Equilibrium and kinetic studies of copper biosorption by dead Ceriporia lacerata biomass isolated from the litter of an invasive plant in China
© Li et al.; licensee BioMed Central. 2015
Received: 28 July 2013
Accepted: 14 April 2015
Published: 25 April 2015
Ceriporia lacerata, a strain of white-rot fungus isolated from the litter of an invasive plant (Solidago canadensis) in China, was little known about its properties and utilization. In this work, the copper(II) biosorption characteristics of formaldehyde inactivated C. lacerata biomass were examined as a function of initial pH, initial copper(II) concentration and contact time, and the adsorptive equilibrium and kinetics were simulated, too.
The optimum pH was found to be 6.0 at experimental conditions of initial copper(II) concentration 100 mg/L, biomass dose 2 g/L, contact time 12 h, shaking rate 150 r/min and temperature 25°C. Biosorption equilibrium cost about 1 hour at experimental conditions of pH 6.0, initial copper(II) concentration 100 mg/L, C. lacerata dose 2 g/L, shaking rate 150 r/min and temperature 25°C. At optimum pH 6.0, highest copper(II) biosorption amounts were 6.79 and 7.76 mg/g for initial copper(II) concentration of 100 and 200 mg/L, respectively (with other experimental parameters of C. lacerata dose 2 g/L, shaking rate 150 r/min and temperature 25°C). The pseudo second-order adsorptive model gave the best adjustment for copper(II) biosorption kinetics. The equilibrium data fitted very well to both Langmuir and Freundlich adsorptive isotherm models.
Without further acid or alkali treatment for improving adsorption properties, formaldehyde inactivated C. lacerata biomass possesses good biosorption characteristics on copper(II) removal from aqueous solutions.
Heavy metal pollution is an increasing environmental problem of worldwide concern. Reducing heavy metals to environmentally acceptable limits in a cost-effective, easily available and environmental friendly manner becomes more and more urgent [1,2]. Biosorption of heavy metals from wastewaters by pretreated fungal biomass has gained growing acceptance since the 1990s [3,4].
The heavy metal ion biosorption by fungal biomass is based mainly on two mechanisms: covalent bonding with functional groups including carboxyl, hydroxyl, phosphate, amino, sulphydryl, and the result of physicochemical inorganic interactions directed by adsorption phenomena [2,5-7]. Therefore, here are several critical parameters affecting biosorption characteristics, such as pH, pretreatment methods, metal species, initial concentration of solutions, quantity of biomass, contact time [8-10].
Many fungi have been extensively studied and proved to be good biosorbents of heavy metals, such as Rhizopus arrhizus [11-14], Aspergillus spp. [6,15-17], Penicillium spp. [17,18] and Saccharomyces spp. [2,19]. However, white-rot fungi were relatively less reported for their biosorption though they were strong degrader of various xenobiotics and detoxicating materials of contaminated effluents [20,21]. They also possess the capacity of heavy metal biosorption .
Ceriporia lacerata is a white-rot fungus first isolated as a new species from white-rotted wood in Japan . Till 2006, only four other reports published about it, referring to its taxonomy, genetics or decomposition [23-25]. Since 2007, C. lacerata has been more widely researched on its clinical significance, wood-decaying effect, metal tolerance and sorption potential and some other characteristics [26-30]. Kim et al.  found that the cadmium(II) removal rates by C. lacerata in stationary and shaking cultures were about 7% and 11%, respectively. However, there is so limited information yet available on this species that its other properties need further study. The objectives of this work were to verify the capacity of dead C. lacerata in copper(II) removal under batch conditions, to determine the influences of parameters involved, and to simulate the adsorptive equilibrium and kinetics.
Materials and methods
Preparation of the biomass
Fungus C. lacerata was isolated from the litter of Solidago canadensis (an exotic plant to China) in Pukou, Nanjing, China. It was cultivated at 25°C in 250 mL flasks containing 100 mL liquid medium composed of malt extract (20 g/L), peptone (1 g/L) and dextrose (20 g/L). After about 10 days incubation on a shaker at 150 r/min, C. lacerata mycelium was washed several times with deionized water, and then inactivated by immersion into 1% formaldehyde. After washing, the mycelium was dried at 60°C for 24 hour (h). Finally, dry mycelium was ground and sieved (mesh size < 0.5 mm).
Copper(II) solutions of 5 to 300 mg/L were obtained by diluting copper(II) stock solution (1 g/L), which was prepared by dissolving CuCl2 · 2H2O (analytical reagent grade, Shanghai Zhenxing Chemical Reagent Factory, China) in deionized water. Solution pH was adjusted with 0.1 mol/L HCl and NaOH and measured by pH meter (PHS-3C, Shanghai Hongyi Instrumentation Co., Ltd, China).
Batch biosorption experiments
where q e (mg/g) is the amount of copper(II) adsorbed on per gram of biosorbent, V (L) is the volume of copper(II) solution in the flasks, C 0 and C e (mg/L) are the initial and equilibrium copper(II) concentration, respectively, and m (g) is the dry weight of dead C. lacerata biomass.
Experiments to evaluate the effect of pH on biosorption were conducted constantly at pH 2.5 to 7.0, with intervals of 0.5, while initial copper(II) concentration was 100 mg/L.
Experiments to analyze the effect of contact time were operated at optimum pH and copper(II) concentration of 100 mg/L. Samples were harvested at 1/12, 1/6, 1/4, 1/2, 1, 2, 4, 6, 8 and 12 h.
Experiments to analyze the effect of initial sorbate concentration were performed at 5, 10, 25, 50, 75, 100, 200 and 300 mg/L (at optimum pH).
Biosorption kinetics analysis
where k’ (h−1) and k P (g/mg · h) are the first and second-order rate constants, respectively, q e and q t are the amounts of copper entrapped on per gram of biosorbent (mg/g) at equilibrium and time t (h), respectively.
Biosorption isotherm analysis
Experiments to evaluate the effect of initial sorbate concentration were also used for biosorption isotherm studies. Langmuir and Freundlich isotherms were used to simulate the experimental data from the batch system at 25°C.
Results and discussion
Effect of pH on biosorption
Previous studies showed that pH value of the solution was an important parameter for both solution chemical properties of metals and surface characteristics of biosorbents [37-41]. According to Asmal et al. , there are three species of copper present in solution: Cu2+, CuOH+ and Cu(OH)2. At low pH (here maybe from 2.5 to 3.5), H+ ions competed with Cu2+ ions for the biosorption sites, that is protonation of the cell wall components negatively affected the biosorption capacity of dead C. lacerata biomass. However, this effect became less with the increase in pH (from 4.0 to 6.0) owing to that the raise of negative charges density on the cell surface offered more metal binding sites [6,7,15]. At this pH Cu2+ and CuOH+ were more favourable copper species. Therefore, just like the results of some works [6,43-45], we also found a sharp increase in biosorption with a slight increase of pH (at around pH 3.5). At higher pH (≥6.5), precipitation of copper(II) hydroxide occurred and precipitated on surfaces of biomass and bottle wall. Furthermore, all those above suggested that ion-exchange played an important role in biosorption of copper(II) ions by dead C. lacerata.
The optimum pH was 6.0 at which copper(II) biosorption capacity of dead C. lacerata biomass reached 6.79 mg/g. The optimum pH values of different reports on copper(II) biosorption by different biomasses differ quite a bit. Phanerochaete chrysosporium fungal biomasses [7,40] and three species of dead fungal biomasses (Cladosporium cladosporioides, Gliomastix murorum and Bjerkandera sp.)  showed the same optimum pH 6.0 for copper(II) removal, while cone biomass of Thuja orientalis showed the optimum pH value to be 7.7  and Chlorella vulgaris algal biomass to be 5.0. The components and structural characteristics of various biomasses are quite diverse, which may be the most important reason for optimum pH differences. There must be other reasons such as different experimental parameters and operating error.
Effect of contact time on biosorption
The equilibrium time of the copper biosorption by fungal biomass is determined by many parameters such as agitation rate of the solution, pretreated methods of the fungal biomass, structural properties and quantity of the biosorbents, the existence of other metal ions and initial copper(II) concentration . Therefore, one species of biosorbent may cost different time (ranging from a few minutes to several hours [7,14,48]) to reach equilibrium under different conditions. One hour as the equilibrium time of copper biosorption in this study was scarcely reported before.
Effect of initial copper(II) concentration on biosorption
At pH 6.0, copper(II) precipitated at initial concentrations higher than 300 mg/L. Under the same conditions, in the solutions of higher concentration, there were much more copper(II) ions around the active sites of C. lacerata biomass. Thus the adsorptive process could proceed more sufficiently, and that is why copper(II) adsorptive capacity increased with the increasing of initial concentration.
Kinetic model constants for copper biosorption by C . lacerata at pH 6 and 25°C
Constants of model
q e = 3.37 mg/g
k’ = 11.05 × 10−2 h−1
R’ 2 = 0.8233
p < 0.05
q e = 6.76 mg/g
k P = 4.68 × 10−4 g/mg · h
R P 2 = 0.9958
p < 0.05
Isotherm model constants for copper biosorption by C . lacerata at pH 6 and 25°C
Constants of models
q max = 8.31 mg/g
K L = 3.45 × 10−2 mg−1
R L 2 = 0.9979
p < 0.05
n = 0.56
K F = 0.52
R F 2 = 0.9696
p < 0.05
The Langmuir model showed that the maximum capacity of adsorbing copper(II) was 8.31 mg/g, which was assumed that at pH 6.0, 8.31 mg copper(II) would form a complete monolayer onto the surface of per gram of dead C. lacerata. The Freundlich model had constants of 0.52 for K F value related to the adsorption capacity and 0.56 for n value related to the adsorption intensity.
Comparison of biosorption capacity with other adsorbents
Copper(II) adsorption capacities (calculated from Langmuir constant q max ) and experimental parameters of various fungal biosorbents from the literatures
C e (mg/L)
q max (mg/g)
NaOH-treated Aspergillus niger
NaOH-treated Botrytis cinerea
Hydrochloric acid-treated waste beer yeast
Immobilized Phanerochaete chrysosporium
Dead Pleurotus pulmonarius (HCHO inactivated)
Dead Schizophyllum commune (HCHO inactivated)
Dead Ceriporia lacerata (HCHO inactivated)
Pretreatments (taking NaOH-boiling and immobilization as examples) could avail copper(II) ions more functional groups to bind. That may be why formaldehyde inactivated C. lacerata biomass had lower biosorption capacity than those pretreated fungal biosorbents. Compared with other unpretreated fungal adsorbents, however, biosorption capacity of C. lacerata was relatively high.
The results illustrated that formaldehyde inactivated Ceriporia lacerata biomass (without acid or alkali treatment for improving adsorption properties) showed a relatively high capacity in removal of copper(II) from aqueous solutions. The optimum operating conditions was proved to be at pH 6.0, contact time of 1 hour, initial copper(II) concentration of 200 mg/L. The pseudo second-order adsorptive model gave the best adjustment for copper(II) biosorption kinetics, while the equilibrium data fitted very well to both Langmuir and Freundlich adsorptive isotherm models. Without further acid or alkali treatment for improving adsorption properties, formaldehyde inactivated C. lacerata biomass possesses good biosorption characteristics on copper(II) removal from aqueous solutions. Prospectively, immobilized or further pretreated Ceriporia lacerata biomass has potential to be used as an efficient adsorbent in treatment of heavy metal polluted waters.
We are grateful for funding from the Key Project in the National Science and Technology Pillar Program during the Twelfth Five-year Plan Period (2011BAC09B01), the Key National Water Special Project of China (2012ZX07204004-003), the CAS Guiding Strategic Project for Science and Technology (XDA05050204), Guizhou R&D Program for Social Development (Qiankehe SY 3144, Qiankehe SZ 3036).
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