Studies were conducted to assess the capability of a moss, Calymperes delessertii Besch, to remove zinc from solutions. In the batch experiments, parameters

studied included effect of pH and initial zinc concentration on sorption. A series of fixed bed experiments were performed to study the system under

dynamic conditions. The bed depth service time (BDST) model proposedn by Hutchins was successfully applied to the system. The fixed bed experiments were also carried out using waste water from a zinc plating factory and results

indicated that moss columns could be used in a clean-up system to remove zinc from electroplating waste water

Lee, C. K.

Low, K.S.

Ng, K.H

Yahya, Asmah

Universiti Putra Malaysia Institutional Repository

Pertanika J. Sci. & Techno!. 2(2): 197-206 (1994)ISSN: 0128-7680© Universiti Pertanian Malaysia PressRemoval of Zinc by the MossCalymperes delessertii BeschC. K. Lee, K. S. Low, K. H. Ng and A. YahayaDepartment of Chemistry,Faculty ofScience and Environment Studies,Universiti Pertanian Malaysia43400 UPM Serdang, Selangor, MalaysiaReceived 23 September 1993ABSTRAKKebolehan satu lumut, Calymperes delessertii Besch, untuk menyinkir zink daripadalarutan telah dikaji. Dalam eksperimen kelompok, parameter-parameter yangtelah dikaji termasuk kesan pH dan kepekatan awallarutan zink pada pengerapan.Satu siri eksperimen turus telah dilakukan untuk mengkaji system ini di bawahkeadaan dinamik. Model 'bed depth service time' (BDST) yang dicadangkanoleh Hutchins telah digunakan dengan kejayaan kepada sistem ini. Eksperimen'fixed bed' pun dijalankan dengan menggunakan air-buangan dari satu kilangpenyaduran zink. Keputusan menu~ukkan turns lumut boleh digunakansebagai satu sistem pembersih untuk menyinkir zink daripada air-buanganpenge1ektrosaduran.ABSTRACTStudies were conducted to assess the capability of a moss, Calymperes delessertiiBesch, to remove zinc from solutions. In the batch experiments, parametersstudied included effect of pH and initial zinc concentration on sorption. Aseries of fixed bed experiments were performed to study the system underdynamic conditions. The bed depth service time (BDST) model proposedby Hutchins was successfully applied to the system. The fixed bed experimentswere also carried out using wastewater from a zinc plating factory and resultsindicated that moss columns could be used in a clean-up system to removezinc from electroplating wastewater.Keywords: moss, zinc, sorption, uptake, simulated wastewater, electroplatingwastewater, BDST model.INTRODUCTIONHeavy metals represent a major risk to the environment because of theirtoxicity. Their removal from water supply and wastewater is thus of utmostimportance.Zinc, one of the heavy metals, is used in the production of non-corrosive alloy, brass, in galvanizing steel and iron products and inelectroplating industries. The problems associated with ingestion of zincare well documented (Elinder 1986).C. K. Lee, K. S. Low, K. H. Ng and A. YahayaVarious methods have been proposed for the removal of zinc fromthe wastewater of the metal finishing industries. They include the use ofevaporation, reverse osmosis and precipitation as hydroxides. These methodsare, however, either costly and complicated or incomplete in metal removal.Hence the search for more efficient and economical means of zinc removalcontinues.The use of bryophytes as a sorbent of metal ions in wastewaterhas not been fully investigated. Mosses appear to be suitable sorbentsfor heavy metals because they possess several interesting properties (Johnson1980). The cell wall has a high polyuronic acid content which makes mossa very good natural ion exchanger. In addition, the highly reduced presenceor absence of cuticle in the moss means the ions have direct access tothe cell wall.Ruhling and Tyler (1970) reported that woodland moss, Hylocomiumsplendens, had a high capacity to sorb heavy metals from solution mainlyvia an ion exchange process. The sorption of some heavy metals by themoss Calymperes delessertii Besch has been reported; the moss could sorblead, copper and cadmium efficiently (Low and Lee 1987, 1991; Lee andLow 1989).This study investigates the sorption characteristics of zinc by the moss,Calymperes delessertii Besch, and the possibility of using it to treatelectroplating wastes.MATERIALS AND METHODSSample PreparationThe collection and preparation of the moss, Calymperes delessertii Besch, havebeen described earlier (Lee et al. 1983). Air-dried samples of the mossin its natural condition were used in all the experiments.A simulated wastewater prepared from A. R. grade anhydrous zincchloride in 0.001 M sodium chloride solution was used in all the experimentsstudying the characteristics of zinc sorption by the moss. Sodium chloridesolution was used to maintain constant ionic strength. Wastewater collectedfrom an electroplating factory situated in an industrial park was used inthe later experiments. The factory specializes in zinc plating and does nothave any facility for wastewater treatment. The wastewater collected wasalkaline and contained traces of nickel and iron in addition to zinc.Contact Time ExperimentsIn all the contact time experiments, except where the effect of pH wasinvestigated, 0.50 g of moss sample was shaken in 400 cm3 of zinc solution.Various concentrations of zinc solution (250, 100 and 50 mg dm-3) in0.001 M sodium chloride were studied.All batch experiments were performed in duplicates at room temperature(27°C). The zinc solution containing the preweighed moss was shaken in198 Pertanika J. Sci. & Techno!. Vol. 2 No.2, 1994Removal of Zinc by the Moss Calymperes delessertii Beschpolyethylene bottles at 200 revolutions per minute (rpm) on a gyratoryshaker. Aliquots of 1 cm3 solutions were withdrawn at predeterminedintervals.In the study of the effect of pH, 0.20 g of moss was equilibratedwith 100 cm3 of 100 mg dm-3 zinc solution with pH ranging from 2 to13 for four hours. The pH of the solution was adjusted by addition of0.1 M hydrochloric acid or 0.1 M sodium hydroxide.Sorption IsothermIn the study of the sorption capacity of the moss for zinc, 0.20 g samplesof moss were shaken in 100 cm3 of zinc solution f9r four hours. Theconcentrations of the solution were varied from 0.5 to 500 mg dm-3•Fixed Bed StudyIn the flow studies, a vertical glass column of internal diameter 14 mmwas used. The moss was packed to aheightoflO, 15 and 20 em, correspondingto 1.25 g, 1.88 g and 2.50 g of moss. The flow rates were controlled bymeans of a peristaltic pump attached to one end of the column. Zincsolutions of 50 mg dm-3 were passed through the column at flow ratesof 20 to 50 cm3 min-I. Eluants were collected in 100 cm3 and analysedfor zinc. The experiments were repeated using wastewater containing 200mg dm-3 of zinc and flow rates of 10 to 100 cm3 min-I.Adsorption-Desorption StudyIn the adsorption-desorption study, a glass column was packed with 2.50g of moss to a height of 20 em. One litre of 2.5 mg dm-3 zinc solutionwas passed through the column at a rate of 10 cm3 min-I.The eluant was collected and checked for its zinc concentration. Thecolumn was then eluted with 1 M nitric acid. Twenty fractions of eluantwith a volume of 10 cm3 each were collected and analysed for zinc.Mter the first adsorption-desorption process, the moss was washed freeof acid by rinsing it with deionized water. The process was then repeatedtwice on the same column of moss.Analysis of ZincThe concentration of zinc in all the experiments was determined usinga sequential scanning inductively coupled plasma atomic emissionspectrometer (Labtest 710 - 2000).RESULTS AND DISCUSSIONZinc Content in MossThe average concentration of zinc in the moss used in this studywas 80 ~g g-l moss. The zinc content was low compared to that of mossesfrom contaminated areas, which was about 1914 ~g g-I moss (Lee et al.Pertanika J. Sci. & Techno!. Vol. 2 No.2, 1994 199C. K. Lee, K. S. Low, K. H. Ng and A. Yahaya1983). Zinc, together with other heavy metals in the atmosphere, was broughtin contact with moss tissues in the form of precipitation and dust (Ruhlinget at. 1968; Lazarus et at. 1970).Contact Time ExperimentsThe reproducibility of the sorption capacity of the moss was demonstratedby equilibrating six replicates of 0.50 g moss in 100 cm3 of 250 mg dm-3zinc solution. A mean of 2.69 X 10-4 mol g-l moss and relative standarddeviation of 5.32% were obtained. Although no attempt was made to groupthe moss according to maturity, results from this reproducibility studysuggest that sorption of zinc by moss was fairly uniform.The rates of zinc sorption by the moss at various initial concentrationsare shown in Fig.I. A very rapid initial uptake followed by a more gradualprocess after the first 5 minutes was observed. This could be due to arapid ion-exchange process followed by chemisorption. This is a typicalsorption pattern for most biological materials (Okieimen et at. 1985).The fractional uptake was inversely proportional to the initial concen-tration. Equilibrium was achieved at 30 minutes' contact time regardlessof the ·initial concentration. This indicates the potential for rapid removalof zinc from solution.•2Time (hours)•...3Fig. 1. Effect of initial zinc concentration on sorption.• 50 mg dm-3 0 100 mg dm-3 ... 250 mg dm-3The effect of pH on sorption of zinc is shown in Fig. 2. In the pHrange of 2.45 to 4.70. there was an increase in sorption. As pH increases,the availability of sorption sites increases and hence the increase observed.At pH higher than 7, precipitation of zinc hydroxide started to occur.200 Pertanika J. Sci. & Technol. Vol. 2 No.2, W94Removal of Zinc by the Moss Calymperes delessertii BeschA similar pattern was observed in the study of copper, lead and cadmiumion (Lee and Low 1989; Low and Lee 1991). Gjengedal and Steinnes (1990)found that at pH lower than 4 the amount of cadmium accumulatedby the moss, Hylocomium splendens, decreased rapidly. This could be dueto the hydrogen ions competing for the sorption sites. At pH 12 zinchydroxide redissolved to form [Zn(OH4) ]2-. There was, however, no uptakeof zinc by the moss. As the pH of the electroplating wastewater collectedwas 12, it would be necessary to adjust the pH before experimentationusing the wastewater.0.4Q)~ca-c.::::lai 0.2c0..(,)ca...LL00 Z 6pHFig. 2. Effect of pH on sorptionSorption IsothermThe results from sorption studies were fitted into a modified Langmuiradsorption isotherm as shown below :N j is the number of moles sorbed per gram of moss at equilibriumconcentration Cr With this equation, the maximum number of moles ofmetal ion sorbed per gram of the moss (N*) can be calculated. A plotof C/N j against Cj is shown in Fig. 3. The linearity of the plot indicatesthe Langmuir isotherm can be applied successfully. The maximum sorptioncapacity is 21.50 mg or 329 ~mol zinc g-l moss.Pertanika J. Sci. & Techno!. Vo!. 2 No.2, 1994 201C. K. Lee, K. S. Low, K. H. Ng and A. Yahaya30r------------.oConcentration (p.p.m.)Fig. 3. Sorption isotherm of zinc on mossFixed Bed ExperimentsThere is a need to perform flow tests .because the data obtained underequilibrium conditions were not applicable in most treatment systems wherethe contact time is not sufficiently long for the attainment of equilibrium.The usefulness of the column is related to how long the bed will last beforeregeneration is necessary. For this purpose, determination of breakthroughCUIYes at various feed concentrations and bed depths is necessary.Fig. 4 shows three breakthrough CUIYes at bed-depths of 10, 15 and20 cm and flow rates (~) of 20 cm3 min-I with initial zinc concentrationof 50 mg dm-s. An arbitrary point of 50% breakthrough is chosen inthis study as the level where effluent concentration is unacceptable. Thetime at which this occurred is labelled as tl / 2• Breakthrough CUIYes withflow rates of 50 and 100 cm3 min -I were similar although breakthroughoccurred faster.The performance of a column can be evaluated using the bed depthservice time (BDST) model (Hutchins 1973). The model states that beddepth and service time bear a linear relationship. The equation can beexpressed ast=ax+bPlots ofBDST (11/2) at breakthrough volume (C/Co= 0.5) against bed depthat different flow rates are shown in Fig. 5.202 Pertanika J. Sci. & Techno!. Vol. 2 No.2, 1994Removal of Zinc by the Moss Calymperes delessertii Besch1200800O.L...-_.......L__---A_oC:----'-----+--_----I- __.......1.__.......1.__--Jo0.80°o 0.•Volume Treated (em3)Fig. 4. Breakthrough curves for simulated wastewater at a flow rate of20 cm' /min and different bed depths• 10 cm, • 15 cm, ... 20 cmThe linearity of the plots in Fig. 5 indicates that the BDST model canbe successfully applied to the zinc-moss system. Mter developing a BDSTequation for one flow rate, equations for other flow rates can be calculated.Using the BDST equation for the flow rate of 50 cm3/min, equations forother flow rates were calculated and plotted as shown in Fig. 5. Thereis good agreement between experimental and calculated values. Using thisprocedure, laboratory tests can be reliably scaled up without further testruns.uc§.QlE 20i=QlU'S:...Qlen00 10Bed Depth (em)Fig. 5. BDST plots at 50% breakthrough for different flow rates0, • 100 cm'/min, 0 50 cm-3/min, b., ... 20 cm'/min-- Experimental values; - - calculated valuesPertanika J. Sci. & Techno!. Vo!. 2 No.2, 1994 203C. K. Lee, K. S. Low, K. B. Ng and A. YahayaWhen the fIxed bed experiments were carried out using electroplatingwastewater after adjusting the pH to 4.2, similar breakthrough CUIVes wereobtained. The agreement between experimental and calculated BDSTequations is shown in Table 1. The breakthrough times ofboth the simulatedand real systems are listed in Table 2. The concentration of zinc inelectroplatingwastewater was four times that ofthe simulated system; howevert1/ 2 for the latter varied from 1.2 to 3 times that of the former dependingon flow rates. At a low flow rate of 10 cm3 min-1 where equilibrium couldbe achieved, comparable t1/ 2 can be obtained for the two systems with markedlydifferent zinc concentrations. This supports the earlier results that equi-librium time is independent of initial concentration. It thus appears thatthe moss column can be used to remove zinc from electroplating wastealbeit a much larger column is required in order to achieve a concentrationof < 1 Ilg cm-3 zinc in the effluent.TABLE 1Experimental and calculated BDST equationsfor flow rates based on f.l. = 100 cm3 min-11005010Experi=entaltl/2 = 0.094x + 0.466t 1/2= 0.194x + 1.026S/2 = 1.224x + 5.303Calculatedtl / 2 = 0.188x + 0.466tl/2 = 0.940x + 0.466204TABLE 2BDST(tI/2) of simulated and actual electroplating wastewaterSimulated ActualCo = 50 mg dm-3 Co = 200 mg dm-3Bed depth Flow rate tl/2 tl/2(cm) (cm3 min-1) (min) (min)10 100 3.4 1.415 100 5.3 1.820 100 7.7 2.410 50 7.7 3.115 50 11.4 3.820 50 15.4 5.010 10 22.0 17.515 10 29.8 23.820 10 41.2 29.7Pertanika J. Sci. & Technol. Vol. 2 No.2, 1994Removal of Zinc by the Moss Calymperes delessertii BeschAdsorption-Desorption StudyFig. 6 shows the result of three consecutive adsorption-desorption processesusing the same column of moss. In all cases no breakthrough was detectedprior to elution with 1 M HN03. Zinc was almost completely eluted inthe 100 cm3 ofacid. About 98% of zinc was eluted in the first desorption, 87%in the second and 103% in the third. The results indicate that elution withacid does not affect the performance of the moss as a sorbent, and the mosscolumn can be repeatedly used to remove zinc from treated wastewaterwhere the concentration is low.1s t 211d 3rd desorptioll~ r rk r ~, , , -r lIT1200aoo400o1 5 9 13 5 9 13 1Volume Eluted (x 10 cm3)5 9 13Fig. 6. Adsorption-desorption process ofzinc in moss columnCONCLUSIONThe moss, Calymperes delessertii Besch is an efficient sorbent for zinc fromsolution. The rate of sorption is rapid and the mechanism appears to involveion exchange. The flow studies indicate that the behaviour of the zinc-mosssystem can be predicted using Hutchin's BDST model. Moss columns arepotentially useful in the removal of zinc from electroplating wastewater.ACKNOWLEDGEMENTThe authors are grateful to Majlis Penyelidikan Kemajuan Sains Negara,Malaysia for their financial support (grant no. 04-07-05-017).REFERENCESELINDER, C.G. 1986. Zinc. In Handbook in the Toxicology of Metals. 2nd. edn., Amsterdam:Science Publishers, pp. 664-675.GJENGEDAL, E. and E. STEINNES. 1990. Uptake of metal ions in moss from artificialprecipitation. Environ. Monitoring and Assessment 14: 77-87.Pertanika J. Sci. & Techno!. Vol. 2 No.2, 1994 205C. K. Lee, K. S. Low, K. H. Ng and A. YahayaHUTCHINS, R.A. 1973. New method simplifies design of activated carbon systems. Chern.Eng. 80:133-138.JOHNSON, A. 1980. Mosses of Singapore and Malaysia. Singapore: Singapore UniversityPress, pp.I-4.LAzARus, H.L., E. LORANGE, and J.P. LOnGE Jr. 1970. Lead and other metal ions in theUnited States precipitation. Environ. Sci. Technol. 4: 55-58.LEE, C.K and KS. Low. 1989. Removal of copper from solution using moss. Environ.Technol. Letters 10: 395-404.LEE, C.K, KS. Low, A. PHOON and S.T. LOI. 1983. Heavy metals in some Malaysianmosses. Pertanika 6: 48-55.Low, KS. and C.K LEE. 1987. The sorption characteristics of lead and copper by themoss, Calymperes delessertii Besch. Pertanika 10(3): 321-326.Low, KS. and C.K. LEE. 1991. Cadmium uptake by the moss, Calymperes delessertiiBesch.Bioresource Technol. 38: 1-6.OKlEIMEN, F.E., D.E. OGEBEIFUN, G.N. NWAlA and C.A. KUMSAH. 1985. Binding of cadmium,copper and lead ions by modified cellulosic materials. Bull. Environ. Contam. Toxicol.34: 866-870.RUHLING, A. and G. TYLER. 1968. An ecological approach to the lead problem. Bot. Notiser.121: 321-342.RUHLING, A. and G. TYLER. 1970. Sorption and retention of heavy metals in the woodlandmoss, Hylocomium splendens. Gikos 21: 92-97.206 Pertanika J. Sci. & Techno!. Va!. 2 No.2, 1994

Removal of Zinc by the Moss Calymperes delessertii Besch

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Removal of Zinc by the Moss Calymperes delessertii Besch

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