cut Basten wort Ye NIA Dog Date Ree: 8/10/2007 No Location: Electronic fournal, Borrower: UAP Conditional TLL: 32884430 Maxcost: $50.001M Request Type: e+ ILLiad LenderString: *VYT,PBU,OKU,OKT,WVU OCLC Number: 27826255 jon: LVIS, GS#P, @AMIBCR, @/BCR Staff Email: fyrill@uafedu Billing Notes: Title: Colloids and surfaces. A, Physicochemical and engineering aspects. Uniform Title: Author Edition: any Imprints Amsterdam ; New York : Elsevier, c1993- Article: Mungasavalli, Deepa Prabhu,: Biosorption of chromium from aqueous solutions by pretreated Aspergillus niger: Batch and column studies. Vol 301 Nox 1-3 Pages: 214-coa Date: july 5, 2007 Dissertation: Verified: OCLC 0927-7757 Borrowing We use Ariel v.3.3 Please don't send mail via Library Rate as it takes 6+ weeks fo Alaska. (Ifyou send via UPS or Notes: Fed Ex type service use 310 Tanana Loop) ShipTo: Univ of Alaska Fairbanks/Rasmuson Library - ILL Rm. 320/P.0, BOX 756807/Fairbanks, Alaska 99775-6807 E-deliver tilde: 907-474-5744 Phone: 907-474-6691 Ariel Address: ill-ariel.elmer.uaf.edu or 137.229.33.21 Odyssey A A ral Ship Via: ARIEL/FAX/USPS ARIELIFAX/U 2. Borrower: UAF Return To: ILL: 32884430 Lender: vyt (Clarkson University Req Date: 8/10/2007 OCLC #: 27826255 Edlucational Resources Center / ILL, Dept 8 Clarkson Ave, P.O. Box 5590 Potsdam, NY_ 13699-5590 1 ShipVis Patron: Chatterjee, Abhijit Colloids and surfaces. A, Physicochemical and e Ship To: Mungasavali, Deepa Prabhu,: Biosorption of | chromium from aqueous solutions by pretreated Asnervillus niver: Ratch and columa studies Univ of Alaska Fairbanks Vol: 301 Nos 13 Rasmuson Library - ILL Rm. 320 Date:_ july 5, 2007 Pages: 214-¢0a P.O. BOX 756807 Verified: | P. chryso- genum (40,3£03%)>A. niger Q9343.0%)>R oryzae (23.5 0.3%). Fungus A. niger is reported to have less affin- ity to Ce(VP compared to other fungal biomass, R. nigricans, R aarrhigus, and A, oryzae [17]. Fungi of Mucorales family (Mucor rouxii or R. arrhizus) were found to possess more chitosan than A, niger [2]. However, pretreating the A. niger biomass to improve the biosorption capacity, and the use of immobi- lized pretreated A. niger biomass in a column for chromium removal have not yet been investigated. Pretreatment of fungal ‘biomass has been found to improve the biosorption capacity ‘of fungal biomass for other metals [6]. There is a potential for the use of the pretreated fungal biomass for sorption of chromium from industrial wastewaters. The development of pretreated fungal biomass is technically feasible because the techniques required for development are relatively simple and technologically viable. Therefore, this present work focuses on, these aspects of chromium biasorption by A. niger biomass. 2, Materials and methods 2.1. Biomass preparation and pretreatment A laboratory strain of A. niger (ATCC 11414) was routinely maintained on Bacto® potato dextrose agar. For experimental purposes, A. niger was inoculated into a liquid medium compris- ing (in g/L) the following: Difco® dextrose, 20; Bacto® peptone, 10; Bacto® yeast extract, 3, in deionized water with pH adjusted 10 5.0 by 1.ON HCL. The cultures were grown in an aerobic con- dition at room temperature (22 + 2°C) with 100 mL ofthe liquid ‘medium in 250 mL. conical flasks on a rotary shaker agitated at 125 pm, All culture work was conducted aseptically. The Fungi _grew as pellicles and were harvested after 4 days of growth by fil- tering the growth media through a 150 um sieve. The harvested fungal pellicles were washed with generous amounts of deion- ized water and autoclaved for 30 min at 121 °Cand 103kPa, The autoclaved biomass was allowed to cool down, hand-pressed, and dried in an oven at 60°C for 24h, This dried autoclaved biomass was ground (© a powder and used directly in metal biosorption experiments or pretreated with various chemicals. Five grams of powdered autoclaved biomass was agitated for 24 in S00 mL of each of the following chemicals: acid (0.1N, HyS04); alkali (.01N NaOH); acetone (50%, v/v) formalde hhyde (10%, vy); cetyl trimethyl ammonium bromide (CTAB) (5%, wiv); polyethylemine (PED (1%, w/v); and 3-(2-amino ethyl amino) propyl timethoxy silane (APTS) (3%, viv). The resulting biomass was filtered, washed thoroughly with atleast afew litres of deionized water and then dried at 40°C for 24h. After drying, the pretreated biomasses were ground into a pow~ der and biomass particles passing through 425 yum sieve were used in biosorption experiments. 2.2. Chromium solution and analysis Stock chromium solution of 1000 mg/L. was prepared by dissolving 2.8283 of potassium dichromate in 11 of deion ized water. The working chromium solution of 10mg/L was prepared by diluting the stock chromium solution, The total chromium concentration in the solution was determined by atomic absorption spectroscopy using a Varian AIO atomic absorption spectrometer [21] 2.3. Batch biosorption studies Allbatch biosorption experiments were conducted in 250 mL Erlenmeyer flasks with 100 mL. metal solution. Sodium acetate buffer (pH 4.0 and 5.0), potassium phosphate butler (pl 60-80), 0.1N NaOH, and 0.1N HCI solutions were used to adjust and maintain the pH of the metal solutions. Buffer solu- vions were notused at lower pl values (2.0 and 3.0) as neligible pH drift occured below 2.5 [22]. Metal solutions were vacuum- filtered through 0.45 ym polycarbonate filters after biosortion experiments. A control with no biomass was also setup foreach run, All experiments were conducted in duplicate and the mean values were used in the analysis of data, 2.3.1. Effect of pretreatment "To study the effect of pretreatment on A. niger biomass, cach pretreated and autoclaved biomass of 0.2 ¢ was shaken in a metal, solution of pH 2.0 for 12h at 175 rpm on a mechanical platform shaker at room temperature (22: 2°C). 2.3.2. Factorial design of experiments ‘A two level full factorial design (2*=16 runs) was chosen, With the total number of runs with replicates being 32. High and low level values of factors such as pH (2.0 and 8.0), temperature ($2 and 302°C), agitation speed (100 and 200 cpm), and mass ofthe adsorbent (0.1 and I g) were varied for each exper imental setup. The samples Were shaken for a fixed time period. of 12 hon a mechanical platform shaker. Temperature was main- tained at desired values using a temperature-controlled storage unit, where the experiments were conducted. The analysis of results was performed by the statistical and graphical analysis, software MINITAB® Release 14 [23], developed by Minitab Inc., USA, 2.3.3. Effect of pH ‘The effect of pH on the biosorption of chromium was invest gated by contacting the best pretreated biomass (0.2g) inthe pET range of 2.0-8.0, with increments of 1. The pH was kept con- stant during the study. The samples were shaken 12h at 175 rpm, at room temperature (222°C), 2.3.4. Kinetics of sorption Tn order to determine the equilibrium time, the sorption mix- ture was agitated at 175 rpm atthe optimum pH. Samples were collected at very short intervals for the first Ih and every hour for (2h after that. Data from the kinetic studies were fitted to the Lagengren and Ho models to examine the biosorption Kinet216 DP Mangasralt ea. / Colloids and Surfoces A: Physicochem. Bg Aspects 301 (2007) 214-223, ies. Non-linear regression was performed with the statistical software STATISTICA for Windows [24] Lagergren [25] showed that the rate of adsorption of pollu- tants on the adsorbent followed a pseudo-first order equation. ‘The non-linear equation is expressed as follows: 41 = all — expt] o where ky isthe Lagergren rate constant for adsorption (h~" de the amount of adsorbate adsorbed at equilibrium (mg); and qr is the amount of adsorbate adsorbed (m/e) at any given time t @. 'A pseudo-socond onder reaction rate equation was proposed by Ho and McKay (26] to study the kinetics of adsorption. The equation is expressed as follows: karat T+ Gated ‘where ky is the pseudo-second order adsorption rate constant (eX(mgh)); and ge and q, are defined cartier. % @ 2.3.3. Isotherm modeling ‘The removal of chromium from the aqueous solution contain- ing 10 mg/L chromium by the best pretreated biomass at various, temperatures was studied by conducting batch experiments at 542, 15-£2, 22 +2 (room temperature), and 302°C. Rep- reseniative masses (0,03, 0.05, 0.1, 0.15, 0.2, 0.4, 0.6, 0.8, and |.0g) ofthe pretreated biomass were agitated at 175rpm for a period equal to the equilibrium time. Data from the isotherm studies were fited to the Langmuir and Freundlich isotherm, ‘models. Non-linear regression was performed with the statistical software STATISTICA for Windows [24] ‘The Langmuir model can be described as follows [27,28 OC. T+ bC. where q is the amount of adsorbate adsorbed per unit mass of adsorbent (mg/g); O° the constant, indicating the mass of adsorbed solute completely required to saturate a unit mass of adsorbent (mg/g); b the constant, related to the energy or net enthalpy of adsorption (Limg); and Cis the equitibrium solute ‘concentration (mg/L). ‘The Freundlich isotherm has the general form (28,29) eo 4 = Kec!" ® where q is the amount of adsorbate adsorbed per unit mass, of adsorbent (mavg); Ki the equilibrium constant indicative of, adsorption capacity (mg/g); Ce the concentration of adsorbate in solution at equilibrium; und n is the adsorption equilibrium, constant indicative of adsorption intensity. 2.3.6. Desorption experiments Chromium metal ions biosorbed on the best pretreated ‘biomass were eluted by acid and alkali solutions. The biomass samples collected on 0.45 um polycarbonate filters after the isotherm study conducted at room temperature (22 ++2°C) were ‘washed into separate 125mL conical flasks containing 100 mL. acid solution (0.1N HCD and alkali solution (0.1N NaOH) in two separate sets. The samples were agitated at 175 rpm for 4h at room temperature (222°C). 24, Thermodynamics of biosorption Gilbbs free energy change (AG) is the fundamental criterion of spontaneity, Reaction occurs spontaneously at a given tem- perature if the value of AG? is negative. The value of AG” can ‘be determined from the following equation (30) AG? = —RTe nb o where AG® is the Gibbs free energy change (ki/mol); R the universal gas constant (8.314 x 10° ki(mot K)); Te the abso- lute temperature (K); and b is the constant, from the Langmuir isotherm model (L/mol); Gibbs free energy change is related to enthalpy change (and entropy change (AS*). The magnitude (of AH? may give an idea about the type of adsorption process involved [30]. This is expressed by the following equation [28}: AG = RT nb AI? ~T.AS° o a where AH? isthe heat of adsorption orenthalpy change (ki/mo!), and AS” isthe entropy change (k3/(mol K)) HP — Teas 2.5. Column biasorption study 2.5.1, Immobilization of pretreated biomass Pretreated A. niger biomass was immobilized in a polysul- fone matrix following the procedure described by Kapoor and Viraraghavan [31], but with certain changes. Seven grams of powdered pretreated biomass and 7 g of polysulfone were mixed in 100 mL of N.N-dimethyl formamide (DMP). The beaker was, immediately sealed to avoid volatilization of DMF and then shaken for approximately 16} on a magnetic shaker for polysul- fone to completely dissolve in DMF and form slurry of uniform, consistency. The slurry was sucked into a 1OmL syringe and allowed 10 drop slowly into a tub of detonized water. Due to the consistency of the slurry and the contact with the ai for 4 brief moment, spherical droplets formed beads upon contact with deionized water in the ub, The biomass was thus immobi- lized within the solidified polysulfone matrix, The beads were cured in a moderately agitated detonized water bath for 24h to diffuse out the DME. After curing, the beads were ai dried for 3 days at room temperature (22 42°C). Finally, the beads were ‘manually screened to remove imegularly shaped beads. 2.5.2. Column study Immobilized pretreated biomass (12.77 g) was packed into 4 Pyrex glass column with an internal diameter of 1.6cm and fa height of 73cm. Bed depth of approximately 55cm was achieved. The bed volume was equal to 110.5 mL. Glass beads ‘were placed on both ends of the column (height of Lem), to allow for even distribution of the influent and also to pre= vent the biomass beads from floating. Glass wool was placed between the glass beads and the biomass beads at the bottom,D.P Mungasovall ea. / Colloids and Sufoces A: Physicochem. Eng. Aspects 301 (2007) 214-223, a of the column. The column was sealed at the bottom using a rubber stopper with a single bore. Tygon tubing was used for the connections. The column was operated in the downflow mode using 2 peristaltic pump with a solution at a concentra- tion of 10 mg/L. of chromium (typical of industrial effluents) boeing pumped at a flow rate of 2.4 mL/min. The bed volume ‘was equal to 110.5mL and the empty bed contact time was 45 min, compared to an equilibrium time of 2h obtained in batch kinetic studies. Initial pH of the metal solution was set at the ‘optimum pH. Samples were collected at very shor intervals ini- tially; subsequently the interval was extended. Samples were analyzed periodically to determine the chromium concentration in the effluent. Once the ratio of effluent to influent concen- tration reached a value of approximately 0.95 of higher, the column study was terminated. At this point, the column was considered to have reached exhaustion. The Thomas and Yan models were fitted fo the columa data. Non-linear regression was performed with the statistical software STATISTICA for Windows [24]. The Thomas modet (32] has the following form (33k: eS exp r/ lgam — CoV) ‘where Ce is the effluent adsorbate concentration (mg/L); Cy the influent adsorbate concentration (mg/L); Kr the Thomas rate constant (Li(minmg)); go the maximum solid phase concentra- tion of the solute (mg/g); m the mass of the adsorbent (g); V the throughput volume (mL); and Q isthe volumetric flow rate (mL/min).Yan etal. [34] developed a new model for heavy metal, removal in a biosorption column, The model is used to describe the binary response regression problem. The logistic equation is expressed as follows: Ce co! [river ® where d is the throughput volume that produces same C./C value at 50% removal and a is the constant, denoting the slope of the function. ®) 2.6. Surface area, pore size, and zeta potential of biomass "The surface area and pore size measurement of powdered autoclaved biomass, powdered pretreated biomass, and immo- bilized biomass were carried out using Micromeritics® ASAP. 2020 accelerated surface area andl porosimetry analyzer. Sur- face charge of the pretreated biomass was measured using a eta potential meter, ZM-77 (Zeta-Meter Inc., NY, USA). 2.7. Fourier transform infrared (FTIR) spectroscopy analysis Infrared (IR) spectra of powdered autoclaved biomass, pre- treated biomass, and pretreated biomass loaded with chromium ‘were obtained using a Fourier transform infrared spectrometer (Perkin Eimer FTIR 1600). For IR studies, S mg of biomass was encapsulated in 400 mg of KBr. “Tate Effect of pretreatment ofA. niger on ieorpio of chromium at p20 ‘oman pe Biceopion capaci Gel) Toate is ‘Acid preteated 20 Akal preted 1 Acetone pers is Fonmaldenydepreeated 22 (CTAB preted 31 PEL preteated 25 APTS preted Le 3. Results and discussion 3.1. Effect of pretreatment Biosorption of chromium ions was found to vary depend- ing on the type of pretreatment (Table 1). All pretreatment methods increased the biosorption of chromium compared to the autoclaved biomass. The autoclaved biomass removed 30% chromium from the reaction mixture. Park et al. (20] also reported approximately 30% removal of chromium using AA niger biomass. The acetone pretteated bfomass showed a biosorption capacity of 1.8 mg/g, which was slightly higher com- pared to autoclaved biomass, Protein and lipid fractions of the biomass surface are reported to be removed by acetone pretreat- ‘ment [16], hence this pretreatment displays a favorable trend for biosorption. The acid pretreated biomass exhibited a slightly better biosorption capacity than alkali pretreated or autoclaved biomass, A similar result was obtained by other researchers {13,16,35,36}.A higher biosorption of anionic species after acid pretreatment can be attributed to the fact that acid hydrolysis, Yields relatively pure amino sugar, which is more easily pro- Tonated at adsorption pH [16]. Therefore, accessibility to the sorption sites mightbe increased [36]. CTAB pretreated biomass ‘exhibited @ maximum biosorption capacity of 3.1 mg/g, which was double the biosorption capacity ofthe autoclaved biomass (1.5mg/g). Bai and Abraham {16} and Loukidow et al. [37] have reported that CTAB pretreatment improved Cr( VI) biosorp- tion of R. nigricans and As(V) biosomption of P.chrysogenum, respectively. Bingo et al. [38] reported that Cr(VD removal efti- ciency of yeasts. cerevisiae, increased trom 55% for unmodified cells to 99.5% for CTAB treated eels. The reason for enfanced removal by cationic surfactant (CTAB, PEL, and APTS) pre- treated biomasses is the enrichment of fungal cell wall with amino [37] and imino groups [16] by these chemicals ‘An increase in surface are of biomass due to pretreatment by surfactant was reported by Bui and Abraham {16}. In our case, the surface area of the CTAB pretreated biomass (1.36 m"/g) was found to be only marginally higher than that ofthe autoclaved. biomass (1.31 m?/), and the pore size of the CTAB pretreated. biomass was 30% larger than that ofthe autoclaved biomass. 3.2, Factorial design of experiments ‘The analysis of variance (ANOVA) for the removal of chromium from an aqueous solution was conducted using the218 (DA Mungasaall et al / Colloids ond Surfaces A: Physicochem. Eng. Aspects 301 (2007) 214-223 ‘Tble2 Estimated effects and eoeficients for reamoval of cromiu fom an aqueous ‘sition obtained trom MINITAB® sofa Tm ‘Code Eoct Coetclnt pValoe Conant 3st 000 Bomar mass ee ito) este | 00] ‘Aghaton spend ae aaa) i one) ot c -s038 -2519 000 “Temperature D478 239000 Biomass mass agitation peed AB 1.60 080.6" Biomass nase pH ©1068 3.84 000 mass nase xtemperture AD 235-118 005 Aiton sped pH bo 338189000 ‘Agitation speed xtempenture = D489 243-000 pl temperate co 85042500 7 Covlationsoefcien ir nt saaeallysiguicantasing Mest at 95% confidence level MINITAB® software and the estimated effects and coefficients for removal of chromium are provided in Table 2. The F-test con ducted totes the feasibility of the model indicated that the main effects and interactions cffects were statistically significant at 95% confidence level with p-value <0.05. It was also observed from test of individual effects that, except forthe p-value of two order interaction AB, al other p-values were significant at 95% confidence level. A regression equation to determine the removal efficiency of chromium formed by combining the coefficients and effects from Table 2 is given as follows: Removal of chromium (%) = 35.51 +5514 + 1418 =25.19C -2.39D ~ 5.344C -L.I8AD + 1.8980 +2.458D +4.25CD 0) ‘where A: biomass mass (g)/100 mL; B: agitation speed (rpm); C: pH; D: temperature (°C); AC: biomass mass x pH; AD: biomass mass x temperature; BC: agitation speed x pll; BD: agitation speed x temperature; CD: pH x temperature. ‘The value of correlation coefficient (r) for the model was found to be 0.99. This indicates that there is a nearly perfect linear relationship between the observed values and the mode! predicted values. The absolute valuc of the coefficient of a particular factor is the measure of its influence on the pereent- ‘age removal of chromium. The positive value of the coefficient indicates that a high level setting of the factor provides beter, ‘adsorption than the low level setting and vice verse for the neg- ative value of the coefficient. The pH and temperature showed, better biosorption of chromium at a low level setting, whereas biomass mass and agitation speed showed better biosorption of ‘chromium at a high level setting. When the pH of the solution ‘was lowered from 8.0 t0 2.0, there was an increase of chromium removal by 30.38%. There was an increase of chromium removal, (11.03%) when the biomass mass was increased from 0.1 t0 1g. A decrease in temperature resulted in an increase of 4.78% in chromium removal. Therefore, it was concluded that pH, ‘biomass mass, and temperature imparted relatively the most goes & Residual chromo concentration, Ce (ag) $ il of he station Eero tat o> Zt pten Fig. 1. Tae eect ofp Hon biosrpion of chomlum and zea potential of CTAB, prteate A. niger Biomass. significant effect on removal efficiency and warranted further investigation, 3.3, Eifect of pH ‘The highest chromium removal by CTAB pretreated A, niger biomass was observed at pH 3.0, and removal efli- ciency decreased with an increase in pH. A similar trend has ‘been reported for a variety of biosorbents [13.15.3841]. Zeta potential measurements provide information regarding the net effective charge on the cell wall surface at different pH values; zetapotential values are presented inFig. I. Asthe pH¥islowered, the overall surface charge on the biomass will become positive or less negative, which will promote a stronger attraction towards, negatively charged Cr(V complex ions in the solution. Hence, biosorption increases wit an increase in the acidity ofthe solu- ‘ion, Butas the pH rises, the concentration of OH” ionsincreases and overall charge on the biomass surface becomes negative. ‘This causes a hindrance to the biosorption of negatively charged chromium ions such as Crz072~, CrO,?™ resulting in a decrease ‘of biosorption of chromium at higher pH levels [12,40]. Hence, it can be concluded that electrostatic attraction plays an impor- tant role in the biosorption of negatively charged chromium ions. from an aqueous solution ata low pH at which the biomass may be positive. Kratochvil et al. [42] reported that the optimum, pH for the efficient removal of total chromium by the seaweed, Sargassum biomass was approximately between 2.0 and 2.5. Maximum Cr(VE) biosorption onto chitin was observed in the pH range of 2.0-3.0 [41]. 3.4. Kinetics of sorption I can be seen that biosorption of chromium consisted of wo phases: a primary rapid phase and a secondary slow phase. The rapid phase lasted for about [5 min and accounted for a major portion ia the total metal biosorption, Chromium removal of 72% was observed in this rapid phase (Fig. 2). A maximum, chromium removal of 76% was achieved after 2h, From 2h to the end of the Kinetic study (12), biosorption was slow andDP Mangasaall et a / Colloids and Surfaces $ ie a ¢ z Observed data : Ao mode! i aera mal i Lagerrea model tte ae “oh ae Time,t (0) Fig. 2, The Lagergron and lo model pos fr the biosorption of chromium on CTAB preted A niger biomass pH 3.0 (Tor 6h only) chromium removal varied by 2%. This is because the kinetics ‘of metal adsorption is usually rapid during the early period of, ‘contact between the adsorbent and adsorbate possibly because of clectrostatic atraction. The active adsorption sites ofthe adsor- bent become involved in chromium complexation as soon as the adsorbent is introduced into the system. It has been sug- gested thatthe slow second phase of chromium uptake may be ‘due «0 the reduced availability of active sites [41]. Since the biosorption of chromium did not increase much after 2h, the ccvilibrium time was found to be 2. This rapid initial uptake is consistent with earlier reports on the biosorption of Cr(VI) by ‘other researchers [12-14,39,43]. A comparison between exper- imental data and the prediction made by the Lagergren and Ho ‘models for the biosorption of chromium by CTAB pretreated biomass for 6h only is showa in Fig. 2. The Flo model exhib- ited a higher comelation coefficient than the Lagengren model ‘and was found to provide a realistic description of the adsonp- tion kinetics of chromium. The analysis of kinetic data by other researchers also showed that chromium biosorption Followed the pseudo-second order kinetic model {12,43} 3.5, Isotherm modeling Both the Langmuir and Freundlich isotherm models were ‘evaluated to examine biosorption. The adsorption parameters calculated for biosorption of chromium on CTAB pretreated biomass at all eemperatures studied are presented in Table 3, ‘Model parameters for biosorption of chromiumt on CTAB pre- A Physicochem Eng Aspects 301 (2007) 214-223, a9 ‘ables Maxinum bosopton opacity and Gibbs ee ener change forthe bisonion ‘of evomiun on CTAB poteted A, niger biomass at vous tempertues “Tenpentare Maximum bisorpion Fre nergy change co capacity (gs) a 3 Tas —210 8 182 =216 2 0s 207 30 6 203 ‘reated biomass were statistically significant at 90 and 95% ‘confidence levels for the Langmuir and Freundlich isotherm ‘models, respectively. The Freundlich model would describe the system better because high correlations were obtained at a higher confidence level. The separation factor R, calculated from the Langmuir isotherm constants indicated that biosorp- tion of chromium on CTAB pretreated A. niger biomass was favorable as values of R were between 0 and 1. The Freundlich ‘constants Kprand I/n were found to be4.3 mg/g and 0.54, respec- tively, at 52°C which were the highest and lowest values for and I/n, respectively, over the temperature range of 5-30°C. High Kp value indicated thatthe chromium adsorption capacity, ‘of CTAB pretreated biomass was high; the low I/n suggested that any large change in the equilibrium concentration of sol- uuble chromium would not result in a change in the amount of chromium sorbed by the pretreated biomass. ‘The biosorption capacity for chromium decreased with an increase in temperature, although it did not show a consis tent pattern. This could be attributed to the possible damage to active sites in the biomass at higher temperatures (Table 4). ‘The maximum sorption capacities shown in Table 4 at various temperatures did not take into account the possible interference offect from other ions in the solution, A decrease in the equi librium biosorption capacity of Pott), Ni(II), and Cr(VD by S. cerevisiae in the temperature interval of 25-40 °C was reported, by Ozer and Ozer [11]. From the thermodynamics point of view, the magnitude of AG decreased slightly with arse in temperature. The negative ‘value confirms the feasibility of the process and the sponta- ‘neous nature of biosorption of chromium on CTAB pretreated ‘biomass. The enthalpy and entropy changes were calculated by plotting the logarithm of the Langmuir constant (6) and inverse of absolute temperature. Enthalpy change (AH°) for biosorption of chromium on pretreated biomass was calculated to be —30.50kH/mol, while entropy change was found to be Tables “The Lang an euch others constants fo chromium bosrpion on CTAB pretest Anger biomas lifeen temperate ‘Tempore FO) Tange conta condich enone e 6 7 ® iy 7 Tin Sur cr our ox 036 3 98 os 142 218 016 ose 038 35 osm ost 2H? 209 009 096 033 Le os 076 502 301 006 09s 063 7 033" 086 7 Galan caicon ie aasicaly rican wnng Fst a 98% onfdene ove Correlation coetcient i sursicallysgieant using es a 90% confidence level20 DP Mangassal et ol /Clloids and Surfaces A: Physicochem. Bg. Aspects 31 (2007) 214-223 & porn 0. N NaOH « Ph ry a Mase of biomass : ‘ie Recovery ofbiosorbed Cr 5 Fig. 3. The desorption pls or HCl and NaOH use tats for bisorpton ‘of enum on CTAB prteted A niger biomass. ~0.033 kImol K). The negative value of &H” showed that the biosorption reaction was exothermic. This was also supported by the decrease in the chromium biosorption capacity of the ‘pretreated biomass with arise in temperature. The high value ‘of enthalpy change showed chat the biosorption of chromium \was very temperature-sensitive and aso implied that in addition, to electrostatic attraction, chemisorption (>29 kV/mol), or com- plexation (8-60 ki/mol) [44] might also be contributing to the biosorption of chromium onto the pretreated biomass. 3.6, Desorption experiments “The result of desorption tests are presented in Fig, 3. NaOH proved tobe a more effective eluant than FIC, with more than 90% chromium being desorbed into the solution, NaOH has been found to be an effective elutant for Cr(VI) by several other researchers {12,13,19]. Park etal. [19] reported that IN NaOH desorbed both Crit) and C(V fom. nigerbiomass, whereas O.5N H1,504 desorted only Crt). ‘highly alkaline pH (8-10) wasleast favorable for chromium _ulsorption by biomass. Such conditions enhanced the weaker- ing of adsorption forces and thus facilitated elution of bound chromium ions and its release into the aqueous system [45]. Several mechanisms including chemisorption, are reported to be involved in the biosorption of chromium. Chemisorption involves an irreversible uptake of metal ions. However, the amount biosorbed during this mechanism (low phase) is signif cantly smaller than the amount biosorbed at equilibrium (results from the kinetic study). Therefore, nearly 95% of chromium was desorbed by NaOH solution. 3.7. Colunn study ‘The column was able to remove greater than 90% chromium up 10 660 min, The bed volume (BV) at breakthrough (10% of the initial concentration) was 14. The column reached exhaus- tion (295% of initial concentration) after 7680 min, treating 18432 mL (167 BY) of chromium solution. The column would ‘need regeneration forthe second cycle al this stage. The observed vvalues and the Thomas and Yan model plots are presented in ‘Gomer dai] hoo mel mode ° ‘ae ry “Throwghpat volume, ¥(m.) Fig 4 The Thomas ant Yon modes for bisorton of chromium on im bilized CTAB prevesed Biomass. Fig 4. After comparing the correlation coefficients (r) obtained from both the models and comparing the q, values, it was Found that both models could adequately describe biosorption ‘of chromium ions on pretreated A. niger biomass. However, the Yan model showed a better fit than the Thomas model. It was observed that the Thomas model over predicted the values, Tho value of maximum solid phase concentration of solute (go) obtained from the Yan model was 2.5 mg/g. The ‘maximum solid phase concentration obtained was based on the bead mass, If based on the biomass mass, the maximum solid phase concentration of metal ions on beads would be two times higher than the values shown above, as the bead compo- sition consisted of 50% biomass and 50% polysulfone. Thus, the qo value based on the mass of biomass would be 5 mg/g, However, when intial chromium concentration of 10 mg/L was, used, the maximum solid phase concentration of chromium on, powdered biomass in batch isotherm experiments at room tem- perature was 10.6mp/g, much higher than that obtained in the column study using beads. The solid phase concentration on the biomass (by integrating the area under the curve) was found to be 5.8mg/g, still much less than the value from batch studies, Fu and Viraraghavan (46] suggested thatthe immobilization of ‘A. niger biomass into the polysulfone matrix brought about a ‘negative influence on dye adsorption as a result of the organic, solvent DME, which might have caused chemical modifications to Fungal biomass. ‘This might also be the case in this study; however, further investigation is necessary. Reduced Cr(VI) biosorption capacity of immobilized R. nigricans and A. flavus biomasses as compared to powdered biomasses in batch studies, ‘was reported by Bai and Abraham [45] and Deepa et al. [47], respectively. ‘The initial pH of the metal solution was set at the optimum pH of 30, The effluent pH varied between 3.0 and 4.0. This ‘pil range is consistent with acidie pH generally encountered in electroplating and similar industrial wastewaters. 3.8, FTIR analysis, ‘The infrared spectra of autoclaved biomass, CTAB pretreated biomass, and CTAB pretreated biomass loaded with chromiumA ungossall et al. / Colloid and Surfaces A eee ‘Teamemitance,%Te Fig. 5. Overy of IR spectrum of atclaved biomass, CTAB preted Dimas, and CTAB preratd biomass loaded with chromium, are shown in Fig. 5. The figure displays a numberof absorption peaks, indicating the complex nature ofthe examined biomass. The infrared absorption wavelengths of each peak and the corresponding functional groups ofthe autoclaved and CTAB pretreted A. niger biomass are presented in Table 5. The broad Absorption peak around 3430-3400.cm~" is indeative of the existence of the -OH groups and the -NH groups (36.48). The 0-H groupstreich can also occur from carboxylic acids (COOH) andis extremely broad, ranging from 3400 10 2400¢m~! which often interferes with C-H absorptions [48], Phosphate fune- tional groups such as P=O, orthophosphate (POg*~), and P-OH. have characteristic absorption peaks at 1150, 1100-1030, and 1040-910em*, respectively [13.37]. C-N stretching can also occur around the same wavelength of 1350-1000em-!. Tobin etal [49] have reported that functional groups such as carboxyl (COOH), amide (-NH), phosphate (-POs*”), and hydroxide Physicochem. Bag Aspects 304 (2007) 214-223, 2 (OH) are responsible for metal sequestering by fungal biomass, ‘The confirmation of these Functional groups onthe IR spectevim of autoclaved and CTAB pretreated biomasses is indicative of theie contribution tothe biosorption of chromium by the A. niger biomass, ‘The IR spectrum of the CTAB pretreated biomass without ctuomium was similar o the IR specirum of the autoclaved biomass; it id not show any characteristic omission or addition ‘of peaks (functional groups) Bai and Abraham (16] presented IR spectra of dead and CTAB pretreated R. nigrican biomass, CCompacison ofthe two spectra showed that the CTAB pretreated £.nigrican biomass spectrum showed an increase in amino and amide stretching and bending, which was taken as a sign of biomass enrichment. Similar observations were also made by Louikidou et al. (37]. No such amino and amide stretching and bending coutd be observed in our case, although it was possible that enrichment of amino and amide groups had occurred and could be detected in the form of a broader and larger spread of troughs Comparing the IR spectrum of CTAB pretreated biomasses without and with chromium, slight changes of all the absorp- tion wavelengths were observed. The IR spectrum of CTAB pretreated biomass with chromium showed the omission of a Single peak, H* (1317.74em~, The absorption wavelength at 1317, 74cm" could be assigned tothe C-N stretching vibration of the chitin-chitosan and protein fractions (16,50) It was also ‘noted that peaks inthe region of lower wavelength (<700cm=!) for autoclaved biomass and CTAB pretreated biomass with- cout chromium appeared to contain multiple absorption peaks in comparison with that of CTAB pretreated biomass loaded with chromium this could be attributed to the interaction between cheomium species and N-containing bioligands [13] Carbohydcates, hexosemines, and proteins, ae the major cell wall constituents; the contributory role of amino groups in chromium binding could be assumed, The negatively charged chromate ons become electrostatically attracted tthe positively ‘Tae eae os of alae and pretacd CTAB biomes ofr ions withr wiou chromium and ie een infare absorpon wavelength (368) label Observed wavelength ange em) Wavelength ange a") Aniganen x 3803400 3500-3200 ‘Bonded ideo groups (OH) 3500-3100 Primary and secondary amines and amides suetehing (N-H sch) Be 2930-2000, 2860-2850, 3000-2850 CH staehing > 2200-2080 2250-2100 C=C groupe 5 160-1640 1870-1640 ©=0 amide I6i0-1580 Primary an secondary amies and aides (N-H bending) 1690-1640 Imins and oxines F 1850-1540 1640-1550 Primacy an secondary amines sn amis (N-H bending) « 60-1450 s0-1375 CH bonding CH) H 1380-1370 1575-1300 ‘Sulfamide bons (=0) © 131774 1330-1000 “Amines (C-N atetching) ' 1260-1230 1300-1000 (C-Osweching of COOH LAL 1160-1150, 1079, 1040-1030 1350-1000 Amines (C-N seth) MN 900-850, 785-750 999-690 CH being * Peak absent in CTAB petated Biomass lod wi chromiummm DP Mugosvel era, Colloids ond Surfaces A: Physicochem ng Aspects 301 (2007) 214-222 ‘charged amines (protonated at low pH) ofthe biomass cell wall (16, 4. Conclusions Pretreatment increased the biosorption capacity of A. niger nass. CTAB pretreated biomass removed 63% chromium from an aqueous solution at pH 2.0, which was higher than the removal achieved by autoclaved (30%) or other pretreated biomasses (36-50%). The kinetics of biosorption of chromium ‘was found to follow Ho pseudo-second order reaction at an optimum pH of 3.0 and equilibrium time of 2h, The columa ccan be operated at an optimum pH of 3.0 in the case of acidic industrial wastewaters; in the case of groundwater, itis not eco rnomical to lower the pH to 3.0 and therefore the system should be designed at the ordinary pH of the water, sacrificing efft- ciency. Isotherm analysis of the data showed that the biosorption pattern for chromium on CTAB pretreated biomass followed the Freundlich isotherm in the entire temperature range stud- ied. Maximum biosorption capacities of 14.5, 15.2, 10.6, and 1.6 mg/g were observed at $2, 152,22 +2, and 30+2°C, respectively, ignoring the effect of possible interference eifect of other ions. Biosorption of chromium on CTAB pretreated ‘A. niger biomass was found to be spontaneous and exothermic in nature, Both electrostatic attraction and chemisorption were involved in the biosorption process, The potential for reusabil- ity of pretreated biomass was examined in the desorption study. ‘More than 90% of chromium was desorbed into solution by NaOH, which was found to be a better elutant than HCI. In the column study, biosorption of chromium by polysul- fone immobilized CTAB pretreated biomass followed the Yan ‘model better than the Thomas model, Based on the analysis, the biosorption capacity of the beads was found to be Smeg/g, \Which was less than the maximum biosorption capacity obtained for powdered biomass in the batch mode. FTIR analysis pro- vvided details of various functional groups present on the fungal bbiomass that contribute to metal sequestering, From this anal- ysis, the role of amino groups on CTAB pretreated biomass ‘Towards chromium biosorption was evident. 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