Non-living biomass of the algae Chara aspera is capable of binding two basic dyes, methylene blue and basic blue 3, from aqueous solution. Factors such as dye concentration, contact time, sorbent dosage and pH of solution were

studied. Maximum sorption capacities of the algae for methylene blue and basic blue 3 are 139.4 and 17.8 mg/g, respectively, as determined from the

Langmuir isothenns

Lee, C. K.

Low, K. S.

Toh, B. L.

Universiti Putra Malaysia Institutional Repository

Pertanika J. Sci. & Techno!. 2(1): 85-92 (1994)ISSN: 0128-7680© Universiti Pertanian Malaysia PressBinding of Basic Dyes by the Algae, Chara asperaK.S. Low, C.K. Lee and B.L. TohChemistry DepartmentFaculty ofScience and Environmental StudiesUniversiti Pertanian Malaysia43400 UPM Serdang, Selangor, MalaysiaReceived 13July 1993ABSTRAK.Suatu algae, Chara aspera, yang bukan hidup boleh menambat dua pewarnaberbes, metilena biru dan basik biru 3, dan larutan akueus. Faktor yangmempengaruhi pengerapan seperti kepekatan pewarna, masa tindakan, dospengerap dan pH larutan telah dikaji. IsotennaLangmuirmenunjukkanbahawamuatan erapan maksimum algae untuk metilena biru dan basik biru 3 adalah139.4 dan 17.8 mg/g.ABSTRACTNon-living biomass of the algae Chara aspera is capable of binding two basicdyes, methylene blue and basic blue 3, from aqueous solution. Factors suchas dye concentration, contact time, sorbent dosage and pH of solution werestudied. Maximum sorption capacities of the algae for methylene blue andbasic blue 3 are 139.4 and 17.8 mg/g, respectively, as determined from theLangmuir isothenns.Keywords: sorption, cationic dyes, algae, Cham asperaINTRODUCTIONThe disposal of coloured substances poses one of industry's major problemsin wastewater treatment. This is because the discharge of coloured wastesis not only damaging to the aesthetic nature of the receiving streams butalso toxic to aquatic life. Dye is one such coloured substance. Thetreatment of dyes is fraught with numerous problems as they are generallystable to light and oxidation and hence cannot be treated by conventionalmethods of aerobic digestion.An alternative method for the total or partial removal of dye is bysorption technique. Various such treatment systems have been developedusing activated carbon as the sorbent (Davis et aL 1973; McKay 1982; McKayet al.1986). While carbon has been used successfully to remove dyes fromsolution, it is, however, expensive. Alternative, cheaper sorbent materials'such as bark (Asfour et al. 1985), rice husk (Nawar and Doma 1989), coal,bentonite clay, cotton waste (Poots et al. 1976a, 1976b), biogas slurry waste(Namasivayam and Yamuna 1992) moss (Lee and Low 1987), banana pith(Namasivayam and Kanchana 1993) and coconut husks (Low and Lee 1990)have been used with varying degrees of success. This paper reports theK.S. Low, C.K. Lee and B.L. Tohpreliminary findings of a study on the effectiveness of an algae, Chara aspera,in removing two cationic dyes from aqueous solutions and the parametersaffecting the sorption process.MATERIALS AND METHODSThe algae Chara aspera was collected from a mining pool in the vicinity of theuniversity. It was cleaned thoroughly before drying at 40cC. Two basic dyes,methylene blue (C.1. 52015) and basic blue 3 (C.1. 51004) were used withoutfurther purification.Contact Time ExperimentsIn these experiments the uptake of the dyes by the algae was conducted byshaking the samples in the dye solutions continuously on a gyratory shaker at200 rpm. Aliquots of 1 ml-solution were withdrawn at regular intervals andanalysed for dye content using a Shimadzu UV-160 UV-visiblespectrophotometer at A.max'S 665 and 654 nm for methylene blue and basicblue 3, respectively. All experiments were conducted in duplicate andvariation in results was generally less than 5 %.Effect ofpHThe effect of pH was studied under equilibrium conditions. The pH ofthe solution was adjusted with either dilute HCI or NaOH beforeexperimentation.Effect ofInitial Dye ConcentrationThe effect of initial concentration was studied by varying the concentrationsof the dye solution from 25-500 p.p.m. Samples were shaken in 100 mlof dye solution and the uptake was monitored at regular intervals.Effect of Sorbent DosageIn the study of the effect of sorbent dosage on dye uptake, the weightof Chara was varied from 0.05-0.50 g for methylene blue and 0.25-1.00 gfor basic blue 3 solutions. The dye concentration for both dyes was maintainedat 100 p.p.m.Sorption IsothermsThe adsorption isotherms for the uptake ofdifferent dyes by Charawere studiedby shaking 0.1 g of Chara with methylene blue solution and 1.00 g Charawith basic blue 3 solution. Concentration was varied from 50 to 800 p.p.m.RESULTS AND DISCUSSIONEffect of pH on SorptionThe effect of pH on the uptake of methylene blue and basic blue 3 byChara is shown in Table 1. In the pH range of 4-10 the sorption was fairly86 Pertanika J. Sci. & Techno!. Vol. 2. No.1, 1994Binding of Basic Dyes by the Algae, Cham aspemconstant for both systems. However, the ability to sorb started to decreasewhen pH was lower than 4. The decrease could be attributed to the presenceof excess H+, making sorption less favourable. Subsequent experimentswere performed without adjusting the pH of the dye solutions (6.3 and4.3 for methylene blue and basic blue 3, respectively).TABLE 1Effect of pH on the sorption of dyesMethylene bluepH Uptake (%)Basic blue 3pH Uptake(%)2.403.486.149.6611.1660.0075.2577.7578.8581.252.174.235.607.899.4317.3627.7126.3128.3927.33Conditions: 0.5 g of algae in 100 ml of 100 p.p.m. dye solution; equilibrationtime: 2 hEffect of Initial Concentration on Sorption IsothermThe effect of initial dye concentration on the rate of sorption is shownin Fig. 1 and Fig. 2. The initial concentration had very little effect onthe contact time required to reach equilibrium. Poots et al. (1978), intheir study on the removal of basic dye using wood as an adsorbent, reportedthe same observation. For both dyes the initial uptake was very rapid,but subsequently slowed down. Equilibrium was attained in about 1 hour.'00 ....-------------,80•6020Concentration (p.p.m.)• 1000250"50040 80 120 160 200 240TIme (min)Fig. 1. Effect of initial concentration on the uptake ofmethylene blue by algae.Condition: 0.1 g algae in 100 ml solutionPertanika J. Sci. & Techno!. Vo!. 2. No. I, 1994 87K.S. Low, C.K. Lee and B.L. Tohloor-------------------.,80Concentration (p.p.m.)• 25• 50... 100o 40 80 120TIme (min)180 200 240Fig. 2. Effect of initial concentration on the uptake ofbasic blue 3 by algaeCondition: 0.5 g algae in 100 ml solutionA long equilibrium time could indicate that the predominant mechanismis physical adsorption and that the process will be reversible. A relativelyshorter equilibrium time would imply that chemisorption is probablyimportant and that regeneration would be more difficult to achieve. Fromthe sorption curves, it appears that the mode of dye sorption on Charais essentially a chemisorption process. Under the same experimentalconditions, Chara was able to remove a larger percentage of methyleneblue (80%) than basic blue 3 (22%). This could be attributed to thedifferent type and number of functional groups in the dyes.Effect of Dosage on SorptionThe effect of sorbent dosage on the uptake of a fixed quantity of dyeis shown in Fig. 3 and Fig. 4. As expected, the percentage sorption ofthe dye increased with increasing dosage. This is due to the greater numberof sorption sites on the aquatic plant.Sorption IsothermsThe results from contact time experiments can be used to determinethe maximum amount of dye sorbed by Chara using a modifiedLangmuir isothermCe/Ne = l/N*b + Ce/N*88 Pertanika J. Sci. & Techno!. Vo!. 2. No. I, 1994Binding of Basic Dyes by the Algae, Chara Asperawhere Ne is the amount ofdye sorbed (mg per gram) of Chara at Ce, the equi-librium concentration of the dye solution (p.p.m.). Plots ofsorption isotherm100 ...----------------......BO60I::>'" 40Dosage (g)• 0.0500.1020.. 0.5040 80 120Time (min)160 200 240Fig. 3. Effect ofsorbent dosage on the uptake ofmethylene blue by algaeCondition: 100 ml of 100 p.p. m. methylene blue; equilibrating time: 2h100D053ge(9)• 0.5080 0 0.75• 1.0080~~ 40::>- --.....,.-:V ..·020 I~a 40 80 120Time (min)180 200 240Fig. 4. Effect ofsorbent dosage on the uptake ofbasic blue 3 by algaeCondition: 100 ml of100 p.p. m. basic blue 3; equilibrating time: 2hPertanika J. Sci. & Techno!. Vo!. 2. No. I, 1994 89K.S. Low, C.K. Lee and B.L. Tohare shown in Fig. 5. The linearity of the plots indicates that Langmuirisotherm can be applied successfully to the dye-Chara system. The maximumsorption capacities (N*) are 139.4 and 17.8 mg/g for methylene blue andbasic blue 3, respectively. These values confirm the earlier observation inthe contact-time experiment that Cham could sorb more methylene bluethan basic blue 3 under similar conditions. The maximum sorption capacityof algae compares favourably with that of moss (185.0 mg/g) (Lee andLow 1987) and coconut husk (99.0 mg/g) (Low and Lee 1990) .•4030•• Basic blue 3• Methylene blue300 400C.lp·p.m.)500 600Fig. 5. Langmuir isotherms for methylene blue and basic blue 3 systemsCondition: methylene blue-O.l g algae in lOa ml ofdye solution;basic blue 3-1. a galgae in lOa ml ofdye solutionComparative Study on the Sorption ofAcidic and Basic DyesIn order to explore the potential of Chara to remove a broader spectrum ofdyes, experiments were conducted using two acid dyes, reactive yellow 2 andreactive orange 16. The results are shown in Fig. 6. The acid dyes showed verylittle affinity for the algae. The difference could be attributed to the nature ofthe algae, whose structure is probably cellulose-based and negativelycharged. The acid dyes dissociate in water to an anionic colouredcomponent and a cationic species. The approach of an acidic dye anion willexperience coulombic repulsion due to the presence of anionic groups inChara. Geundi (1991) also reported that acidic dyes showed less affinity thanbasic dyes on maize cob. However, Poots et at. (1976a) reported that thesorption of acid dye on wood was quite successful although a longer time wasrequired to reach equilibrium.90 Pertanika J. Sci. & Technol. Vol. 2: No.1, 1994Binding of Basic Dyes by the Algae, Chara Aspera100 y---------------------,•80;Q) 60~illCo:::J~40.• Methylene blueo Basic blue 3• Reactive yellow 2o Reactive orange 16o ~20 I(•v'-' ~ - ~0 40 80 120 160 200 240Time (min)Fig. 6. Sorption ofcationic and anionic dyes by algaeCondition: 0.5 g algae in 100 ml of 100 p.p. m. dye solutionCONCLUSIONThis preliminary study shows that the algae Cham aspera, an easily availableaquatic plant, has the potential to remove basic dyes from solution. Methyleneblue showed greater adsorptivity than basic blue 3. Cham aspera is, however,ineffective in binding with acidic dyes.ACKNOWLEDGEMENTSFinancial assistance through IRPA grant no. 4-07-05-017 is acknowledged.REFERENCESAsFOUR, H.M., a.A. FADAL, M.M. NASSAR and M.S. EL-GEUNDI. 1985. Equilibrium studies onadsorption of basic dyes on hardwood. j. Chern. Tech. Biotechnol. 35A: 21-27.DAVIS, R.A., J-K HARMUT and M.M. CLEMUS. 1973. Removal of organic material byadsorption on activated carbon. Chern. and Ind. 1: 327.GEUNDI, M. 1991. Colour removal from textile effiuent by adsorption techniques. WaterRes. 25(3): 271-273.LEE, C.K and KS. Low. 1987. The removal of cationic dyes by a natural moss. I: Adsorptionstudies. Pertanika 10 (3): 327-334.Pertanika J. Sci. & Technol. Vol. 2. No. I, 1994 91K.S. Low, C.K. Lee and B.L. TohLow, KS. and C.K LEE. 1990. The removal of cationic dyes using coconut husk asan adsorbent. Perlanika 13(2): 221-228.McKAy, G., G. RAMPRASAD and P.P. MoWLI. 1986. Equilibrium studies for the adsorptionof dyestuffs from aqueous solutions from low-cost materials. Water, Air, Soil PoUut.29: 273-283.McKAY, G. 1982. Adsorption of dyestuffs from aqueous solutions with activatedcarbon. I: Equilibrium and batch contact-time studies. J ChlWt. Tech. BiotechnoL 32:759-772.NAMASIVAYAM, C. and N. KANCHANA. 1993. Removal of Congo red from aqueoussolution by waste banana pith. Perlanika J Sci. & Techol. 1: 33-42.NAMASIVAYAM, C. and R.T. YAMUNA. 1992. Removal of Congo red from aqueous solu-tions by biogas waste slurry. J ChlWt. Tech. Biotechnol. 53: 153-157.NAWAR, S.S. and H.S. DOMA. 1989. Removal of dyes from effluents using low-cost agricultural by-products. Sci. Total Environ. 79: 271-279.POOTS, VJ.P., G. Mc KAy and lJ.HEALY. 1976a. The removal of acid dye from effluentusing natural adsorbents. I. Peat. Water Res. 10: 1061-1066.POOTS, VJ.p., G. Mc KAy andlJ. HEALY. 1976b. The removal of acid dye from effluentusing natural adsorbents. II. Wood. Water Res. 10: 1067-1070.POOTS, VJ.p., G. McKAy and 1J. HEALY. 1978. Removal of basic dye from effluent usingwood as an adsorbent. J Wat. Pollut. Cont. Fed. 50: 926-935.92 Pertanika J. Sci. & Techno!. Vo!. 2. No.1, 1994

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