Key Laboratory of Bio-resources and Eco-environment (Ministry of Education), College of Life Science, Sichuan University, Chengdu, Sichuan 610064, PR China
Yaan Vacational College, Yaan 625000, PR China
h i g h l i g h t s
Pleurotus ostreatus was fabricated into nanoparticles by high-energy nano-impact grinding.
P. ostreatus nanoparticles as a new nano-bisorbent for removal of Mn(II).
The size distribution of PONP measured by small angle X-ray scattering.
SEM, EDS and FTIR spectra were used to characterize the nano-biosorbent.
The maximum Mn(II) adsorption capacity of PONP is higher than many other adsorbents.
a r t i c l e
i n f o
Article history:
Received 9 December 2012
Received in revised form 5 March 2013
Accepted 7 March 2013
Available online 16 March 2013
Keywords:
Pleurotus ostreatus
Nanoparticles
Nano-biosorbent
Mn(II)
Adsorption kinetic
Adsorption isotherm model
a b s t r a c t
The objective of this study was to investigate the use of Pleurotus ostreatus (P. ostreatus) nano-particles
(PONP) as a new nano-biosorbent to remove Mn(II) from aqueous solution. Scanning Electron Microscope
(SEM), Energy Dispersive Spectrometry (EDS), Fourier Transform Infrared Spectrometry (FTIR spectra),
Small-angle X-ray Scattering (SAXS) were used to characterize the nano-biosorbent. Adsorption experiments were carried out by batch experiments to investigate the effects of different experiment parameters including pH of the solution, adsorbent dose, initial Mn(II) ion concentration and contact time on
adsorption capacity of PONP. The adsorption equilibrium study exhibited that Mn(II) adsorption of PONP
was better tted by Langmuir isotherm model. The maximum Mn(II) adsorption capacity of PONP was
130.625 mg/g at 298.15 K, which was higher than many other adsorbents. Pseudo-second-order kinetic
model was the best one to predict the sorption kinetics with a maximum adsorption capacity of PONP
attained within 30 min. PONP showed great potential in wastewater treatment due to the high adsorption capacity.
Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.
1. Introduction
Nanotechnology, as a novel method, has become one of the
most popular technologies for the removal of metal cations from
aqueous solution over the past few decades. Nano-particles mainly
including nano-sized inorganic material derived from metals and
metal oxides (i.e., silver nano-particles, TiO2, SiO2, Al2O3 and ZnO,
Fe3O4 magnetic nano-particles), carbon nanotube and synthetic
nano particles (i.e., synthetic nanostructured Fe(III)Cr(III) mixed
oxide [1]) have been applied widely as adsorbents for the treatment of metal cations efuents. The advantages of various types
of nano-particles adsorbents are tiny in particulate diameter, large
external surface area, high density of reactive surface sites and
great intrinsic reactivity of surface sites and small internal diffusion resistance [2]. However, these nano-adsorbents have many
Corresponding author. Tel.: +86 28 85414644; fax: +86 28 85418262.
E-mail address: xuheng64@sina.com (H. Xu).
obvious shortcomings such as high preparation cost, strict operational conditions, high energy consumption. These shortcomings
which may restrict application areas of nano-particles adsorbents
in wastewater treatment already became a serious problem cannot
be ignored. Fortunately, a number of naturally available, low-cost
and effective adsorbents including activated olive bagasse [3],
Chitosan [4], Dehydrated peanut hull [5], Cedar sawdust [6] and
some types of edible mushrooms (such as Pleurotus platypus [7],
Lentinus sajor-caju [8]) have been successfully employed as adsorbents for removing various kinds of metal cations and dyes from
waste water in recent years. Pleurotus ostreatus is a normal edible
mushroom, which is extensively cultivated in South China. Because
of wide source of raw materials and technological innovation,
PONP combine the merits of nano-particles adsorbents and lowcost adsorbents. It retains high surface-area-to-volume ratio and
low capital and operational costs.
It is worthwhile to note that adsorbent particle size has a significantly effect on water pollutants removal in previous researches.
1385-8947/$ - see front matter Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.03.044
60
Investigators [913] found that adsorption capacity of heavy metals or dyes increased with the decrease in adsorbent particle size.
Tian et al. [9] studied spent Tricholoma lobayense for removal of
Congo Red (CR) from aqueous solution. The CR removal percentages increased from 81.27% to 92.75% when the particle size of
adsorbent decreased from 60 mesh to 200 mesh. They came to
the conclusion that both removal ratio of CR and adsorption capacity increased with the decrease in adsorbent particle size. Liu et al.
[10] used ammonium citrate modied spent Lentinus edodes as
adsorbent to remove Pb(II) from aqueous solution. Particle size of
adsorbent was proved by PlacketBurman design that it had a
positive effect on Pb(II) removal. Gupta et al. [11] studied on the
removal of Cr(VI) from aqueous solution using carbon slurry and
found that the adsorption capacity increased with the decreasing
of particle size of the adsorbent. Chen et al. [12] applied L. edodes
to the bioremediation of chromate contaminated water. Three
sizes of the biosorbent, 2 mm, 1 mm and 450 lm, were used in
100 mg/L Cr(VI) for adsorption. Total removal of Cr(VI) achieved
was the highest at 450 lm among these three sizes.
Albadarin et al. [13] removed chromium ions from aqueous solution using raw dolomite. Experiments were performed using different particle sizes of the adsorbent (0.1802.0 mm). Results specied
that the amount of Cr(VI) adsorbed onto dolomite decreases with an
increase in the particle size of the adsorbent. These results of such
studies can demonstrate that the adsorption capacity of adsorbent
particle may be enhanced by reducing the size of particle. But very
few literatures are available on metal ions removal using nanoparticles biosorbent.
Toxic metals contamination of the environment such as copper,
lead, cadmium, nickel, mercury, manganese is a severe global environmental issues. It has long been known that Mn is one of the
most widely used metals in the world and one of the important
indexes of the water pollutants. As an essential element for
humans, animals and plants, Mn is required for their growth,
development, and maintenance of health. But excess manganese
is detrimental to health. In China, the maximum recommended level of Mn(II) in drinking water is 0.1 mg/L as well as the provisions
of World Health Organization. Overdose exposure to Mn(II) in the
environment may result in the occurrence of manganese poisoning, which can adversely affect human body system such as nervous system, immune system and reproductive system. Chronic
inhalation of high levels of Mn can induce a neurodegenerative disorder, Parkinson, lung embolism and bronchitis [14].
To our knowledge, no similar report about nano-size mushroom
applied to waste water treatment is available up to now. Furthermore, our study was the rst one in which P. ostreatus was fabricated
into nanoparticles by high-energy nano-impact grinding (HENIG).
HENIG as a closed high-energy milling machine and through the
quick multidimensional swing motion of its tank, is able to make
the irregular motion of milling medium in the tank. The motion
can generate a tremendous impact force with increased impact
times, prolong the motion trace, augment the impact energy and lessen the impact blind spots. Its working efciency increased several
dozen times over the traditional ball millers. The particles of broken
substance processed by HENIG reach nano-grade. Because HENIG
are high-energy millers, mushroom nes are easy to be cooked
and carbonized in the quickly increasing temperature in the machines. To solve the problem, cycling water cooling in a jacket of
the tank are adopted to effectively control the temperature during
the processing. Numerous kinds of mushroom contain too much sugar or oil or colloid that might stick onto the balls and the tank or palletized in the ball miller, which reduce the milling effect. The humid
milling method have solved the problem of stickiness. To improve
milling effect, mushroom are crashed and water is added to form
specied size, and then made with ball miller into nano-size, nally
dried with spray after having reached milling effect.
298.15 K on a constant temperature breeding shaker (SUKUN, SKY211B) with a shaking of 150 rpm.
The effects of pH (from 2 to 7, initial Mn(II) concentration
100 mg/L, adsorbent dose 0.4 g/L), initial Mn(II) concentration
(from 50 mg/L to 200 mg/L, pH 6, adsorbent dose 0.4 g/L) and
adsorbent dose (from 0.4 g/L to 14 g/L, pH 6, initial Mn(II) concentration 200 mg/L) were investigated by varying any one of the process parameters and keeping the other parameters constant. After
adsorption, suspension was centrifuged for 2 min at the speed of
3500 rpm in a low speed centrifuge (ZONKIA, SC-3610).The supernatant was diluted in order to achieve measuring range of AAS. The
Mn(II) adsorption capacity (qe)was calculated as follows:
qe mg=g
C0 Ct
M
The adsorption isotherms were studied by varying the concentration of Mn(II) solutions ranging from 50 to 200 mg/L at pH 6
with a known amount of adsorbent (0.4 g) and four different temperatures (278.15 K, 283.15 K, 293.15 K and 303.15 K), respectively. Three isotherm models, Langmuir, Freundlich and Temkin
isotherm model, were employed to explore the adsorption
mechanism.
The linear equation of Langmuir isotherm model [15] is expressed as follows:
where Ce represents the equilibrium concentration of the heavy metal ion in the solution (mg/L), qe represents the amount of metal ion
uptaken per unit mass of the biomass at equilibrium (mg/g). The value of Q represents the maximum amount of metal ion uptaken per
unit mass of the biomass (mg/g), b is the Langmuir constant related
to the energy of adsorption (L/mg). The values of Q and b can be
determined from the slope and intercept of the linear plot of Ce/qe
versus Ce, respectively.
To predict whether an adsorption system is favorable or unfavorable, the dimensionless separation factor of equilibrium parameter RL which dened by Webi and Chakravort [16] is calculated
using the following equation:
ln qe ln K f
1
ln C e
n
RT
qe
lnK T C e
RT
b
1
RL
1 bC 0
Ce
1
Ce
qe Qb Q
61
where Kf is the Freundlich constant related to the adsorption capacity (mg/g), and n is the Freundlich exponent related to the intensity
qe B ln K T B ln C e
lnqe qt ln qe k1 t
t
1
t
qt k2 q2e qe
where k2 (g mg1 min1) is the rate constant of the pseudo secondorder adsorption.
Intra-particle diffusion model [21] is expressed as follows:
qt kid t1=2 C
10
where kid is the intra-particle diffusion rate constant (mg g1 min)
and C is the lm thickness.
Elovich model [22] is also used to model the adsorption data,
which is described as follows:
Qt
1
1
lnxy ln t
y
y
11
62
63
64
oxide(27.12 mg/g) [32], pabeads SP70 resin (4.2 mg/g) [33], anular
activated carbon (2.54 mg/g) [34].
3.3. Adsorption isotherms
Fig. 8a. Adsorption isotherm of Mn(II) ions by PONP adsorption (pH 6, contact
time 30 min, adsorbent dose 0.4 g/L).
65
Fig. 8b. Langmuir isotherm polts for Mn(II) ions adsorption onto PONP.
Fig. 8c. Freundlich isotherm polts for Mn(II) ions adsorption onto PONP.
Table 1
Modeled adsorption isotherm equation, isotherm parameters, and distribution
coefcient for the adsorption of Mn(II) on PONP at different temperatures.
5 C
Fig. 8d. Temkin isotherm polts for Mn(II) ions adsorption onto PONP.
20 C
30 C
93.4579
0.1374
0.1271
0.0678
0.0463
0.0351
0.0237
0.9992
103.0928
0.1770
0.1015
0.0535
0.0363
0.0275
0.0185
0.9988
75.188
0.0405
0.3306
0.1980
0.1413
0.1099
0.0760
0.9884
60.6913
13.3690
0.9474
76.9996
20.7469
0.9252
30.8921
7.0871
0.9009
9195.1179
6.2502
0.9431
1.4742 107
4.5592
0.9158
11.4834
8.4522
0.8804
10 C
66
3.4.1. Pseudo-rst-order
Pseudo-rst-order was suggested by Lagergren [19] for the
adsorption of solid and liquid systems. The adsorption of Mn(II)
from the solution to adsorbent can be considered as a reversible
process with equilibrium being established between the liquid
and solid phases.
According to the linear form of pseudo-rst-order model (Eq.
(8)), a linear t between ln(qe qt) versus contact time (t) was
made. The rate constants (k1), the R2 and the qe values were given
in Table 2. The adsorption rate constants (k1) was calculated from
the slope of the linear plot of ln(qe qt) versus t.
The theoretical equilibrium adsorption capacity values derived
from pseudo-rst-order kinetic model were considerably different
from the experimental values for all the three different initial concentrations of Mn(II). The values of distribution coefcient (R2) of
pseudo-rst-order model (R2 = 0.93560.9886) was low. Therefore,
the biosorption of Mn(II) onto PONP biomass does not t pseudorst-order kinetic.
3.4.2. Pseudo-second-order
Pseudo-second-order is based on the assumption that the
adsorption rate is determined by the square of the number of vacant adsorption sites on the surface of adsorbent [20].
The rate constants (k2), the R2 and the qe values were given in
Table 2. It was clear from these results that the R2 values were very
high (0.99971) for the Mn(II) biosorption. At the same time, the
theoretical equilibrium adsorption capacity values calculated from
pseudo-second-order kinetic model were very close to the experimental values for all the three different initial concentrations of
Mn(II). The results also revealed that the pseudo-second-order
model was more suitable for the process than other three models,
which had been conrmed in Fig. 9. These results implied that the
biosorption of Mn(II) onto PONP biomass adheres to the pseudo
second-order kinetics which further suggest that chemi-adsorption
is the rate controlling step [39].
Table 2
Kinetic parameters for the adsorption of Mn(II) onto PONP.
Kinetic models
Parameters
Pseudo-rst-order
20.2125
0.1189
0.9447
10.3481
0.0949
0.9886
Pseudo-second-order
62.5
0.0145
0.9997
131.5789
0.0206
0.9999
Elovich
x (mg/g min)
y (mg/g)
R2
50 mg/L
3.8841 1014
0.2734
0.9908
1.3310
0.9675
39.3337
1.9476
0.9401
130.625
3.7289
0.9950
61.9426
67
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