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Journal of Chemical Technology and Biotechnology

J Chem Technol Biotechnol 77:539545 (online: 2002) DOI: 10.1002/jctb.601

Biosorption from aqueous solutions by eggshell membranes and Rhizopus oryzae: equilibrium and kinetic studies
Bogdana Koumanova,1 P Peeva,1 Stephen J Allen,2* KA Gallagher2 and MG Healy2
1 2

Department of Chemical Engineering, University of Chemical Technology and Metallurgy, Soa 1756, Bulgaria School of Chemical Engineering, Queens University of Belfast, David Keir Building, Stranmillis Road, Belfast, UK

Abstract: This study assesses the use of eggshell membranes and Rhizopus oryzae as media for the biosorption of p-chlorophenol (p-CP), 2,4-dichlorophenol (2,4-DCP), 3,5-dichlorophenol (3,5-DCP), reactive dye and cadmium from aqueous solutions. The performance of the adsorbents was quantied by measuring the equilibrium uptake and the batch rate kinetics from solutions. The constants in the Freundlich, Langmuir and RedlichPeterson isotherm models were calculated through the linearization of the equations and linear regression. The kinetics of the adsorption systems for cadmium and a reactive dye have been assessed in a batch stirred adsorber. The effect of the process parameters such as pH, adsorbate concentration, adsorbent dosage, adsorbent particle size, temperature and agitation speed are reported. The external mass transfer coefcients are reported for some different system conditions. Both materials are determined to be effective adsorbents and could nd application in the treatment of contaminated wastestreams. # 2002 Society of Chemical Industry

Keywords: Eggshell membrane; Rhizopus oryzae; biosorption; isotherms


NOTATION

aL aR b Ce C0 Ct kf Kf KL KR ms M n qe Ss t

Langmuir isotherm constant (dm mg ) RedlichPeterson isotherm constant (dm3mg1) RedlichPeterson isotherm constant (dimensionless) Equilibrium liquid phase solute concentration (mg dm3) Initial solute concentration (mg dm3) Solute concentration at time t (mg dm3) External mass transfer coefcient (cm s1) Freundlich isotherm constant (dm3g1) Langmuir isotherm constant (dm3g1) RedlichPeterson isotherm constant (dm3g1) Concentration of particles in liquid (g dm3) Mass (g) Exponent in Freundlich equation (dimensionless) Equilibrium solid phase concentration (mg g1) Specic surface (cm2cm3) Time (s)

INTRODUCTION

Biosorption is talked of frequently in relation to the

removal of metal ions.1,2 In addition, this study aimed to asses the suitability of biosorption for the removal of organics from water. In biosorption it is accepted that the cell wall and its associated functional groups are responsible for the metal biosorbent property of dead cells. However, the mechanism of binding is relatively poorly understood.3 This may be due to the many possible binding sites on the variety of biomolecules present in microbial cell walls. It is also strongly believed that biosorbents show preferences for heavy metals, reecting the size of their ionic radii.4 Biomass materials by their nature are cheap and abundant. They may be generated as a waste byproduct from large-scale fermentation, as is the case with Sacchromyces cerevisiae,5,6 or produced in large quantities by nature as is the case with Ascophyllum nodosum.2 It is currently believed that biomass-based technologies can either enhance the performance of, or replace altogether, certain conventional methods for the removal of constituents from water. It is believed that some of these technologies are actually competitive with existing non-biomass-based treatments.7 This is true particularly if the biomass is produced as a waste product from another industrial process, eg enzyme fermentation8 or brewing, as mentioned above. Biomass from fungal/bacterial sources is also a renewable material which can be replaced, which is a

* Correspondence to: Stephen J Allen, School of Chemical Engineering, Queens University of Belfast, David Keir Building, Stranmillis Road, Belfast, UK Contract/grant sponsor: Ministry of Education, Science and Technologies, Soa, Bulgaria; contract/grant number: X-604 (Received 21 November 2001; accepted 30 November 2001)

# 2002 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2002/$30.00

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distinct advantage over other non-renewable adsorbents. The ability to regenerate the adsorbent as distinct from renewing or growing new material is not under investigation. However, it is accepted that the regeneration of an adsorbent is of importance in many applications. Despite this stiff opposition numerous examples exist where biosorbents can out-perform non-biomassbased alternatives. For example Rhizopus oryzae removes 2.5 and 3.3 times more uranium than ionexchange resin or activated carbon respectively.9 Two commercial biosorbents are also available. They are made from consortia of biomass types and processed in various ways to create Algasorb2 and Bio-Fix2.10 Within the class of fungi known as the Zygomycetes the order of Mucorales is very abundant Mucorales are saprophytes (ie they obtain organic matter in solution from dead or decaying tissues of plants or animals), Rhizopus oryzae is a member of this order. This fungus contains chitosan as a major component. Chitosan is the polymer of n-glucosamine which has undergone little or no acetylation and is found as a cell wall component of R oryzae and other Mucorales fungi.11 Chitin is the acetylated form of the glucosamine polymer. These biopolymers are signicant constituents of R oryzae, therefore it stands to reason that the adsorption performance of this biomass is likely to be very signicantly dictated by these bioploymers. In addition, by harvesting R oryzae during the late exponential growth phase it is possible to maximise production of chitosan in the cellular structure,12 thereby facilitating improved adsorptive performance. Initial investigations in the context of dye biosorption have been based upon extrapolation of data and information obtained from studies into heavy metal and humic/fulvic acid biosorption. The work by Zhou and Banks13 has shown Rhizopus species to be capable of humic/fulvic biosorption via adsorption to the chitin/chitosan cell wall component. The same authors have however noticed differences in process kinetics, thus suggesting the existence of different biosorption mechanisms. Chlorophenols are one of the more hazardous pollutants found in industrial wastewaters and require careful treatment before discharge into a receiving body of waters. Activated carbon adsorption is one of the most widely used methods for removal of organic compounds from efuents. In granular or powdered form it has a good capacity for the adsorption of organic molecules such as chlorinated phenols. However, the high cost of activated carbon and the inherent expensive regeneration of spent carbon are two of the reasons that have stimulated interest in examining the feasibility of using cheaper adsorbent materials. Fly ash, peat, soil, rice husk and wood are some adsorbents which have been used for organic pollutants.1419 Live and dead biomasses are available as abundant and cheap biosorbents.2023 A full evaluation of the economic viability of the utilisation of these adsorbents is essential.
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MATERIALS AND METHODS

Eggshell membrane (ESM) is located on the inner surface of the shell of a hen's egg. Eggshell membrane is a dual membrane whose structure can be described as an intricate lattice meshwork of large and small bres which interlock with each other to form a tenacious sheath.24 By mechanical dissection, the two membranes can be separated, as a clear plane cleavage exists between these two layers. Apart from collagen, eggshell membrane is considered to contain polysaccharides.25 The ESM used for the study of the adsorption of the phenols was obtained from a local farm in Co Down. For the preparation of the ESM a 25% (w/v) aqueous acetic acid solution was rst used to dissolve the eggshell. The membrane was then taken out of the beaker and twice cleaned with fresh distilled water and dried overnight at a temperature of 40 C. The dried membrane was ground and sieved to the required particle size range of 355500 mm. The materials used as adsorbents for the experiments were eggshell membrane and R oryzae (autoclaved), 300500 mm. Rhizopus oryzae was purchased from the International Mycological Institute, Surrey, UK, as IMI Strain 266680 and was isolated from soil in Sri Lanka. The freeze-dried spores were re-activated and then cultured in malt extract broth (MEB; 17 g dm3 malt extract and 3 g dm3 mycological peptone dissolved in distilled water and adjusted to pH 5.4 0.2). The MEB was inoculated using a standard sterile technique and incubated at 32 C for 3 days in an orbital shaker set at 175 rpm. Three ceramic beads were inserted into each batch of broth to break up the lamentous growth as much as possible. The biomass was harvested and washed thoroughly in tap water followed by distilled water and oven-dried at 50 C to constant mass. The dried biomass was ground in a hammer mill. The ground biomass was then sieved and the various fractions retained. Only the 300 500 mm size fraction was used in the investigations. Pure p-CP, 2,4-DCP and 3,5-DCP (>97%), obtained from Fluka, were used as adsorbates in this study. The solutions were prepared by dissolving quantities of the adsorbates in distilled water. Initial concentrations were varied between 2 and 50 mg dm3. For the dye and cadmium systems, initial concentrations up to 1000 mg dm3 were employed. Samples containing only water and biosorbent were treated in the same procedure to avoid a possible interference during the UV-measurements. The dye used in these studies, Levax Brilliant Red E-4BA, is produced by the company Dystar, the dyestuff company of Bayer and Hoechst in Frankfurt, Germany. The structure and the molecular weight of any dye are kept secret by Dystar.10 Experimental equilibrium adsorption data were obtained as follows. A known amount of adsorbent (ranging between 0.1 and 0.5 g dry weight) was weighed into each of several Erlenmeyer asks and shaken with 50 cm3 of aqueous solutions of pollutant of varied concentration at a
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constant temperature of 20 C for either 6 days (the time required for equilibrium to be reached for the cadmium and phenols), or 21 days (for the dye system). Blanks containing no adsorbate and replicates of each adsorption point were used for each series of experiments. The pH of the solution, before and after the adsorption process, was measured with a LPH 430T pH-meter, TACUSSEL electronique. After ltering through a Whatman1 GF/A lter paper the solutions were analysed using a Perkin-Elmer 323 UV-Vis NIR Spectrophotometer to determine the residual concentration of the studied compound. p-CP was analysed by UV absorbance at 280 nm (eggshells as adsorbent) and 226 nm (R oryzae as adsorbent), 2,4-DCP at 285 nm and 3,5-DCP at 278 nm. The dye concentration of the bulk phase was measured with a Perkin-Elmer Lambda 12 UV-Vis Spectrophotometer at the maximum wavelength. Metal ion concentrations were determined using a Perkin-Elmer 400 Series ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometer). The batch study was set up according to previous studies.2628 After the adsorbent was added to the dye or metal ion solution, samples were taken at least every 10 min during the rst hour, every 30 min afterwards until the end of the second day and every hour during the third day.

phase equilibrium adsorbate concentration; expressed as milligram adsorbate per dm3 of solution (x-axis). These data will then be represented mathematically by isotherm relationships such as the Langmuir, Freundlich and RedlichPeterson adsorption isotherms. These relationships are described elsewhere.29,30 A summary of the isotherm relationships is presented as: Langmuir : or Freundlich : Redlich--Peterson : qe KL Ce 1 aL Ce Qm Ce Ce Kd KR Ce b 1 aR Ce 1 2 3 4

qe

n qe Kf Ce

qe

ADSORPTION MODELS AND DATA ANALYSIS

The adsorption process is a mass transfer operation which can be described mathematically by an equilibrium process and a rate process. The equilibrium is established between the concentration of the material dissolved in the water and that bound to the adsorbent. To facilitate the description of an adsorption process in terms of a batch equilibrium process a nite amount of adsorbent is brought into contact with various concentrations of the adsorbate. Batch equilibrium studies yield information as to the total capacity of an adsorbent for a particular material in single component systems. Additionally, isotherm constants, necessary in the mathematical modelling of sorption systems, may be obtained from representation of the equilibrium data as isotherm plots. The results are presented as plots of solid-phase equilibrium metal concentration; expressed perhaps as milligram adsorbate per gram adsorbent (y-axis), versus the liquid-

The assumptions associated with the Langmuir model are well known.31 The Freundlich model assumes a heterogeneous adsorption surface with sites that have different energies of adsorption and are not equally available. The Freundlich isotherm is more widely used but provides no information on the monolayer adsorption capacity in contrast to the Langmuir model. The RedlichPeterson model is described as combining elements of both of the other models and is often used to describe equilibrium over a wide concentration range. KR approximates to KL, the Langmuir constant. The slope and intercept of the transformed data plots were used to estimate the two parameters in the Freundlich and Langmuir equations and the aR and b values in the RedlichPeterson model (Table 1). Adsorption isotherms are a useful quantitative tool when representing the adsorption capacity of an adsorbent for a given solute. However isotherms are obtained under equilibrium conditions, whereas in most adsorption treatment applications the retention time is too short for equilibrium to be attained. For this reason we must obtain information on the time dependence of adsorption processes by carrying out process-orientated kinetic studies. In adsorption, the rate of uptake will be affected by various system variables or parameters. During the adsorption mechanism there exists a series of resistances to mass transfer. These may be either `external resistances' in the case of the resistance encountered

Table 1. Isotherm constants for R oryzae and ESM adsorption systems

Adsorbate p-Chlorophenol on R oryzae 2,4-Dichlorophenol on ESM 3,5-Dichlorophenol on ESM Cadmium on R oryzae Cadmium on ESM Reactive dye on R oryzae Reactive Dye on ESM

KL 0.581 0.344 0.319 0.361 24.27 8.143 2.10

aL 0.052 0.143 0.100 0.019 0.33 0.042 0.006

R2 0.985 0.996 0.994 0.860 0.760 0.947 0.61

Kf 0.635 0.448 0.309 1.090 32.49 43.62 6.450

n 0.756 0.484 0.695 0.518 0.19 0.248 0.650

R2 0.989 0.989 0.987 0.777 0.85 0.898 0.671

KR 0.581 0.344 0.319 0.361 0.33 8.143 2.10

b 1.135 1.023 0.878 0.890 1.41 0.762 0.16

aR 0.035 0.134 0.133 0.071 0.77 0.129 21.82

R2 0.976 0.996 0.991 0.850 0.721 0.895 0.911 541

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by solute molecules as they diffuse as a solute `lm' onto the adsorbent particle surface, or `internal resistances' in the case of that encountered by solute molecules as they diffuse through the liquid lling the pores on its way to the adsorption site. The former is characterised by the external mass transfer coefcient and the latter by pore and solid diffusivities. Kinetic models which consider one type of resistance alone are termed single resistance models. These determine the relative effect of lm diffusion (external mass transfer) on the adsorption rate in isolation.2628 By plotting a concentration decay curve we can see how the rate of adsorption changes with time. If we assume that the resistances to mass transfer posed by the bulk aqueous phase and uptake at the adsorption site to be negligible,32 then we can concentrate on the internal and external mass transfer resistances caused by diffusion and the boundary layer as being responsible for controlling the rate of mass transfer. Models which concentrate on one type of resistance in isolation are called single resistance models. A straightforward, but also less accurate, method of obtaining a measure of resistance to external mass transfer is by obtaining kf (external mass transfer coefcient) by the initial slope method of Spahn and Schlunder.33 This entails a graphical differentiation of concentration decay at time zero, since at t = 0 Cs 0 and Ct C0. The expression is shown below in eqn (5). The initial slope of this plot of Ct /C0 v t plot will give a slope from which kf can be extracted: 2  3 Ct d 6 C0 7 6 7 5 4 dt 5 kf Ss
t0

Figure 1. 2,4-DCP adsorption isotherms and model ts on eggshell membranes.

RESULTS AND DISCUSSION

It is well known that the most critical parameter in the adsorption of chlorinated phenols that affects biosorption capacity is the pH of the sorption medium. A series of experiments demonstrated that the pH of the initial model solutions was 6.0 and after addition of the biosorbent it initially remained the same. Measurement of the pH at the end of the sorption process demonstrated that it had changed to pH 7. The results indicate that for chlorophenol adsorption, pH change is only signicant in the acidic region, pH 1.06.0. The nature of the biosorbent inuences the pH of the medium. It was established that the uptake of dichlorophenols by eggshell membrane was higher than that of p-CP. The highest values of uptake in the case of 2,4-DCP (C0 2.5 mg dm3) were 48.2% (0.1 g sorbent) and 71.2% (0.3 g sorbent), respectively. The values for 3,5-DCP (C0 4.3 mg dm3) were 37.2% and 74.4%, respectively. The uptake of p-CP from the solutions with initial concentrations ranging from 2 to 30 mg dm3 was very low (no more than 5%).
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The adsorption isotherms determined for 2,4-DCP and 3,5-DCP on eggshell membranes have the general shape of a Type I isotherm in the Brunauer classication.34 Sample isotherms according to Langmuir, Freundlich and RedlichPeterson in linear form are given in Fig 1. The isotherm constants for both compounds are useful parameters for predicting adsorption capacities. These have been calculated and their values are presented in Table 1. Figures 14 compare plots of the equilibrium isotherm and the model ts. Figure 2 shows the model ts for 3,5-DCP and for example the data obtained are correlated better by the Langmuir and RedlichPeterson isotherms than the Freundlich isotherm. The adsorption is affected by the substituents of the aromatic ring which modify the electron density of the aromatic ring.35 Chlorine decreases the electron density of the aromatic ring and as a result the interaction of the system with the biosorbent will increase with increasing basicity. The higher chlorine content in the phenol molecule strongly inuences the adsorption uptake. The adsorption capacity determined for both dichlorophenols is very similar. The lower adsorption capacity for p-CP compared with those for 2,4-DCP and for 3,5-DCP conrms this statement. The adsorption isotherm for p-CP has the general shape of a Type I isotherm of the Brunauer classication. In the case of this biosorbent the adsorption

Figure 2. 3,5-DCP adsorption isotherms and model ts on eggshell membranes.

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Figure 3. p-CP adsorption isotherms and model ts on RO, 300500mm.

isotherm is described better with the Freundlich model. Compared with eggshell membranes R oryzae has a greater adsorption capacity for p-CP. The relative uptake of p-CP was higher at lower concentrations. It was 77.8% at a C0 of 4.5 mg dm3 (0.5 g sorbent) and decreased to 48.1% at a C0 of 48.5 mg dm3. When the sorbent quantity was 0.3 g the uptake was 55.5% and when the initial concentration of p-CP was increased it decreased to 32.1%. Apart from the equilibrium studies, batch studies were undertaken to determine external mass transfer coefcients for the sorption processes. It can be seen that agitation rate affects the uptake with time. The mass transfer coefcients shown in Table 2 demonstrate how increasing agitation shears the boundary layer, reducing resistance to mass transfer and increasing the effective rate of mass transfer for all three adsorbate systems. The effective rate of adsorption falls as initial concentration is increased. In theory a concentration gradient between the bulk solution and the external surface should help drive adsorption, therefore as the initial concentration increases we would expect to see an increased rate of adsorption due to the corresponding reduction in concentration gradient. The smaller relative decrease in kf for the R oryzae dye as opposed to the Cd uptake system is not entirely unexpected since McKay and colleagues27,28 showed kf to be independent of initial dye concentration during the uptake of dyes by chitin which is a signicant component of the biomass used. The reason given was that all parameters in the system which affect

mixing power number and energy dissipation rate are constant. Adsorbent particle size has a minimal effect on the rate of uptake of the adsorbates by the R oryzae. Adsorption as a surface phenomenon would be inuenced by surface area, therefore we would expect the rate to decrease as the particle size increased due to the subsequent reduction in surface area of the larger adsorbent. The results shown can be justied by saying that R oryzae is predominately microporous. Therefore, external surface area contributes very little to overall surface area. Hence any increase in adsorption rate is purely dependent upon the decrease in diffusional resistance and not on additional available surface area. The rate of cadmium uptake is minimally increased by increased adsorbent dosage. Dye uptake rates appear to be independent of this parameter. Mathematical analysis assumes spherical adsorbent particles, consequently varying adsorbent dosage and hence surface area available for adsorption, Ss, caused minimal variation in kf, supporting this approximation. Decreasing solution pH increases the rate of dye uptake. The rate of metal ion uptake shows the opposite trend with effective rate increasing with increasing solution pH. This is in agreement with the strong pH dependence shown in equilibrium studies. Table 2 shows the adsorption rate of dye to be slightly increased by temperature with cadmium adsorption uptake showing a decreased rate. There is no obvious trend in these results. Therefore it may be possible that no Arrhenius dependence is in effect and that no activation energy threshold must be encountered during adsorption in these systems. Adsorption systems which encountered more signicant chemisorption may have a more obvious Arrhenius dependence. By comparing experimental decay curves with data predicted by single resistance mass transfer models it is possible to evaluate the usefulness of that model. This generates the theoretical, or predicted, concentration decay curves which can then be correlated with experimental data to give an indication of the goodness of t. An example of this is shown in Fig 5 which shows experimental and theoretical data for the uptake of cadmium by R oryzae under different conditions. With very few exceptions adsorption of dye and cadmium under the inuence of all process parameters is favourably predicted by the model as t 0. However it appears that as time increases past the initial few minutes this favourable prediction breaks down. Since this model is concerned with resistance to mass transfer by external surface boundary layers which will be overcome as t 0, then the results are proof of the models' limited usefulness. Deviation between experimental and theoretical data at longer contact time may be attributed to the effect which intraparticle diffusion has on the overall rate of adsorption.

Figure 4. Equilibrium isotherm for R oryzae and reactive dye.

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Table 2. External mass transfer co-efcients for dye and cadmium uptake

System variable

Reactive dye on R oryzae, kf (104) cm s1

Cadmium on R oryzae, kf (104) cm s1 5.128 4.103 5.128 9.450 11.077 10.256 9.143 5.103 4.103 2.051 1.325 2.762 4.608 3.986 2.564 3.057 3.111 3.859 2.051 4.103 5.128 4.103 4.223 4.103 5.128 3.077 2.751

Agitation rate (rpm) 100 1.540 200 2.051 300 1.542 400 2.561 500 3.080 Initial conc (mg dm3) 100 4.103 200 4.103 300 2.564 400 2.051 500 2.062 Particle size (mm) 50180 1.059 180300 1.934 300500 1.382 500710 2.098 Adsorbent dosage (g dm3) 0.25 2.564 0.5 2.564 1.0 3.077 1.5 2.564 2.0 2.064 Solution pH 1.5 5.411 3.0 3.077 4.5 3.464 6.0 2.564 Temperature ( C) 5 2.668 20 3.077 30 3.103 40 3.103

inuenced by the presence of chlorine in the compounds. The biosorption data in this study show that eggshell membranes are a suitable material for reduction of the concentrations of some chlorinated phenols in water. R oryzae has a higher sorption capacity for p-CP. Here, the Freundlich isotherm appears to describe the sorption process more favourably. Dye and cadmium equilibrium adsorption can be successfully modelled using either the Langmuir, Freundlich or RedlichPeterson isotherms. The description by the Langmuir model conrms chemisorption as the rate-controlling step, since the reactive dye is supposed to react with reactive groups on the surface of the ESM. The single resistance model allowed the resistance to mass transfer posed by the external boundary layer to be described. It was found that agitation rate, initial adsorbate concentration, and temperature all affected the external mass transfer coefcient which was used as an effective adsorption rate parameter. In general the model was able to predict adsorption decay in the very early stages of adsorption. Dye uptake was very sensitive to pH changes in the adsorption system. Maximum dye uptake was observed at pH 2 but decreased sharply as the pH value increased.

ACKNOWLEDGEMENTS

The present work has been supported by the Ministry of Education, Science and Technologies (project No X-604), Soa, Bulgaria.

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CONCLUSIONS

Of the three isotherms considered, the Langmuir and RedlichPeterson sorption models adequately describe the equilibrium processes for chlorophenol adsorption. The equilibrium uptake appears to be

Figure 5. Comparison of theoretical and predicted concentration decay data for the uptake of cadmium by R oryzae showing the inuence of agitation rate on decay.

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