utilization and Mine Environment (10) Liu, T.; Chen, Z.; Li, Z.; Fu, H.; Chen, G.; Feng, T.; Chen, Z.
Protection, Hunan University of Science and Technology, Preparation of magnetic hydrochar derived from iron-rich Phytolacca
acinosa Roxb. for Cd removal. Sci. Total Environ. 2021, 769,
Xiangtan 411201, China No. 145159.
Zhixian Li − School of Resource & Environment and Safety (11) Deng, R.; Shao, R.; Ren, B.; Hou, B.; Tang, Z.; Hursthouse, A.
Engineering and Hunan Province Key Laboratory of Coal Adsorption of Antimony(III) onto Fe(III)-Treated Humus Sludge
Resources Clean-Utilization and Mine Environment Adsorbent, Behavior and Mechanism Insights. Pol. J. Environ. Stud.
Protection, Hunan University of Science and Technology, 2019, 28, 10.
Xiangtan 411201, China; orcid.org/0000-0002-5793- (12) Zhang, Y.; Zhao, C.; Chen, G.; Zhou, J.; Chen, Z.; Li, Z.; Zhu,
0052 J.; Feng, T.; Chen, Y. Response of soil microbial communities to
additions of straw biochar, iron oxide, and iron oxide−modified straw
Complete contact information is available at: biochar in an arsenic-contaminated soil. Environ. Sci. Pollut. Res. 2020,
https://pubs.acs.org/10.1021/acsomega.3c02685 27, 23761−23768.
(13) Zhu, G.; Lin, J.; Yuan, Q.; Wang, X.; Zhao, Z.; Hursthouse, A.
Notes S.; Wang, Z.; Li, Q. A biochar supported magnetic metal organic
The authors declare no competing financial interest. framework for the removal of trivalent antimony. Chemosphere 2021,
282, No. 131068.

■ ACKNOWLEDGMENTS
This work was supported by the Natural Science Foundation
(14) Chen, G.; Ma, Y.; Xu, W.; Chen, Z.; Li, Z.; Zhou, J.; Yu, W.
Remediation of cadmium-contaminated soil by micro-nano nitrogen-
doped biochar and its mechanisms. Environ. Sci. Pollut. Res. 2023, 30,
48078−48087.
of Hunan Province China (no. 2023JJ30230), the Scientific (15) Du, J.; Wang, C.; Zhao, Z.; Chen, R.; Zhang, P.; Cui, F. Effect
Research Fund of Hunan Provincial Education Department of vacuum ultraviolet/ozone pretreatment on alleviation of ultra-
(no. 21B0451), the Teaching Research and Reform Project of filtration membrane fouling caused by algal extracellular and
Hunan Province (HNJG-2022−0174), the Open Foundation intracellular organic matter. Chemosphere 2022, 305, No. 135455.
of Hunan Province Key Laboratory of Coal Resources Clean- (16) Jiang, F.; Ren, B.; Hursthouse, A.; Deng, R.; Wang, Z.
Distribution, source identification, and ecological-health risks of
Utilization and Mine Environment Protection (no. E22301), potentially toxic elements (PTEs) in soil of thallium mine area
and the National Natural Science Foundation of China (no. (southwestern Guizhou, China). Environ. Sci. Pollut. Res. 2019, 26,
41501343). 16556−16567.

28473 https://doi.org/10.1021/acsomega.3c02685
ACS Omega 2023, 8, 28467−28474
ACS Omega http://pubs.acs.org/journal/acsodf Article

(17) Li, Y.; Yang, X.; Geng, B. Preparation of immobilized sulfate-

reducing bacteria-microalgae beads for effective bioremediation of
copper-containing wastewater. Water, Air, Soil Pollut. 2018, 229, 54.
(18) Meng, D.; Li, J.; Liu, T.; Liu, Y.; Yan, M.; Hu, J.; Li, X.; Liu, X.;
Liang, Y.; Liu, H.; Yin, H. Effects of redox potential on soil cadmium
solubility, Insight into microbial community. J. Environ. Sci. 2019, 75,
9.
(19) Chen, G.; Ran, Y.; Ma, Y.; Chen, Z.; Li, Z.; Chen, Y. Influence
of Rahnella aquatilis on arsenic accumulation by Vallisneria natans
(Lour.) Hara for the phytoremediation of arsenic-contaminated water.
Environ. Sci. Pollut. Res. 2021, 28, 44354−44360.
(20) Chen, Z.; Li, Z.; Chen, G.; Zhu, J.; Liu, Q.; Feng, T. In situ
formation of AgNPs on S. cerevisiae surface as bionanocomposites for
bacteria killing and heavy metal removal. Int. J. Environ. Sci. Technol.
2017, 14, 1635−1642.
(21) Zhang, Y.; Huang, F. Indicative significance of the magnetic
susceptibility of substrate sludge to heavy metal pollution of urban
lakes. Scienceasia 2021, 47, 9.
(22) Chen, Y.; Cao, J.; Zhao, J.; Wu, J.; Zou, X.; Fu, S.; Zhang, W.
Labile C dynamics reflect soil organic carbon sequestration capacity,
Understory plants drive topsoil C process in subtropical forests.
Ecosphere 2019, 10, No. e2784.
(23) Chen, G.; Feng, T.; Li, Z.; Chen, Z.; Chen, Y.; Wang, H.;
Xiang, Y. Influence of sulfur on the arsenic phytoremediation using
Vallisneria natans (Lour.) Hara. Bull. Environ. Contam. Toxicol. 2017,
99, 411−414.
(24) Zhu, J.; Wallis, I.; Guan, H.; Ross, K.; Whiley, H.; Fallowfield,
H. Juncus sarophorus, a native Australian species, tolerates and
accumulates PFOS, PFOA and PFHxS in a glasshouse experiment. Sci.
Total Environ. 2022, 826, No. 154184.
(25) Yu, H.; Xiang, Y.; Zou, D. The effect of Eulaliopsis binata on the
physi-chemical properties, microbial biomass, and enzymatic activities
in Cd-Pb polluted soil. Environ. Sci. Pollut. Res. 2016, 23, 19212−
19218.
(26) Yu, S.; Chen, Y.; Zhao, J.; Fu, S.; Li, Z.; Xia, H.; Zhou, L.
Temperature sensitivity of total soil respiration and its heterotrophic
and autotrophic components in six vegetation types of subtropical
China. Sci. Total Environ. 2017, 607-608, 160−167.
(27) Li, X.; Meng, D.; Li, J.; Yin, H.; Liu, H.; Liu, X.; Cheng, C.;
Xiao, Y.; Liu, Z.; Yan, M. Response of soil microbial communities and
microbial interactions to long-term heavy metal contamination.
Environ. Pollut. 2017, 231, 908−917.
(28) Chen, Y.; Zhang, Y.; Cao, J.; Fu, S.; Hu, S.; Wu, J.; Zhao, J.;
Liu, Z. Stand age and species traits alter the effects of understory
removal on litter decomposition and nutrient dynamics in subtropical
Eucalyptus plantations. Global Ecol. Conser. 2019, 20, No. e00693.
(29) Zhou, Y.; Ren, B.; Hursthouse, A.; Zhou, S. Antimony ore
tailings, heavy metals, chemical speciation, and leaching character-
istics. Pol. J. Environ. Stud. 2019, 28, 485−495.
(30) Deng, R.-J.; Jin, C.-S.; Ren, B.-Z.; Hou, B.-L.; Hursthouse, A. S.
The potential for the treatment of antimony-containing wastewater by
iron-based adsorbents. Water 2017, 9, 794.

28474 https://doi.org/10.1021/acsomega.3c02685
ACS Omega 2023, 8, 28467−28474