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Najas Graminea Del., in Taiwan FAU Institutional Repository http://purl.fcla.edu/fau/fauir This paper was submitted by the faculty of FAU’s Harbor Branch Oceanographic Institute. Notice: ©1999 Elsevier Science Ltd. This manuscript is an author version with the final publication available at http://www.sciencedirect.com/science/journal/02731223 and may be cited as: Lee, C‐L., Wang, T. C., Lin, C‐K., & Mok, H‐K. (1999). Heavy Metals Removal by a Promising Locally Available Aquatic Plant, Najas graminea Del., in Taiwan. Water Science and Technology, 39(10‐11), 177‐181. doi:10.1016/S0273‐1223(99)00272‐3 Pergamon Wal . Sci. Tech. Vol. 39. No. 10-11. pp. 177-1 81,1 999 e 1999 Published by Elsevier Science Ltd on behalf of the fA WQ Printed in Great Britain. All rights reserved 0273- 1223/99 S20.OO + 0.00 PH: S0273-1223(99)00272-3 REAVY MEATALS REMOVAL BY A PROMISING LOCALLYAVAILABLE AQUATIC PLANT, NAJAS GRAMINEA DEL., IN TAIWAN Chon-Lin Lee* , Tsen C. Wang***, Ching-Ku Lin* and Hin-Kiu Mok** •Department ofMarine Environment, National Sun Yat-sen University. Kaohsiung, Taiwan. Republic ofChina • • Institute ofMarine Biology. National Sun Yat-sen University. Kaohsiung. Taiwan. Republic of China ••• Harbor Branch Oceanographic Institution, Florida, USA ABSTRACT This study uses an aqua tic plant, Najas graminea Del., to treat man- mad e wastew ater containing single andlor binary components of copper, lead, cadmium and nickel. Adsorption experiments demonstrate that the adsorption pro cess co rrespo nd to the Lagergren kinetic model with the rate constant close to 0.01 min" ; meanwhile, the equilibrium results corre sponds to the Langmu ir adsorption isotherm. Nota bly, the rate constants of metals are not sig nificantly differ ent between each other. Competitive effect on the adsorpt ion kinetics of cadmiu m is insignificant with the background solute (lead ) concentration up to 10 mgli; while significant dev iation obse rved with concentration of lead reached 100 mgli. In addition, the maximum adsorption density of cadmium is reduced by around 50% in the pre sence of 100 mg/I of lead. A'simulated copper plating wastewater is also treated by Najas graminea Del. to demonstrate its efficiency in removing metals from wastewater with mult i-cations/anions. 10 1999 Publi shed by Elsevier Science Ltd on behalf of the IAWQ. All rights reserv ed . KEYWORDS . Bio-rernediation; aquatic plant; heavy metals; sustainable technology. INTRODUCTION The feasibility of using aquatic plants to remove toxic metals has received extensive interest (Muramoto and Oki, 1983; Sela et al., 1988; Sela et al. , 1989; Gupta and Chand ra, 1994). These aquatic plants include microalgae (Maeda and Skaguchi, 1990; Wilde and Benemann, 1990), seaweed (Kuyucak and Volesky, 1989), aquatic bryophytes (Whitton et aI., 1991; Mouvet et aI., 1993), duckweed (Sajwan and Omes, 1994), etc. Eichhornia crassipes has been successfully applied not only in removing organics and metals (Wolverton et aI., 1977), but also as a bio-indicator for assessment of metal pollution (Zaranyika et aI., 1994). This sustainable technology, occasionally referred to as phyto-remediation, has several merits such as low energy consumption, low operation cost, fast growth rates, and simple growth requirement (Sajwan and Omes, 1994). Suitable plants can be applied in a retention pond, constructed wetland or phyto-reactor, Of particular interest, Najas graminea Del. (a floating aquatic plant) has high specific metals adsorption 177 178 c.-L. LEE et al. capability as welI as ease of culture and harvesting. Therefore, this plant is selected to treat man-made wastewater .containing single andJor binary components of copper, zinc, lead, cadmium and nickel. Both kinetics and equilibrium experiments are performed to examin e the competitive adsorption behaviors among metals . EXPERIMENTAL Materials. The water used in all the .experiments was purified using Milli RO PluslMiIIi Q water purification devices . Standards (1,000 mgll) of metals, sodium chloride (99.5%), calcium chloride (99.5%), sodium hydroxide (99%) were purchased from Merck. Analytical standards of metals (#7878 and #7879) for quality control were purchased from the Analytical Products Group, Inc., USA). The stock buffer solutions were prepared by 1,020 ~I glacial acetic acid and 5.745 g sodium acetate and diluting to 100ml with DI water. Finally, standard material (aquatic plant, Lagarosiphon Major, CEC Community Bureau of Reference B.c.R. Nr. 60) was used as a control sample for quality control. Procedures . Kinetic studies of metal adsorption on plants were carried out by the following procedure. .Weighted biomass (around 1.0 g) was added to metal solutions (50 ml) in 120 ml Erlenmeyer flasks equipped with screw caps and then incubated in a .shaker (150 rpm, Wisdo , SB-9D) . Two hours. of contacting time was used in the equilibrium experiments. All experiments were performed in duplicate (average relative difference of measured concentrations is 3.2±6.2% for n=245). At the end of the experiments, the contents ofthe flasks were strained to separate the biomass from the supernatant. Next, the supernatant solution was directly measured or after dilution if necessary with a Hitachi Model Z-8000 Polarized Zeeman Atomic Absorption Spectrophotometer to measure the metal concentrat ion remaining in the solution. The biomass was stored for future digestion with nitric acid in a microwave digester (MLS­ 1200 Mega Milestone). The amountsof metal adsorbedand dried weightof biomass were used to calculate specific adsorption capability (metal adsorbed! dried weight of biomass). The protocols used were validated through exploration of the key variables : time, metal concentration (initial and final) and metal content in the biomass. The overall mass balance (average at 110±6.1%) indicates that errors from the walI adsorption or precipitat ion should be negligible . In addition, the Proficiency Environmental Testing Program from the Analytical Products Group is also used to finely tune the AAS performance. (a) (b) 00 . 31. c; Co E t 60 ,0 24 ,0 c C .g ~e. ~ i 16.0 '2 40 .0 ~ u .!! ~ "2 ! 20.0 ~ •• Q -e Q. u •• -f-..-,~---.~-r-~r-----r---.--.-......., •• O ~ S ~ 1~ I U M ~ 2 5 ~ ~ o U ~ ~ •• 40.0 ... 120 .0 160,0 200 0 C. exposure co nce nlr.Uion(mgIL} C. ex pos ure concenlration(mgIL ) Figure J". Adsorption isotherms ofsingle metal ((a) lead and (b) cadmium)) on Najas graminea Del. RESULTS AND DISCUSSION Figure 1 shows the adsorption isotherms of single metal on Najas graminea Del. Lead has a stronger adsorption tendency than cadmium regarding its adsorption density on the biomass. As these two metals compete with each other for a limited number of adsorption sites, the adsorption of cadm ium is reduced in the presence of lead (Fig. 2). In order to quantify the extent of change in adsorption kinetics , the Lagregren kinetic model (Periasamy and Namasivayam, 1995) is used: log (qc-q) = log qo- k tJ2.303 Heavy metals removal using an aquatic plant 179 Where qe and q are the amounts of metal adsorbed at time t (minute) and equilibrium time, respectively, and k is the rate constant of adsorptio n (min -I). Linear plots of log (qe-q) vs. t show the applicability of the Table I. Comparison ofcomposition in real and 100.0 simulat ed copper plating wastewater 80.0 p ~ Parameters Copper. Simulated "0 plating copper > 0'" 60 .0 wastewater" plating Ee "0 wastewater 0 400 ;f!. PH 2.12 5.00 P.. 0 ...... • Total hardness as CaC0 , 840.00 200 1(' Ptloa IOmWL 3 838.20 0 + P ~ 'OOtngJl Chloride, mg/l 282.20 434.00 0.0 Copper, mg/l 98.00 100.00 60 ' 20 180 2' 0 300 Tim e(min ) Nickel, mg/I 11.80 10.00 Figure 2. Kinetic study ofadsorption ofcadmium (10 mgll) in Sodium,mg/l 64.00 2290 .80 the presence oflead by Najas graminea Del. Calcium as CaC0 3, mg/I 80.00 80.00 Magnesium as CaC0 3, mg/I 760.00 758.20 • Periasamv and Namasivavarn, 1995 above model. At 10 mg/l of lead (Fig. 2), the adsorption behavior of cadmium is not significantly altered in both equilibrium (maximum adsorption density of 3.28 and 3.45 mg/g) and kinetics (k=0.218 and 0.220 min-I, respectively). However, as the concentration of lead raised up to 100 mg/l, the plateau adsorption density of cadm ium reduced to almost 40% (2.05 mg/g) and the kinetics rate constant reduced almost 70% (0.071 min-I). Contrarily, the lead adsorption behavior is not influenced by the presence of cadmium. According to Figure 3, the lead (concentration of 10 mg/l) adsorption density and its adsorption kinet ics are not signifi cantly influenced by the presence of cadmium, even with cadmium concentration as high as 100 mg/l. Meanwhile, as the concentration of lead raised up to 100 rng/l, the competition effect is observable with cadmium concentration as low as 10 mg/l, These phenomena lead to a conclusion that the stronger adsorbate has a stron ger background solute effect. In addition, the competition effect becomes important if the total adsorption sites becomes saturat ed. (a) (b) 100.0 100,0 R 80 .0 00 0 -e "0 2 ~ > 0 ~ E 60 0 r E 60 0 e e ~ e- '5 40.0 n 40.0 a. a. .... • Cd' """'- .... • Cd' """'- 20 .0 0 Cd · '~ 20.0 C Cd .I ~ + Cd- 1ClClrr9\. + en -1 C1:'n¢ 0 .0 0 .0 60 120 '60 2' 0 300 50 120 160 140 300 Time (min) Tome(min ) Figure 3. Kinetic study oflead « a)10 mgll and (b)IOO mg/I) in the presence ofcadmiun by Najas graminea Del. A simulated copper plating wastewater (composition given in Table I) is also treated by Najas Graminea Del., to demonstrate its efficiency in removing metals ' from wastewater in the presence of multi­ cations/anions.
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