Biosorption of Cadmium (Ċ) From Aqueous Solutions by Industrial Fungus Rhizopus Cohnii
Biosorption of Cadmium (Ċ) From Aqueous Solutions by Industrial Fungus Rhizopus Cohnii
Biosorption of Cadmium (Ċ) From Aqueous Solutions by Industrial Fungus Rhizopus Cohnii
Abstract: An important filamentous industrial fungus, Rhizopus cohnii (R. cohnii), was used as an efficient biosorbent for removing
cadmium from wastewater. The sorption conditions, such as pH, the dose of biomass and the initial concentration of cadmium were
examined. Two kinds of adsorption models were applied to simulate the biosorption data. The uptake of cadmium was higher in weak
acid condition than in strong acid condition. Nearly no sorption of cadmium occurred when the pH value was lower than 2.0.
Biosorption isothermal data could be well simulated by both Langmuir and Freundlich models. Langmuir simulation of the
biosorption showed that the maximum uptake of cadmium was 40.5 mg/g (0.36 mmol/g) in the optimal conditions, which was higher
than many other adsorbents, including biosorbents and activated carbon. In addition, the reusability results showed that after five
times of sorption and desorption process, the sorption capacity of R. cohnii could still maintain nearly 80%, confirming its practical
application in cadmium treatment. Fourier transform infrared spectrum revealed that carboxyl, amino and hydroxyl groups on
biosorbent R. cohnii surface were responsible for the biosorption of cadmium.
Key words: biosorption; Rhizopus cohnii; biosorbent; cadmium
Foundation item: Project(50830301) supported by the National Natural Science Foundation of China; Project(50725825) supported by the National Science
Fund for Distinguished Young Scholars of China
Corresponding author: LUO sheng-lian; Tel: +86-731-88821967; E-mail: [email protected]
DOI: 10.1016/S1003-6326(09)60264-8
LUO Jin-ming, et al/Trans. Nonferrous Met. Soc. China 20(2010) 1104í1111 1105
that many kinds of fungi are capable of removing heavy were referred to as “biosorbent R. cohnii” in this work.
metals during sewage treatment, such as fungus The activated carbon with similar diameter was obtained
Aspergillus niger[7], fungus Phanerochaete from Shanghai Xingchang Activated Carbon Co., Ltd,
chrysosporium[8], white-rot fungus[9], fungal biomass China. The adsorbents were all stored in desiccators for
of Mucor racemosus[10] and the by products of the following experiments.
brown-rot fungus L. edodes[11].
Rhizopus species are important filamentous fungi 2.3 Analytical technique
that have been widely used in modern industries for The concentrations of cadmium ions were
processing traditional fermented foods, industrial determined by the flame atomic absorption spectrometry
enzyme production and organic acids such as fumaric (FAAS) using Z2000 polarized zeeman atomic
and lactic acid production[12í13]. Abundance of this absorption spectrophotometer (Hitachi, Japan). The
kind of biomaterial was thrown away after application. hollow cathode lamp was operated at 5 mA and the
This biomaterial contains plenty of chitin and lignin, analytical wavelength was set at 228.8 nm.
which are very efficient in heavy metals biosorption[14].
Plenty of myceliums in the byproduct have many 2.4 Batch biosorption and desorption experiments
important bene¿ts for human beings, such as degrading 20, 50 and 100 mg/L of cadmium solution were
organopollutants[15] and sorbing heavy metals such as conducted to determine optimal pH, contact time and
chromium[16]. dosage (dry mass). Biosorbent R. cohnii was mixed with
This study aimed at using the industrial fungus Cd(Ċ) solution and agitated in an incubator at 150 r/min,
Rhizopus cohnii (R. cohnii) to remove cadmium in 298 K. The effect of pH was investigated in the range of
simulated wastewater. The factors that affect biosorption 1.5í6.5 at the dosage of 1.0 g/L and contact time of 12 h
capacity, such as pH, the dosage and reusability of (to ensure that equilibrium was reached). The pH values
biosorbent and the initial cadmium concentration were in the solutions were monitored by a FE20 pH electrode
examined. Freundlich and Langmuir isotherm models (Mettler Toledo, Shanghai, China). The kinetics of Cd(Ċ)
were used to simulate the biosorption characterization. sorption on biosorbent R. cohnii was also studied. The
Moreover, Fourier transform infrared spectrum was dosage was 1.0 g/L and the pH was adjusted to 4.5.
employed to understand the biosorption mechanism. Samples were taken and analyzed at the following time
intervals: 0.25, 0.5, 1.0, 2.0, 4.0 and 6.0 h. The optimum
2 Experimental dosage was examined in the range of 1.0í15.0 g/L.
The desorption study was conducted at the initial
2.1 Preparation of reagents and medium Cd(Ċ) concentration of 20, 50 and 100 mg/L under
All reagents used were of analytical grade and previously determined optimal adsorption conditions.
purchased from Shanghai Pharmaceutical Co. Ltd. in After the biosorption of Cd(Ċ), the biosorbent was
China. The 1 000 mg/L Cd( Ċ) stock solution was eluted with 20 mL 0.1 mol/L HNO3 for 1 h at 150 r/min.
prepared by dissolving the exact quantities of the Then, the biosorbent was washed with deionized water
3CdSO4·8H2O in deionized-distilled water. The working till the pH of the eluate was in the range of 5.0í5.5. This
concentration of Cd(Ċ) solution was prepared from cycle was repeated 5 times. Samples were taken after
suitable serial dilution of the stock solution. The every adsorption and desorption process by filtering
deionized-distilled water used in this experiment was through 0.45 μm filter units (Millipore, Ireland). The
obtained from a Milli-Q system (Millipore, USA). cadmium concentrations in the filtrate were analyzed
The yeast peptone sucrose (YPS) medium contained with the methods mentioned above. All experiments
3.0 g/L yeast extract, 10 g/L peptone and 20 g/L sucrose. were done three times, yielding an experimental error of
The pH of the medium was adjusted to 4.5. less than 5%.
Table 1 Biosorption rate constants and Qe values from pseudo-¿rst-order and pseudo-second-order kinetics for biosorption of
cadmium on biosorbent
Cadmium Expt. Qe/ Pseudo-¿rst-order kinetic Pseudo-second-order kinetic
concentration/(mg·Lí1) (mg·gí1) í1
Cal. Qe/(mg·g ) í1
K1/(g·mg ·h ) í1
R 2
Cal. Qe/(mg·gí1) K2/(g·mgí1·hí1) R2
20 3.8 2.3 0.8 0.92 4.0 1.1 0.99
50 7.2 4.3 1.5 0.91 7.5 0.8 0.99
100 14.0 8.0 1.7 0.89 14.3 0.6 0.99
Expt.üExperimental; Cal.üCalculated.
1108 LUO Jin-ming, et al/Trans. Nonferrous Met. Soc. China 20(2010) 1104í1111
the sorption capacity of biosorbent R. cohnii did not procedure[6]. Several isotherm equations have been used
significantly decrease after five cycles. As shown in for equilibrium models of biosorption systems. The two
Table 2, over 80% of the sorption capacities remained most commonly used isotherm equations, the Langmuir
after five adsorption-desorption cycles. The sorption and Freundlich, have been applied in this study:
capacity only decreased by 0.7, 0.9 and 2.3 mg/g at the
Ue 1 U
initial Cd(Ċ) concentrations of 20, 50 and 100 mg/L, e (3)
q bQmax Qmax
respectively. Moreover, the desorption efficiencies were
all above 95% during five cycles at different initial where Qmax (mg/g) is the maximum amount of metal ion
Cd(Ċ) concentrations. per unit mass of adsorbent to form a complete monolayer
The application possibility of adsorbents depends on the surface; b is the equilibrium adsorption constant,
not only on the sorptive capacity, but also on how well and is related to the affinity of the binding sites. Qmax
the biomass can be reused. The reusability of biosorbent represents a practical limiting adsorption capacity when
R. cohnii was evaluated by repeating the adsorption and the surface is fully covered with metal ions. It allows the
desorption experiments for five times. The high comparison of adsorption performance, particularly in
desorption efficiency indicated that nitric acid was the the case of where the adsorbent was not fully saturated.
efficient desorbent agent for cadmium desorption (Table
1
2). Its efficiency is based on the competition between the ln q ln K ln U e (4)
n
protons and the cadmium ions adsorbed by the
where K and n are the Freundlich constants’ system
biosorbent, which will be released if the eluant
characteristics, indicating the adsorption capacity and
concentration is high enough and there is not a steric
impediment[24]. However, excessive amounts of
adsorption intensity, respectively[1].
hydrogen ions could reduce the biosorption capacity of Both of them represent the equilibrium amount of
the biomass[7]. Therefore, the reuse of the biomass in metal removed (q) as a function of the equilibrium
biosorption after elution of biosorbed cadmium ions will concentration (ȡe) of metal ions in the solution,
require hydrogen ions to be removed from the biomass. corresponding to the equilibrium distribution of ions
In this case, the biomass was regenerated by being between aqueous and solid phases as the initial
washed with deionized water until the pH of the wash concentration increases. To measure each isotherm,
solution was in the range of 5.0í5.5. It was noticed that initial cadmium concentrations were varied while the
the first acid treatment was responsible for more than biomass mass in each sample was kept constant.
half of the biosorption decrease (Table 2). However, the Equilibrium periods of 2 h for sorption experiments were
decrease of sorption capacity at different initial Cd(Ċ) used to ensure equilibrium conditions. This time was
concentrations was not significant after five cycles. chosen considering the results of kinetics, which was
Similar deleterious effect of the acid treatment on the determined previously.
biomass was also observed when endophytic fungus (EF) To estimate the cadmium uptake capacity of
Microsphaeropsis sp. LSE10 was used as biosorbent[1]. biosorbent R. cohnii, we did not only compare its
performance with other reported biosorbents, but also
3.4 Effect of initial concentration employed activated carbon, a widely and practically used
Analysis of equilibrium data is important for adsorbent, as control adsorbents to run the sorption
developing an equation that can be used to compare capacities comparison experiments.
different biomaterials under different operational The initial concentration of metal ions in the
conditions and to design and optimize an operating solution plays a key role as a driving force to overcome
Table 2 Desorption of Cd(Ċ) from biosorbent R. cohnii at different initial concentrations of Cd(Ċ) for five times
20 mg/L 50 mg/L 100 mg/L
Cycle Sorption Desorption Sorption Desorption Sorption Desorption
capacity/(mg·gí1) efficiency/% capacity/(mg·gí1) efficiency/% capacity/(mg·gí1) efficiency/%