Applied Surface Science 258 (2012) 6345–6352

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Applied Surface Science
journal homepage: www.elsevier.com/locate/apsusc

Fly ash adsorbents for multi-cation wastewater treatment
Maria Visa ∗ , Luminita Isac, Anca Duta
Transilvania University of Brasov, Dept. Renewable Energy Systems and Recycling, Eroilor 29, 500036 Brasov, Romania

a r t i c l e

i n f o

Article history:
Received 17 January 2012
Received in revised form 7 March 2012
Accepted 8 March 2012
Available online 21 March 2012
Keywords:
Fly ash
Heavy metals
Adsorption
Wastewater treatment

a b s t r a c t
Class “F” fly ash (FA), collected from the Central Heat and Power (CHP) Plant Brasov (Romania), with
oxides composition SiO2 /Al2 O3 over 2.4 proved good adsorbent properties, and was further used for
obtaining a new substrate with good adsorption capacity for heavy metals from multi-cation wastewater
treatment. Firstly, the new adsorbent was characterized by AFM, XRD, DSC, FTIR and the surface energy
was evaluated by contact angle measurements. The experimental data suggested that the new type of
substrate is predominant crystalline with highly polar surface.
The substrate was used for removing the Pb2+ , Cd2+ and Zn2+ cations from mixed solutions. The results
show high efficiency and selective adsorption the Pb2+ and Zn2+ cations.
The optimized adsorption parameters were further used in thermodynamic and kinetic studies of the
adsorption processes. The Langmuir and Freundlich models were used to describe the processes. The
pseudo-second order kinetics could well model all the processes, indicating a surface concentration of
the adsorption sites with the same order of magnitude as the cation concentrations.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Combined heavy metals cations result in wastewaters from
many industrial processes, such as electroplating, inorganic pigment manufacturing, wood processing, photographic operations
and petroleum refining. The heavy metals are also utilized in rubber, pesticides and plastics. Many compounds of heavy metals are
easy soluble in water and can be adsorbed by living organisms
part of the food chain. Some heavy metals (copper, cobalt, iron,
manganese, vanadium, strontium and zinc) are accepted in small
concentration for living organisms but excessive levels of essential
metals can be detrimental to the organisms. Non-essential heavy
metals (including cadmium, lead and copper) are dangerous for
living organisms because they tend to bio-accumulate and in time
they cause serious health effects [1] (cancer, liver damage, renal
disorder, visceral cancers, insomnia, depression, lethargy, vomiting). Particularly children will be at risk to consume more food with
heavy metals resulting in a reduction of growth, and a damage of
the nervous system and the brain.
Although Zn2+ is considered to be relatively nontoxic (is a cofactor in over 100 enzymes reactions) its excessive inhalation (as
fumes) may cause the diseases. The toxicity symptoms – nausea, vomiting, skin, eyes yellow, “Zinc chills”, epigastria pain, or,
lethargy, neuropathy, low blood pressure and fatigue – appear at
high Zn intakes.

∗ Corresponding author. Tel.: +40 729109355; fax: +40 268410525.
E-mail addresses: maria.visa@unitbv.ro, visamro2000@yahoo.com (M. Visa).
0169-4332/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2012.03.035

To minimize the human and environmental exposure to these
hazardous heavy metals the US Environmental Protection Agency
(US EPA) established the limits of cadmium, lead and zinc that
may be discharged into wastewater at: 0.01 mg/L, 0.006 mg/L and
0.80 mg/L, respectively.
The heavy metals can deactivate the active sludge (poisoning
the bacteria) from the secondary treatment plants [2]; therefore
the chemical treatment must remove heavy metals before the
biological step. The most common and widely used method for
removing heavy metals from wastewater is chemical precipitation
using caustic soda or lime [3]. This method is not expensive but
requires a large amount of chemicals, resulting in a high quantity of
sludge that requires a supplementary treatment. Moreover, according to the precipitate’s solubility, the residual amount of dissolved
heavy metal may exceed the discharge limit.
Other methods for advanced heavy metal removal are ion
exchange, reverse osmosis, ultra filtration, electrochemical deposition and adsorption.
Although largely used in industry, adsorption, particularly ion
exchange, presents several disadvantages like pH sensitivity, nonselectivity, and cost. Replacing synthetic substrates with low-cost
adsorbents is therefore intensively studied and there were reported
materials for heavy metals removal obtained from agriculture and
forest wastes such as bagasse fly ash [4] sugar beet pulp [5] activated carbon derived from bagasse [6], maple saw dust [7], clay
[8,9] volcanic ash bone char [10] humus [11] or bituminous coal.
Heavy metals (cadmium, copper, zinc, nickel) removal was
reported on scrap rubber, bituminous coal, peat [12], natural zeolite [13] while 4A zeolite synthesized by dehydroxylation of low

identified by atomic absorption spectrometry. bottom ash. and was further used for obtaining controlled adsorbent structure. Pb2+ cations on fly ash according with reference [15] and present study.07 0. 20 mA. The chemical composition of fly ash and the surface aspect strongly depends on the initial source (type of coal). exchange capacity 2. obtained from fly ash. the new adsorbent was obtained from the slurry under stirring for 72 h.87 Coal fly ash Fly ash Fly ash Fly ash zeolite Bagasse fly ash Rice husk ash FA-Z 18. having a grain diameter between 100 and 400 ␮m. 2. Metal 2+ Zn Cd2+ Pb2+ Adsorbent Adsorption capacity (mg/g) Coal fly ash Fly ash Bagasse fly ash Rice husk ash FA-Z 6. Based on the results obtained in testing this new substrate in removing heavy metals from aqueous solutions. High content of the SiO2 . The major constituents and trace elements from raw fly ash. followed by stirring at room temperature till constant pH and conductivity values (10. D8 Discover Bruker diffractometer. Adsorption experiments Two series of experimental tests were done on threecomponent solutions of Cd2+ . and the surface energy was evaluated based on contact angle measurements using the sessile drop method (OCA20 Contact Angle-meter. The thermal stability of the samples was investigated by differential scanning calorimetry (DSC – Diamond Pyris DSC. 2 range from 20 to 80◦ ) and complementary data were obtained by FTIR spectroscopy (Spectrum BX Perkin Elmer spectrophotometer.04 30. The adsorption capacity of raw fly ash is rather low but can be improved. thus occupying the adsorption sites depends on the components’ affinity and substrate energy. Zn2+ .44 2. To evaluate the adsorption efficiency and investigate the adsorption isotherms. K␣1 = 1. The sample was noted FA-Z. and may lead to completely different efficiencies. Fly ash is a waste mainly used in cement manufacturing (due to the large amounts of silica and alumina oxides) but fly ash can also be used as adsorbent material.or bi-pollutant systems but industrial wastewaters have usually a more complex composition.24 2.58 Trace elements [ppm] This paper Ba Cu Zr Sn Pb As Ni Zn Cr V Mn Co Ti 700 60 100 3 35 100 55 160 100 115 800 12 >3000 a This paper This paper grade kaolin is reported to remove Cu(II) and Zn(II) ions at neutral and alkaline pH [14]. Data Physics Instruments). The results are compared with those obtained when using macro. The FA is of F class because the sum of the major oxides SiO2 .61 2000. by reducing the air pollution threats and cleaning the wastewater.11 5. Zn(II).5406 A. Zn2+ .3. therefore washing before use is compulsory.2. Characterization of new adsorbent The FA-Z crystalline structure was evaluated by XRD (Advanced ˚ 40 kW.30 18.8 285–566 12. and respectively.24–2.and microporous cationic exchangers. the next step will be to test the adsorption capacity of the substrate on real/industrial wastewaters. Materials synthesis The raw fly ash was supplied by the CHP Brasov. This paper presents the results of adsorption on a new substrate.0 3. The pH value of the raw fly ash was evaluated by mixing 100 g of FA with 1000 mL ultra pure water. This concentration is significantly lower compared with the 5–8 N usually reported.02. 0–1350 mg/L. at atmospheric pressure and 100 ◦ C.08 1./L).6 1. solving two major environmental problems.66 0./L)) and microporous cation exchangers (Purolite C100 gel.32 22.0 Table 2 Fly ash composition.7 18. the cations solutions were stirred up to .6–8 95. Romania directly from electro-filters. / Applied Surface Science 258 (2012) 6345–6352 Table 1 Summary of adsorption of Cd2+ .3 11.1. 2.8 equiv. Materials and methods 2.2 1.  = 2500–16. Visa et al. Scharlau Chemie). Ntegra Spectra. Raw ash contains soluble compounds. Previous studies proved that conditioning by alkali treatment (1–3 N) can be a viable path for enhancing the adsorption efficiency of heavy metals [16] or multi-component systems of heavy metals and dyes [17]. This is the reference sample. 2.88 14.4 proved good adsorbent properties. is over 70 wt% and has low lime content [18]. 0–350 mg/L (ZnCl2 . large surface area and particle size distribution. used as adsorbent for removing Pb2+ . Perkin Elmer).000 nm).5–13. Pb(II) ions removal from wastewater using fly ash.4 44. Cd2+ and Zn2+ from three-cation solutions. Scharlau Chemie).6346 M. low cost and good adsorbent properties (porosity. 0–700 mg/L (CdCl2 . Fly ash has potential applications in wastewater treatment because of its chemical composition. The large majority of the studies report on mono. colorimetry and gravimetric analysis and the results are presented in Table 2. fly ash washed (FA-W).97 5. The coal combustion products (CCP) are: fly ash (FA) (>60% of CCP). To activate fly ash. NaOH solution 3 M was used at a 1/10 g/mL ratio between the sample and the activation solution. The first set of experiments used the novel adsorbent (FA-Z) and the second set used commercial macroporous (Purolite C150. The surface was characterizes in terms of BET surface (Tri Star II 3020 – Micromeritics). Al2 O3 and Fe2 O3 . Major oxides [%] SiO2 Al2 O3 Fe2 O3 CaO MgO K2 O Na2 O TiO2 MnO LOIa 53. scan speed 2 s/step.2. morphology (AFM. Al2 O3 is advantageous in the process of restructuring. 1. This fly ash with oxides composition SiO2 /Al2 O3 over 2. usually by chemical treatment.0 equiv. exchange capacity 1. NT-MDT model BL222RNTE).710 mS). Loss of ignition.98 198. step size 0. In the 1000 mL volumetric flask with reflux condenser.63 1. boiler slag and flue gas desulfurization materials. being already reported in developing zeolites.05 8. Table 1 summarizes some of the recent results of Cd(II). where the composition includes also other cationic and non-ionic components. and Pb2+ .21 Fly ash washed Fly ash Fly ash Bagasse fly ash Treated rice husk ash FA-Z 483. on a thermo-stated heating plate. on the burning process and combustion equipment (type of furnace).

The crystalline degree of FA-Z is estimated at 45. based on the calibration curves. the metal uptake qe (mg/g) was evaluated using the initial and current. Supplementary information was obtained using the FTIR spectra.] 240 min at room temperature (20–25 ◦ C). Cu2+ . Pb2+ and Cu2+ removal on humic acid [9. presented in Table 3 [28] were considered as reference in investigating the experimental results. Aliquots were taken each 15. 6347 Na 6Al 6Si 10O 3212H 2O Hematite 6000 (2) 5000 αSiO 2quartz 4000 Mullite Hematite 3000 Al 2O 3γ. Cd2+ removal on fly ash from single.u. the amount of heavy metals ions adsorbed can be calculated with Eq. Results and discussions 3. heavy metal concentrations t i (ccation and ccation ). Preliminary experiments proved that heavy metals losses due to adsorption to the container walls and to the filter paper were negligible. By removing the soluble compounds there is a relaxation in the system.Ca)5 (Al6 Si30 O72 ·18H2 O). In this case. Mn2+ adsorption on zeolites [23].Na. 90.303 (2) where KL is the Lagergreen constant. This model is based on the assumption that the rate limiting step may be a chemical adsorption involving the valence forces through sharing or exchange of electrons between the adsorbent and the adsorbate [18. 3.27]. for a given amount of FA-Z substrate (ms = 0.65%. cristobalite) are mostly absent in the new material (FA-Z). The fly-ash based substrates have a composition close to a zeolite (SiO2 /Al2 O3 over 2. Ni2+ .or double-pollutant solutions [24] Another possible kinetic model which can be applied in adsorption processes on porous materials is the interparticle diffusion model.8 nm. which can be assigned to the Si Al O asymmetric stretching while the band recorded at 657. when stirring was briefly interrupted and the substrate was removed by filtration. qeq is the amount of metal ions adsorbed from the solution with the equilibrium concentration.75 g FA-Z.4. 2.5 g).9 nm and Pb = 283.the Langmuir isotherm – linearization: For the kinetic studies. . The IR spectrum can be splitted on two groups of vibration: one is internal vibration of the framework units (SiO4 )− or (AlO4 )− and the other group of vibrations indicate the links between the framework units in the structure of FA-Z. 240 min. while the new crystalline phases in FA-Z are sodium aluminum silicate (Na6 [AlSiO4 ]6 ·4H2 O). ZEEnit 700). The adsorption parameters were calculated considering the Langmuir and Freundlich equations [26. in a given solution volume (V = 100 mL).6 (natural pH value in the three-cations solutions with FA-Z) to 6. 45. being an indicator of the adsorption capacity and 1/n represents a dimensionless parameter.4).K. Zn2+ . Co2+ . as given in Eq. 1.K. at: Cd = 228. qe is the equilibrium uptake value and qt the current metal uptake. This confirms that chemical restructuring occurs within FA-W. Ceq Ceq 1 = + qeq qmax · a qmax (5) where qmax (mg/g) represents the maximum monolayer adsorption capacity.5. Visa et al.66 cm−1 .11]. Characterization The diffractograms (Fig. confirmed by the shift of the 950–1500 cm−1 absorbance band in the IR spectra of FA-W and FA-Z.1.K.the pseudo first-order equation [19]: KL log(qe − qt ) = log(qe ) − t 2. Zn2+ (350 mg/L) respectively Pb2+ (1350 mg/L). this could be correlated with the substituted Al atoms in the tetrahedral forms of the silica frameworks.22].6 involving a slow release of the alkali traces resulted from synthesis.ε SiO 2cristobalite 2000 (1) 1000 20 30 40 50 60 70 80 2 theta [degree] Fig. The residual metal concentrations in the supernatant were analyzed by AAS (Analytic Jena. 60.the Freundlich isotherm – linearization: ln qeq = ln kF + 1 ln Ceq n (6) where kF is Freundlich adsorption constant. the working pH value increased from 5. In this type of material. 120 180. sodium aluminum silicate hydroxide hydrate (Na8 (AlSiO4 )6 (OH)2 4H2 O). Zn = 213. The optimal contact time was evaluated on suspensions of 0. Adsorption isotherm The adsorption isotherm data were experimentally obtained after optimizing the adsorption processes at 90 min with 0. (1): qe = (c i cation − ct )×V cation ms (1) The kinetics of the heavy metals adsorption was modeled by the following equations: . sodium aluminum silicate hydrate (phillipsite) (Na6 Al6 Si10 O32 ·12H2 O). therefore the frequency regions corresponding to different types of vibrations in zeolites. XRD of (1) FA-W and (2) FA-Z. as a measure of the adsorption density. including Cu2+ . The IR spectrum of FA-Z shows a sharp peak with high intensity at 962. t. (4) [25]: q = kid t 1/2 + C (4) 2.5 g FA-Z in 100 mL multicomponent solutions of Cd2+ (700 mg/L). The model is mentioned in literature for many systems.H3 O)(SiAl)O3 ·H2 O and other phases of the aluminosilicates.3 nm. 30. tobermonite (Ca.77 cm−1 can be assigned to the Si Al O symmetric stretching. / Applied Surface Science 258 (2012) 6345–6352 (Na. In all cases.M.Ca) 5Al 6Si 30 O 72 18H 2O 9000 FA-Z FA-W Na 6[AlSiO 4]64H 2O 8000 7000 Intensity [a. then the substrate was removed by vacuum filtration and the supernatant was analyzed. . a is a constant related to the adsorption free energy. water molecules are associated with the cations and are in .the pseudo-second order kinetic equation [20] and a comparison of linear and non-linear methods [21]: t 1 t = + qt qe k2 q2e (3) where k2 is the equilibrium rate constant for the pseudo secondorder adsorption which can be evaluated from the slope of the plot. 1) show that some crystalline phases of FA-W (quartz and mullite. The adsorption kinetic . clinoptilolite (Na. Ceq .

Fig. IR spectrum (a) raw fly ash.74 cm−1 which is characteristic of the bended mode in the water molecules. The shift of the Si Al O asymmetric stretching peak to slightly higher values may also raise the possibility of the “lubricant” effect of the adsorbed water molecules within the FA-Z material. To test the thermal stability and water bonding of the FA-Z material.6348 M. Visa et al. 3. / Applied Surface Science 258 (2012) 6345–6352 Table 3 Characteristics of IR bands associated with zeolite-A (common for all zeolites). the thermal alkali treatment for producing FA-Z is responsible for a significant reorganization at/of the surface as the AFM image in Fig. corroborated with the previous surface and structural data. recorded at 1639. Fig. DSC test were done (in nitrogen flow) with a scan rate: 2 ◦ C/min at temperatures between 30 and 550 ◦ C. 2c. 3. these indicates a new type of organization in the FA material. Type of IR band Internal tetrahedral Asymmetric stretch of T O bond Symmetric stretch of T O bond External linkage Double ring Symmetric stretch Asymmetric stretch Frequency [cm−1 ] 1500–950 660 670–500 750–820 1050–1150 T = Si or Al. The AFM images were used for surface morphology studies. confirming the water peak at 1639. The main characteristics of FA-W and type of zeolite FA-Z are presented in Table 4. The dissolution of the soluble compounds from raw FA lead to a new topography of the FA-W surface resulting in more homogeneous and smooth surfaces. (b) FA-Z. and a decrease in the average pores diameter. . Fig. The IR spectrum of the sample after the DSC analysis is shown by the line (c) in Fig. Cation adsorption involves mainly electrostatic forces therefore the surface energy of the new substrate (FA-Z) can strongly influence the adsorption process.74 cm−1 . The surface area of the FA-W and FA-Z were analyzed and the results show a strong increase in the specific surface. 2. and (c) FA-Z – DSC. The polar and disperse contributions to the surface energy of FA-Z were calculated according to the model developed by Owens. But. explaining the peak with less intensity. AFM topography and average roughness. Wendt. some extent hydrogen bonded to the oxygen ions of the framework. Robel and Kaelble and are presented in Table 5. 3c confirms.

for these two ions. 0. experiments were done on synthetic mixtures containing three cations Cd2+ . 90 min.25 14. 4a–c for the cadmium. Sample Specific surface area (BET) [m2 /g] Micropores volume (t-plot) [cm3 /g] Micropores surface (t-plot) [m2 /g] Average pores diameter [nm] FA-W FA-Z 6.0 1. Zn2+ immobilization.426 0. in the same experimental conditions and the results are presented in Fig.97 0. dose of FA-Z in 100 mL of solution. almost similar removal efficiencies (close to 70%) being registered at 1. efficiency vs. in all cases the adsorption efficiency on the microporous substrate is c b a 100 100 100 90 80 80 2+ Pb (mixture)/FA-Z 40 20 60 50 40 30 50 100 150 Time [min] 200 250 40 2+ 20 0 0. Adsorption experiments The new substrate synthesized from fly ash was tested for heavy metals removal from wastewater. the removal efficiency increases.0 0. As expected considering the participants in the processes. 4a and b. this was the set as optimal contact time in all further experiments. substrate’s dosage and initial cations’ concentration) were optimized considering the maximum removal efficiency of Cd2+ . Zn2+ immobilization. 90 min. / Applied Surface Science 258 (2012) 6345–6352 6349 Table 4 Characteristics of FA-W and FA-Z. If the hydrated shell is small.430 also explains the data presented in Fig.2. contact time. .261 0. Zn2+ immobilization.0004 0. contact time.074 0. on FA-Z. 6a–c.097 0. supporting the assumption of an adsorption process without dehydration. Visa et al. The adsorption studies carried out to estimate the heavy metal removal from wastewater. calculated using the following Eq.30]). Table 6 Properties of the dehydrated and hydrated heavy metal cations.75 g.09 27. (b) Cd2+ . contact time. 3. dosage. showing an efficiency decrease for contact times longer than 240 min. efficiency vs. 4.4 1. Zn2+ and Pb2+ . The experimental data show a very efficient lead removal. is caused by a positive surface charge leading to repulsions between the surface ( SiOH2+ ) and metal ions (positive).4 Table 5 The energetic characteristic of FA-Z surface. Pb2+ and Zn2+ ions. The dynamic adsorption results are presented in Fig. 0. The removal efficiency of lead is close to 100% because at pH >6 exist the tendency for precipitation [32].2 15.0030 2. The process parameters (contact time. lead and zinc adsorption on FA-Z. Previously reported results [31] showed that fly ash washed with HCl had poor cadmium removal efficiency <5%. (a) Cd2+ .4 0. efficiency vs. The FA-Z substrate is highly efficient ( > 90%) for the removal of all cations at concentrations below 100 ppm. .8 1. hydrated cation or the need for supplementary reaction energy if adsorption occurs with dehydration. up to 99% for the Pb2+ cation (Table 6. Pb2+ .91 The data show a high global surface energy and a large polar component. These data can be linked with the cation’s transport rate toward the substrate but can have also other reasons like occupying more active sites with a single large. using fly ash.6 0 10 0 2+ 60 Cd (mixture)/FA-Z 2+ Zn (mixture)/FA-Z 2+ Pb (mixture)/FA-Z 20 0 Efficiency [%] 2+ Zn (mixture)/FA-Z Efficiency [%] Efficiency [%] Cd (mixture)/FA-Z 60 80 70 2+ mass [g] Zn (mixture)/FA-Z 2+ Pb (mixture)/FA-Z 2+ Cd (mixture)/FA-Z 0 200 400 600 800 1000 1200 Ci [mg/L] Fig.6 0. Pb2+ . This observation can be explained by the ionic radii of the metal ions and Heavy metal Cadmium Lead Zink Anhydrous ionic radius [nm] Hydrated ionic radius [nm] 0. hydrated cations (Cd2+ and Zn2+ ).5 g FA-Z/100 mL sol.3 g of FA-Z dispersed in 100 mL of solution. thus for advanced wastewater treatment. At high cation concentrations the adsorption efficiency rather is low for the large volume. The adsorption equilibrium for cadmium and zinc needs 90 min to be settled therefore. The adsorption efficiency of this new type of substrate was compared with those of C100 micro-porous and C150 macro-porous cation exchangers. (c) Cd2+ . 5).2 1. while a dosage of 0. dosage. showed that the efficiency follows the order Pb2 > Zn2+ ≥ Cd2+ . Pb2+ .M. [29. The results indicate that the adsorption efficiency depend of the pH value and for the amount of substrate (Fig. (7): = e i − ccation ) × 100 (ccation (7) i ccation e i where ccation and ccation are the initial and equilibrated cations’ concentrations (mg/L). initial concentration.14 37.52 32.2 0.5 g/100 mL allows almost complete lead removal.122 0. Surface energy [mN/m] Disperse contribution [mN/m] Polar contribution [mN/m] 207.61 174. after a very short contact time and on a broad concentration range. recommending the material as a good adsorption substrate. The data also show that cadmium and zinc have a much lower affinity for the FA-Z substrate. higher substrate dosage is required. another preliminary process like precipitation. Also.

dose of FA-Z.75g.5 × 10−4 0.171 12.492 – – 0.9 × 10−4 0. Lead speciation indicates the formation of Pb2 (OH)3+ . except lead adsorption on the microporous cation exchanger.0166 0.0053 – 0. Further adsorption–desorption studies will be employed to elucidate this aspect. / Applied Surface Science 258 (2012) 6345–6352 describes the adsorption mechanism for all the three cations.425 1. (c) Zn2+ immobilization efficiency vs. 6.918 0. Considering the pseudo-second order kinetics. on all the investigated substrates.518 0.947 0. which could be expected considering the FA-Z composition and/or the pores distribution with active sites of various energy. Uptake kinetics of the heavy metals The models described in Section 2.355 0. as expected.9289 – 1. the Pb2+ adsorption capacity is high both on FA-Z (2500 mg-Pb2+ /g) and on C100 microporous (2000 mg Pb2+ /g) confirming that the FA-Z contains mezopores with a large number of active sites opened for the low volume lead cation. Adsorption isotherm and mechanism higher than on the macroporous.3. being also able to efficiently replace the cations exchanges in current lead removal processes even when mixed with other species. contact time.286 30. Table 7 Kinetic parameters of the heavy metal adsorption.854 0.662 0. Table 8 presents the adsorption parameters for the heavy metal ions (Cd2+ .4 were tested for the Cd2+ .75g.913 0. in the working conditions (pH < 7) the lead cation is dehydrated/slightly hydrated.5g.231 0.852 0. The kinetic parameters are presented in Table 7.318 KL [min ] 2 2 . On the other hand.3g) Efficiency [%] 80 70 60 50 40 30 20 10 0 0 1 2 3 4 5 6 7 pH Fig.1.011 2. 5.995 1.0.365 37.407 0.44 1 1 0. for the pseudo-second order mechanism.211 79.999 – – – – – – 0.3g) 90 2+ Pb /FA-Z(0.133 0.453 0. 2+ Zn /FA-Z(0.0.037 – – 3.5g.3g) 100 2+ Cd /FA-Z(0.1. where the values are significantly lower than those evaluated based on kinetic studies.995 0. Zn2+ and Pb2+ removal by adsorption on FA-Z and by ion exchange.972 0.934 0.881 0.5g.002 18. Zn2+ and Pb2+ ) calculated from the slope of the linearization plots of the two isotherm equations.886 0.0094 2500 2000 172. The data recommend thus the FA-Z substrate for lead selective adsorption from complex cation mixtures.366 0. concentration.954 0. (a) Cd2+ immobilization efficiency vs.75g.046 2. Visa et al.740 0. Pb3 (OH)4+ or other poly-nuclear compounds in alkaline media [33] but.6350 M.0122 2. It is also to notice that for cadmium and zinc removal the macroporous cation exchanger gives almost similar results as FA-Z. the mono-layer adsorption described by the Langmuir equation supports the chemisorption mechanisms for the cadmium 3. supporting the conclusion that diffusion does not represent a limiting step in the processes on FA-Z or on cation exchangers. 3. with the maximum adsorption capacity having values close to those obtained in the kinetic investigations. the lead adsorption rate is much lower comparing to the other two cations. On the cation exchangers. the FA-Z substrate is slightly more effective than the microporous ion exchanger.757 – 0.87 59.766 0. The linearization proved that the pseudo-second order kinetic well Cd (mixture)/FA-Z Cd (mixture)/C100 microporous Cd (mixture)/C100 macroporous 70 60 100 50 40 30 20 60 40 Pb (mixture)/FA-Z Pb (mixture)/C100 microporos Pb (mixture)/C100 macroporos 10 50 100 150 200 250 60 50 40 30 20 10 0 0 Zn (mixture)/FA-Z Zn (mixture)/C100 microporos Zn (mixture)/C100 macroporos 70 80 20 0 90 80 Efficiency [%] Efficiency [%] c b 80 Efficiency [%] a 0 0 50 Time [min] 100 150 200 0 250 50 100 Time [min] 150 200 250 Time [min] Fig. (b) Pb2+ immobilization efficiency vs.9291 – 0. In lead removal. chemisorption is the representative mechanism.1. for all the three cations.995 2. The results also proves that cadmium and zinc adsorption can follow more parallel mechanisms. On FA-Z. Type of FA n=1 n=2 −1 Lead (Pb2+ ) FA-Z C100 microporous C150 macroporous Cadmium (Cd2+ ) FA-Z C100 microporous C150 macroporous Zinc (Zn2+ ) FA-Z C100 microporous C150 macroporous Interparticle diffusion R k2 [g/(mg min)] qe [mg/g] R Kid (mg/g min1/2 ) C R2 – – – 0.684 0.4.0.417 1.940 0.969 0. The pH value increases with the fly ash dosage.833 0.

Removal of lead and chromium from wastewater using bagasse fly ash-a sugar industry waste.-l. De Luca. T. was obtained from fly ash and was investigated as substrate for complex adsorption processes in a tri-component pollutant system. A. Sci.924 0. B. Cu and Cr(III) removal from water in Malaysia: post treatment by high quality limenstone.999 – 1. Adsorption of heavy metals from aqueous solutions on synthetic zeolite. Trgo.387 0. J. De Vivo. Ahmaruzzaman. Energy Combust. J. 99 (2008) 1578–1583.699 2. Environ. 4.997 0. Sugar beet pulp pectin gels as biosorbent for heavy metals: preparation and determination of biosorption and desorption characteristics. Handlingar 24 (4) (1898) 1–39. Water Res. Duta. [8] D. Lead ion adsorption could not be modeled by the Langmuir equation but.37 × 10−5 0. Ni. fly ash is chemically altered to form a material having the SiO2 /Al2 O3 over 2. [14] M.94 – 0.037 0.356 59.919 qmax [mg/g] and zinc cations. Kungliga Svenska Vetenskapsakademiens.999 0.999 0.M. Res. Dut¸a˘ . or The metal compounds are the hydrated cations which can adsorb with partial or total de-hydration (Eq. Sorption of copper(II) from aqueous solution by peat.105 5. González.009 – – 1354. [10] C.513 0. The Freundlich equation. Cheung. Blázquez. with smooth and regular surface and with highly polar surface. Ho. H. Zn. Water Res.939 0. Italy. ´ Removal of zinc. Van Deventer. A review on the utilization of fly ash. Purif. The process selectivity was analyzed considering the ionic radii of the heavy metals. 27 (1993) 821–827. A. Duran. 100 (2003) 53–63. J. 7 (2008) 373–378. 92 (12) (2011) 3082–3090.A. Manage. The adsorption studies proved that the novel material is highly active in lead removal from mixtures also containing cadmium and zinc. Lima. Visa et al. 36 (2010) 327–363. G. Shukla. C. .0003 0.A. Gupta. K. ´ M. Fava. B.0008 0.J.B. Colloids Surf. Bogatu. can support this type of approach. Conclusion A new adsorbent material.0005 0. opened to this cation.A.S. 58 (2008) 353–358. J.N. Pb. Lead removal on FA-Z is more efficient when compared also with the highly effective micro-porous cation exchanger. (8) and (9)). [4] V. 158 (2004) 77–97. [6] D. Adsorption of chromium from aqueous solutions by maple saw dust.992 0. Based on mild hydrothermal treatment.105 3.-n. ISBN: 9780444531599. Water Res. Bioresour. [11] S. Water Res.S. [19] S. This recommends the new material for replacing the traditional synthetic ion exchanger in cation removal and especially in selective lead adsorption from mixtures containing more cations. Acknowledgements This paper is supported by the Sectoral Operational Programme Human Resources Development (SOP HRD). 271 (2004) 312–328. Ruello. ural zeolite – a comparison of adsorption isotherms.F. G. G. Senturk. Visa.933 1.915 0. Manage. Water Air Soil Pollut.L. Sorption kinetic analysis for the removal of cadmium ions from effluents using bone char. A. J. Hazard. J.M. (8) and (9).708 0. Wang.927 30. Ali. [16] M. Environ. as presented by [34]: 2( SiO− ) + M2+ → ( Si O)2 M (8) 2( AlO− ) + M2+ → ( Al O)2 M (9) In this case removal the heavy metals (Cd2+ and Zn2 ) can be described with Eqs. Ozdes. Environ. 256 (2010) 5486–5491. Simultaneous adsorption of dyes and heavy metals from multicomponent solutions using fly ash. References [1] St.4. Technol.010 0. / Applied Surface Science 258 (2012) 6345–6352 6351 Table 8 Adsorption isotherm parameters.N.998 0. The Cd2+ and Zn2+ cations can adsorb by chemically bonding with the active site ( SiO− ) and ( AlO− ) and can form complexes on the surface (Eqs.961 42. Terdkiatburana. J. Technol. Sci. ˜ [5] Y. Single and co-adsorption of heavy metals on humic acid. Surf.L.5 and 6. [7] L. well describing lead adsorption. Grezzi.857 17. (10)) Substrate + Me(H2 O)n z+ ⇔ substrate − Me(H2 O)n−x z+ + xH2 O(10) where 0 ≤ x ≤ n [20]. J. L. Eng. 38 (2004) 1893–1899.991 4. Aziz. 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Parameters Langmuir isotherm FA-Z Cd/(Cd + Pb + Zn) Pb/(Pb + Cd + Zn) Zn/(Zn + Cd + Pb) C100 microporous Cd/(Cd + Pb + Zn) Pb/(Pb + Cd + Zn) Zn/(Zn + Cd + Pb) C150 macroporous Cd/(Cd + Pb + Zn) Pb/(Pb + Cd + Zn) Zn/(Zn + Cd + Pb) Freundlich isotherm a [L/mg] R2 n KF R2 28. Mohan. K. J. Structural reorganization of class F fly ash in alkaline silicate solutions. Single and multicomponent adsorption of cadmium and zinc using activated carbon derived from bagasse – an agricultural waste. for all the cations. Battistoni. Albanese.S.717 195. Colloid Interface Sci.L. Lee.194 142.662 14. Tadé.864 0. Geochem. the adsorption efficiencies are comparable with those obtained on FA-Z. Heavy metal shoch load in activated sluge uptake and toxic effects. [3] H.W. M. About the theory of so-called adsorption of soluble substances. Porter. A 211 (2002) 49–66. 36 (2002) 2304–2318.618 – 54.286 2. F. Yu. The optimum pH corresponding to the maximum adsorption was found between 5. Appl. Barakat.K. Adsorption removal of Cd(II) and Pb(II) ions from aqueous solutions by using Turkish illitic clay.V.0016 0. Mckay. Advanced Cd2+ removal on dispersed TiO2 -fly ash. A. zinc and cadmium cations. M. 45 (2011) 886–892. Sci. The adsorption efficiencies on the novel FA-Z material were compared with similar data obtained using micro. Zhang. Dorris Ca. Using the macroporous cation exchanger. Lagergren. Mata. M. S. Prog. Ariffin. Mater. Ballester. Z.462 0. Medvidovic. M.S. Munoz. Margrave. [2] P.401 0. The data prove that there is a high affinity of the fly ash based substrate for lead under competitive adsorption conditions.K.0059 0. J. Singh. Adlan. 150 (2009) 289–301.and macroporous cation exchangers. as a key parameter influencing diffusion and binding with the active sites.

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