Chemical Engineering Journal 171 (2011) 431438

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Chemical Engineering Journal

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Sorption of noroxacin by lotus stalk-based activated carbon and iron-doped activated alumina: Mechanisms, isotherms and kinetics
Weifeng Liu, Jian Zhang , Chenglu Zhang, Liang Ren
Shandong Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Shandong University, Jinan 250100, China

a r t i c l e

i n f o

a b s t r a c t
Two low-cost adsorbents, iron-doped activated alumina (Al2 O3 /Fe) and lotus stalk-based activated carbon (LAC) were employed to remove noroxacin from aqueous solutions. Sorption of noroxacin to both Al2 O3 /Fe and LAC showed a strong pH-dependent behavior. The maximum sorption capacity (21.58 mol/g and 922.70 mol/g) occurred at pH 6.5 and 5.5, respectively for Al2 O3 /Fe and LAC, which is near the pHpzc of the sorbent. While the equilibria adsorption isotherm data on LAC t well to the Langmuir equation, both Langmuir and Freundlich models correlated the isotherm data on Al2 O3 /Fe quite well. The sorption kinetics of both sorbents followed the pseudo-second order model. Several possible mechanisms for the adsorption systems were proposed. For the sorption on Al2 O3 /Fe, surface complexation and cation bridging were dominant mechanisms responsible for noroxacin removal, while hydrophobic interaction, cation exchange and -electron-donoracceptor interaction were likely important mechanisms for the sorption on LAC. 2011 Elsevier B.V. All rights reserved.

Article history: Received 10 February 2011 Received in revised form 29 March 2011 Accepted 30 March 2011 Keywords: Sorption Noroxacin Mechanism Iron-doped activated alumina Activated carbon

1. Introduction The presence of antibiotics in aquatic environments is raising an emerging concern recent years, regarding their potential risks to human and ecological health. Noroxacin (NOR) is a synthetic, broad-spectrum antibacterial compound that belongs to uoroquinolone class organism, which presents high antibacterial activity against both Gram-negative and Gram-positive bacteria through inhibition of DNA gyrase [1]. It has been extensively used in human and veterinary treatments as well as in aquaculture application, many of which cannot be completely metabolized in humans or animals, and are eventually discharged into the environment [2]. However, traditional wastewater or water treatment procedures cannot completely remove this compound and it may present a risk to human health through contaminated drinking water. Removal of noroxacin residue from aquatic environment is therefore considered important and serves as an attractive case study. Technologies available for this purpose include adsorption [3], photodegradation [4] and chlorine oxidation [5]. Adsorption is considered a simple and effective method to remove contaminants within water and wastewater. Till present time, only small amount of researches focused on antibiotics removal from aque-

Abbreviations: LAC, lotus stalk-based activated carbon; Al2 O3 /Fe, iron-doped activated alumina; NOR, noroxacin. Corresponding author. Tel.: +86 531 88363015; fax: +86 531 88364513. E-mail address: zhangjian00@sdu.edu.cn (J. Zhang). 1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.cej.2011.03.099

ous solutions using alternative adsorbents. Previous research on NOR sorption by different environmental matrices included silica, alumina [3], soils [6], and carbon nanotubes [7], but limited information is known about its adsorption by activated carbon. Activated carbon is the most widely used adsorbent today because of its extended surface area, well developed porosity and high adsorption capacity. However, its feasibility for large scale wastewater application is restricted due to the economic defect, resulting mainly from the high-cost precursors, such as coal, wood, and coconut shells. Therefore, developing economically available activated carbon or alternative adsorbent which is inexpensive and comes in abundant amount naturally is of interest. Activated alumina ( -Al2 O3 ) is a commercially available adsorbent that has been extensively used to remove various water contaminants. To our knowledge, there have been very few investigations on the sorption of noroxacin with oxide minerals. Lorphensri et al. [3] has reported the adsorption of noroxacin by -Al2 O3 , but such research is still limited in literature by now. Impregnation with metal ions has proven to be an effective way to improve the sorption ability of activated alumina for certain substances [8,9]. The impregnates can change the nature and surface properties of -alumina, on which not only adsorption, but also chemical reaction and catalytic decomposition of different adsorbates may take place [8]. To our best knowledge, however, no research has been conducted on the removal of NOR by iron modied alumina presently. Consequently, it is attractive to understand the sorption behavior and mechanisms

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for the uptake of NOR by this effective and inexpensive material. The objectives of this study were to investigate the performance of iron-doped activated alumina for adsorption of noroxacin from wastewater. The performance of Al2 O3 /Fe is also compared with that of a low-cost activated carbon prepared from a hydrophytes residue, lotus stalk. The NOR sorption behavior on these two materials has never been reported in literature. Detailed adsorption studies were conducted as a function of pH to obtain insight into the sorption performances and mechanisms. Sorption isotherms and kinetics were also investigated. The results from this study will provide useful information for potential NOR removal as well as its environmental risk assessment. 2. Materials and methods 2.1. Chemicals Noroxacin (99.8%, standard grade) was purchased from Fuchi Biological Technology Co. (China) and used as received. Important physicochemical properties of noroxacin are [10,11] MW: 319.331 g/mol; aqueous solubility: 161,000 mg/L at pH 5, 400 mg/L at pH 7, and 910 mg/L at pH 9; and pKa: 6.22 and 8.51. The commercial -alumina support, which was supplied by Wufeng Aluminum Magnesium Technology Co., Zibo, China, had stated minimum purities of 99%. Other chemicals used in this study were of analytical grade. Distilled water was used throughout for solution preparations. 2.2. Sorbent preparation and characterization Lotus stalk-based activated carbon (LAC) was fabricated according to the method described elsewhere [12]. The irondoped activated alumina (Al2 O3 /Fe) was prepared by an equilibriumdepositionltration method, to obtain a high dispersion of iron deposited phase on alumina support. In detail, as received activated alumina was crushed and sieved into particles of 100140 mesh prior to use. 2 g of the -Al2 O3 support was mixed with 400 mL of 103 M Fe(NO3 )3 solution, then shaken at 200 rpm in a temperature controlled shaker (SHZ-88, Shanghai) at room temperature. After 20 h, which is sufcient for the maximum iron loading, the solid mass was separated from the solvent by a vacuum air pump, and received a gentle wash with distilled water. The iron impregnated -Al2 O3 was then dried at 105 C for 12 h followed by calcination in air at 350 C for 2 h. The Fe loading amount on -Al2 O3 was 0.97 wt% as detected by inductively coupled plasma atomic emission spectroscopy (ICP-AES). Surface area and pore characteristics of adsorbents (Al2 O3 /Fe and LAC) were determined from nitrogen adsorption/desorption isotherms at 77 K using a surface area analyzer (Quantachrome Corporation, USA). The surface chemistries of Al2 O3 /Fe and LAC before and after NOR adsorption were detected using a Fourier transform infrared radiation (FTIR) spectrometer (Fourier-380 FT-IR, America), where the spectra were recorded from 400 to 4000 cm1 . Boehm titration method [13] was employed to determine the number of surface functional groups on LAC. The pH at the point of zero charge (pHpzc ) of Al2 O3 /Fe and LAC particles were estimated from a batch equilibrium method described by Babic et al. [14]. 2.3. Sorption experiments Batch equilibrium sorption experiments were performed at 21 1 C. Synthetic noroxacin solution with initial concentration of 100 M was prepared freshly within 1 day of use. This relatively high concentration value was chosen to represent the condition of

wastewater directly near a contamination source, e.g. pharmaceutical companies. Experimentally, a weighed quantity of sorbents (0.01 g for LAC and 0.4 g for Al2 O3 /Fe) were dispersed in 100 mL NOR solution at desired initial concentration, pH, and ionic strength (10 mM NaCl). Samples were equilibrated by shaking in a water bath at 200 rpm in dark for 24 h (LAC) or 16 h (Al2 O3 /Fe). After equilibration, the samples were ltered and the residual NOR concentration was analysed by an UVvis spectrophotometer (UV-754, Shanghai) at the maximum absorption wavelength of 273 nm. Solution pH was adjusted to the required value with 0.1 M HCl and 0.1 M NaOH. Control experiments without adsorbents were conducted in the same manner to account for possible noroxacin losses as sorption to glass tubes and other reactions in solution, although little solute loss was detected under our experimental conditions. The solidwater sorption coefcient, Kd (L/m2 ), was employed in this study, because the solid and aqueous-phase distribution of a compound determines its mobility, bioavailability, and susceptibility to transformation reactions [6]. Kd is dened as Kd = CS /Cw , where Cw ( mol/L) is the equilibrium aqueous NOR concentration. CS ( mol/m2 ) is the equilibrium sorbed concentration, which can be calculated as CS = (C0 Cw )V MS A (1)

where C0 ( mol/L) is the control NOR concentration at the end of the experiment; V (L) is the volume of solution; Ms (g) is the mass of solid sorbent, and A (m2 /g) is the sorbent specic surface area. Area-normalized concentrations were computed because interactions of noroxacin with the sorbents were anticipated to occur by an adsorptive mechanism. The effect of solution pH on noroxacin removal by the sorbents was tested in pH range of 3.510.5. Experiments were conducted in a similar manner as described above, except that the sorbent dose was 0.007 g/100 mL for LAC and 0.3 g/100 mL for Al2 O3 /Fe to control the NOR removal percent between 40% and 90%. For Al2 O3 /Fe, blank asks without NOR solute were also performed to test the dissolution amount of Al3+ and Fe3+ in distilled water. Dissolved Al3+ and Fe3+ concentrations in the solution were analysed by ICPAES. Adsorption isotherms were conducted at three pH levels with initial NOR concentrations ranging from 80 to 500 mol/L. 2.4. Desorption experiments Immediately after the equilibrium sorption experiments as described above, the adsorbent was ltered and gently washed with distilled water to remove any unadsorbed NOR molecular trapped between the adsorbent particles. Next, a desorption treatment was applied by adding 100 mL of either (i) 0.01 M NaCl, (ii) 1 M NaCl, (iii) 0.2 M MgCl2 , (iv) methanol, (v) 0.1 M NaOH or (vi) 0.25 M EDTA (only for Al2 O3 /Fe) to the solid. Desorption solutions were shaken in dark for 24 h (LAC) or 16 h (Al2 O3 /Fe) before analysis for dissolved noroxacin mass. 3. Results and discussion 3.1. Physical properties of adsorbent Different structure characteristics of the two samples are evident as shown from the pore size distributions in Fig. 1. The pores of LAC mostly locate in the range of micropores and small mesopores with average pore width of 3.41 nm, indicating a micromesoporous structure in activated carbon. While Al2 O3 /Fe shows a typically mesoporous structure (most pores 38 nm, average pore width 5.33 nm). The calculated BET surface area of LAC is 1289.1 m2 /g, in which the micropore and external surface areas are

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0.5

0.4

Volume (cm3/nm/g)

LAC

0.3

Transmittance %

0.2

1558.7

1181.8

1071.7

LAC-NOR
746.4 803.1 1452.7 1260.3

0.1

0.0

12

16

20 4000 3500 3000 2500 2000 1500 1000 500

Pore whith (nm)

0.12 0.10

Wavenumbers (cm-1)

b
Al2O3/Fe

Volume (cm3/nm/g)

0.08 0.06 0.04 0.02 0.00

Transmittance %

1636.4

Al2O3/Fe-NOR
3441.4

12

16

20

550.5

Pore whith (nm)

Fig. 1. Pore size distributions for LAC (a) and Al2 O3 /Fe (b).

4000

3500

3000

2500

2000

1500

1000

500

509.4 m2 /g and 779.7 m2 /g, respectively. Al2 O3 /Fe has a BET surface area of 140.6 m2 /g with no microspores. 3.2. Chemical properties of adsorbent Surface oxygen-containing functional groups within activated carbon determine its surface acidity/basicity, and act as a crucial factor affecting its adsorption capacity and selectivity. The existence of several acidic and basic groups on LAC can be veried from Boehm titration. Specically, it contains 0.749 mmol/g of carboxylic group, 0.405 mmol/g of lactonic group and 0.567 mmol/g of phenolic group, thus giving a total acidity of 1.721 mmol/g. The total number of basic functional groups was 0.894 mmol/g. The presence of oxygen functionalities can also be conrmed by the FTIR spectra of LAC. As shown in Fig. 2a, the spectra band observed at 1558.7 cm1 corresponds to the stretching vibrations of C O, originated from carboxyl, lacton or basic functional groups (e.g. chromene and pyrone structures). Peaks around 1181.8 cm1 and 1071.7 cm1 can be assigned to CO bonding [15]. Surface functional groups of Al2 O3 /Fe as determined by FTIR spectra are depicted in Fig. 2b. The very broad peak centered at 3441.4 cm1 is ascribed to be OH group in AlOH or FeOH [16]. The peak around 1636.4 cm1 comes from HOH bending while the peak around 550.5 cm1 can be recognized to AlO or FeO groups [17]. The point of zero charge of adsorbent (pHpzc ) is a pH point where the amount of negative charges on a sorbent surface just equals the amount of positive charges [16]. When solution pH < pHpzc ,

Wavenumbers (cm-1)
Fig. 2. FTIR spectra of LAC (a) and Al2 O3 /Fe (b) before and after noroxacin adsorption.

the adsorbent surface will be protonated by the excess H+ ions, thereby acquiring a positive charge. When solution pH > pHpzc , the adsorbent surface will be deprotonated by the OH ions and thus acquiring a negative charge. The plots to determine the point of zero charges for Al2 O3 /Fe and LAC are shown in Fig. S1. The pHpzc for Al2 O3 /Fe and LAC were found to be 6.53 and 5.48, respectively. The relatively low pHpzc for LAC is probably caused by the large amount of acidic functional groups on its surface. 3.3. Effect of pH and sorption mechanisms In adsorption of noroxacin, solution pH is considered to be the most important factor affecting the sorption performance, as it can alter the charge and species of noroxacin as well as the sorbent surface properties. To evaluate the inuence of pH on adsorption, studies of noroxacin adsorption onto Al2 O3 /Fe and LAC were conducted within pH range of 3.510.5. 3.3.1. Mechanisms of NOR sorption to Al2 O3 /Fe The extent of noroxacin sorption onto Al2 O3 /Fe as a function of pH is presented in Fig. 3a. Strong adsorption occurred in pH range of 5.57.5 with the maximum adsorption extent (21.58 mol/g, removal rate 90.14%) at pH 6.5, which is near the

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0.020 Cation 0.016 Zwitterion Anion 100

Kd (L/m )

0.012

60

0.008

40

0.004

20

0.000 3 4 5 6 7 8 9 10 11

pH

0.20 Cation 0.16 Zwitterion Anion

100

Kd (L/m )

0.12

60

0.08

40

0.04

20

0.00 3 4 5 6 7 8 9 10 11

pH
Fig. 3. pH-sorption prole of noroxacin onto Al2 O3 /Fe (a) and LAC (b) (C0 = 100 mol/L, I = 0.01 M NaCl, sorbent dose = 3 g/L for Al2 O3 /Fe and 0.07 g/L for LAC). The dashed lines represent the fraction of cationic, zwitterionic and anionic forms of noroxacin.

pHpzc of Al2 O3 /Fe. Above and below this rang, rapid and gradual decrease of the NOR adsorption was observed. A similar trend was also found during the sorption of noroxacin to aluminum oxides [3]. The weak sorption at extremely low and high pH ranges can be attributed to the great electrostatic repulsive force between NOR and the mineral surface, i.e. both noroxacin and Al2 O3 /Fe became predominantly positively charged at low pH (<4.5) and

Fig. 4. Schematic diagrams for surface complexation (a) and cation bridging (b) interactions between noroxacin and Al2 O3 /Fe surface. Mn+ represents H+ , Al3+ or Fe3+ ions on the edge of Al2 O3 /Fe surface.

Specious fraction (%)

80

Specious fraction (%)

80

negatively charged at high pH (>8.5), thus could repel each other. The adsorption mechanisms of uoroquinolone antimicrobials to soils [18] and oxide minerals [3,19] have been investigated by several researchers. Generally, primary sorption interactions of antimicrobials with model sorbent phases have been documented to be cation exchange [18], surface complexation [19] and cation bridging [20]. Based on the experimental results and previous researches, several possible adsorption mechanisms of noroxacin onto Al2 O3 /Fe can be proposed in this study. The rst mechanism is surface complexation mechanism. It is known that noroxacin is capable of bonding with multivalent metal ions such as Al3+ , Fe3+ and Mn2+ to form strong complexes [21,22]. Surface complexation has been well established for the sorption of uoroquinolone compounds to metal oxides [19]. It is reasonable to hypothesis that stable complexation formed between noroxacin and Al2 O3 /Fe surface during the sorption. Considering the structures of Al/Fenoroxacin complexes, a possible NORAl2 O3 /Fe chelating interaction is hypothesized to occur in this study [23]. Noroxacin is likely to form an energetically favorable mononuclear bidentate complex (i.e., a six-membered ring) with the Fe and Al atom on the Al2 O3 /Fe surface through the keto oxygen and one of the Os of the carboxylate. The proposed surface complexation structure is depicted in Fig. 4a. Cation bridging is another important mechanism probably involved in the sorption of NOR to Al2 O3 /Fe. Because of the presence of free H+ in the solution, Al2 O3 /Fe may be protonated with extra H+ bonding to the surface. In addition, the edge Al/Fe atoms in Al2 O3 /Fe mineral are ready to be protonated in forms of Al3+ and/or Fe3+ , some of which bond in the diffuse interlamellar space. These edge sites cations (H+ , Al3+ and Fe3+ ) can intercalate with the anionic COO group of NOR to form a cation bridge. This cation bridge interaction is generally very stable in aqueous environments [6,20]. Moreover, Al3+ and Fe3+ cations are considered to be more effective than H+ in promoting adsorption of noroxacin on Al2 O3 /Fe surface due to their stronger electric charges, providing a stronger electrostatic attraction for the anionic carboxyl moiety of noroxacin. The cation bridge model of adsorption of NOR to Al2 O3 /Fe surface is presented in Fig. 4b. The same mechanism has also been proposed in the sorption of quinolone acid derivatives to clay mineral surfaces by Nowara et al. [20]. It is fairly well-known that sorption of chelating compounds will signicantly increase the solubility of oxide minerals through the ligand-promoted dissolution mechanism [24]. However, the solubility of Al2 O3 /Fe was not notably promoted by contacting with NOR as compared to distilled water at pH 4.58.5 when intensive adsorption occurred (Fig. 5).

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0.4

Soluable Al concentration (mg/L)

6 5 4
3 4 5

no NOR NOR

0.3 0.2 0.1 0.0

10

11

3 2 1 0

10

11

pH
Fig. 5. Solubility of Al and Fe (inset) from Al2 O3 /Fe sample as a function of pH in the presence and absence of noroxacin.

This may be attributed to the cation bridging interaction that consumed Al3+ and Fe3+ cations and hindered their dissolution and diffusion into the bulk solution. FTIR spectra of Al2 O3 /Fe after equilibrating with noroxacin showed little difference from that of virgin Al2 O3 /Fe (Fig. 2b). This may be due to the low NOR sorption amount on Al2 O3 /Fe (922.7 and 21.5 mol/g for LAC and Al2 O3 /Fe, respectively at optimal pH), causing minimal changes on the IR signals. Desorption studies were conducted to obtain further insight into the mechanism of interactions between noroxacin and the adsorbents (Table 1). NaCl solutions were employed to respect the importance of electrostatic interaction. Less than 8% of the sorbed noroxacin was recovered by NaCl solutions of various strengths, implying a less important role of electrostatic interactions in the sorption process. Magnesium(II) cations are known to form solution phase complexes with noroxacin [25]. Only 8.42% of the sorbed noroxacin mass was desorbed by 0.2 M MgCl2 , suggesting that attachment of NOR molecules with the Al2 O3 /Fe surface is very strong and cannot be easily dissociated by the complexation of NOR with Mg2+ . Methanol was used to determine the role of hydrophobicity in noroxacin sorption. Less than 2% of sorbed noroxacin was recovered by a methanol wash, indicating a negligible contribution of hydrophobic interaction to the adsorption. As much as 83.1% of the sorbed noroxacin was desorbed by the presence of NaOH solution. This implied that the dominant mechanism in the sorption of noroxacin on Al2 O3 /Fe should be strong chemical interactions, which may originate from surface complexation and/or cation bridging. Finally, EDTA, a strong chelating agent capable of forming inner sphere complexes with iron/alumina oxides, was used to competitively displace sorbed noroxacin. More than 60% of the sorbed noroxacin was recovered by EDTA addition, providing evidence for the surface complexation mechanism. 3.3.2. Mechanisms of NOR sorption to LAC Fig. 3b shows the sorption coefcients as a function of pH for the adsorption of NOR onto LAC. The adsorption achieved its maximum (922.70 mol/g, removal rate 95.10%) at pH 5.5 and decreased signicantly when pH was higher or lower than this range. The observed sorption behavior can be attributed to a combination of pH-dependent speciation of noroxacin and surface charge characteristics of LAC. Noroxacin has two proton-binding sites (carboxyl and piperazinyl group) with reported pKa values of 6.22 and 8.51, respectively. With these two pKa values, noroxacin can exist in cationic form, zwitterionic form or anionic form depending on the

solution pH (see Fig. S2). As can be seen from the speciation (Fig. 3), at pH below 6.2 the cationic form of NOR is predominant. At pH 6.28.5 the three forms coexist with the zwitterionic form being dominant. The anionic form dominates at pH higher than 8.5. The surface of LAC was positively charged at pH lower than pHpzc (5.48) and negatively charged at pH higher than pHpzc . Thus, electrostatic interaction between charged NOR and charged LAC surface is expected to occur in the sorption process. At pH < 4.5 and pH > 8.5, most NOR molecules had the same sign of charge as LAC and could repel each other, causing the sorption greatly depressed. As shown in Fig. 3b, at pH 4.56.0 where the NOR sorption was strong, cationic NOR was the dominant specie in the solution (98%62%). Especially, the cationic form account for 83.98% of the total molecule when the maximum sorption occurred at pH 5.5. This suggested that cationic NOR acted as a vital contributor to the overall noroxacin sorption onto LAC. Accordingly, cation exchange is proposed to be an important mechanism participating in the adsorption process. In principle, the protons binding to LAC surface due to the extra H+ in bulk solution were exchanged by the positively charged piperazinyl group within noroxacin. This exchange mechanism can be conrmed by the fact that the solution pH increased after NOR sorption at pH 4.55.5, but the increasing extent was much lower than that of distilled water with LAC. It is possible that cation exchange released partial protons from LAC surface to the bulk solution. Note that at pH 5.56.5, part of the LAC surface was still protonated so cation exchange could also take place. Cation exchange has been proposed to be an important mechanism in the sorption of uoroquinolone compounds to soils [6,18]. The schematic diagram for this mechanism is presented in Fig. S3. Activated carbon is an organic semiconductor with delocalized electrons on its surfaces, thus shows electrondonor properties [26]. The -electron-donoracceptor (EDA) interaction is, therefore, considered to participate in the sorption of NOR onto LAC. Phenol groups with an unshared pair of electrons on the oxygen atom, as well as deprotonated carboxyl groups on the carbon surface can act as electron-donors [26]. On the other hand, the benzene ring on NOR can function as a -electron-acceptor due to the strong electron-withdrawing ability of the uorine group. Based on the EDA theory, a -donor compound and a -acceptor compound are ready to interact with each other and the interaction is generally strong. Another possible mechanism is hydrophobic interaction between the carbon surface and NOR molecule. The basic graphitic structure of activated carbon provides hydrophobic sites, which can interact with hydrophobic molecules. Although NOR is most hydrophobic at pH between its two pKa values, where the sorption extent was not the maximum, hydrophobic interaction can still took place during the sorption process. As such, the contribution of hydrophobic interaction to NOR sorption could not be excluded, despite the lack of substantial evidence for this process. FTIR spectra of LAC after adsorption conrmed the presence of noroxacin on LAC surface as shown in Fig. 2a. New peaks at 1452.7, 803.1 and 746.39 cm1 in the FTIR spectrum of LAC after NOR sorption occurred, all of which can be assigned to bending modes of aromatic rings, indicating the attachment of benzene ring of NOR onto LAC surface. This serves an evidence for the EDA interaction between LAC and noroxacin molecules. Additional peak at 1260.3 cm1 can also be detected, which came from the asymmetric CN stretching, suggesting the involvement of piperazinyl group of NOR in the interaction with LAC. This result is in keeping with the cation exchange mechanism proposed above. As shown in Table 1, less than 9% of the sorbed noroxacin was recovered from LAC by NaCl solutions of various strengths. This implied that the sorption mechanism was stronger than nonspecic electrostatic interactions for NOR. The amount of desorbed noroxacin by MgCl2 increased to about 21.2% of the sorbed mass,

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Table 1 Percentage of sorbed noroxacin mass desorbed by various treatments. Adsorbent Al2 O3 /Fe LAC 0.01 M NaCl 7.21% 2.26% 1 M NaCl 4.72% 8.26% 0.2 M MgCl2 8.42% 21.16% Methanol 1.86% 13.39% 0.1 M NaOH 83.10% 60.81% 0.25 M EDTA 65.82%

denotes treatments not tested. Table 2 Langmuir and Freundlich isotherm parameters for adsorption of noroxacin on Al2 O3 /Fe and LAC. Adsorbent pH Langmuir isotherm Qm ( mol/g) Al2 O3 /Fe 4.5 6.5 9.5 4.5 5.5 9.5 62.8931 102.0408 64.1026 1250.0000 1428.5714 1111.1111 KL (L/ mol) 0.0171 0.0195 0.01321 0.1905 0.1250 0.0714 R
2

Freundlich isotherm Kf ( mol/g (L/ mol)1/n ) 3.9279 6.0599 5.8580 683.4818 624.7178 414.0141 1/n 0.4656 0.5156 0.3960 0.1102 0.1459 0.1761 R2 0.9877 0.9907 0.9931 0.9386 0.9060 0.9095

LAC

0.9817 0.9931 0.9869 0.9994 0.9996 0.9974

presumably due to competing NOR complexation with Mg2+ in the aqueous phase. About 13.4% of the sorbed noroxacin mass was recovered by methanol treatment, suggesting that hydrophobic interaction between LAC and noroxacin molecules did took place but not a major mechanism. Finally, as much as 60.8% of the sorbed noroxacin was desorbed by 0.1 M NaOH, indicating that strong chemical interactions, which may come from cation exchange and/or EDA interaction, are dominant mechanisms in the sorption noroxacin on LAC. 3.4. Sorption isotherms Sorption isotherm is critical to evaluate the sorption capacity of adsorbents as well as to understand the nature of sorbatesorbent interactions. The adsorption isotherms of NOR onto Al2 O3 /Fe and LAC were examined. The initial experiments were conducted at pH values of pH 4.5, 6.5, 9.5 for Al2 O3 /Fe and 4.5, 5.5, 9.5 for LAC, spanning the sorbatesorbent charge states for these two adsorbents. Two commonly used models, the Langmuir [27] and Freundlich [28] equations were employed to correlated the experimental data, which can be expressed respectively as Qe = Qm KL Ce 1 + KL Ce
1/n

erogeneous surfaces. The good application of both models implied that besides adsorption onto specic sorption sites through chemical interactions such as surface complexation and cation bridging, sorbatesorbate interaction may also play an important role in the sorption process by Al2 O3 /Fe. This is reasonable because NOR solution under environmental pH is a complex mixture of cationic, zwitterionic and anionic forms, the interactions between which would be complicated and nonspecic interactions such as electrostatic repulsion may be signicant. The maximum NOR sorption occurred at pH 6.5 according to the Langmuir parameter Qm and Freundlich parameter Kf . Values of 1/n were less than 1, suggesting that the sorption of NOR onto Al2 O3 /Fe was a favorable process. On the other hand, the sorption isotherms of NOR on LAC can be described better by the Langmuir model than the Freundlich model for all pH levels, due to the high correlation coefcient values of the former (R2 > 0.997). This result implied that monolayer sorption of NOR on LAC probably occurred. It could be that cation exchange and/or EDA interaction dominated the process, and the sorption amount reached the maximum when the available sites were saturated with NOR molecules. The Freundlich constant 1/n were less than 1 indicating a favorable adsorption process [3].

(2) 3.5. Sorption kinetics (3) The kinetics for adsorption of noroxacin onto Al2 O3 /Fe and LAC were also examined. The experimental data were tted by the pseudo-rst-order model Eq. (4) and pseudo-second-order model Eq. (5) [29]: ln(Qe Qt ) = ln Qe k1 t t 1 t = + 2 Qt Qe k2 Qe (4)

Qe = Kf Ce

where Qe ( mol/g) is the amount of NOR adsorbed at equilibrium; Qm ( mol/g) is the maximum NOR adsorption capacity; KL (L/ mol) is the Langmuir constant that is related to the apparent energy of adsorption; Kf ( mol/g(L/ mol)1/n ) is the Freundlich constant indicating the relative adsorption capacity, and n is a constant depicting the sorption intensity. As-tted Langmuir and Freundlich parameters for the adsorption of noroxacin onto Al2 O3 /Fe and LAC are listed in Table 2. As shown in Table 2, both the Langmuir and Freundlich models correlated the sorption isotherms on Al2 O3 /Fe quite well, with all R2 values higher than 0.98. The Langmuir equation is derived from the assumption of monolayer adsorption on specic homogenous sites, while the Freundlich model represents adsorption on het-

(5)

where Qe and Qt ( mol/g) are the amounts of NOR adsorbed at equilibrium and at time t (h); k1 (1/h) and k2 (g/( molh)) are the pseudo-rst-order and pseudo-second-order rate constants.

Table 3 Kinetic parameters of the pseudo-rst and second-order models for adsorption of noroxacin on Al2 O3 /Fe and LAC. Adsorbent Qexp ( mol/g) Pseudo-rst-order model k1 (1/h) Al2 O3 /Fe LAC 22.9515 954.0353 0.4312 0.2312 Qcal ( mol/g) 19.7608 734.7277 R2 0.9913 0.9715 q (%) 38.742 55.119 Pseudo-second-order model k2 (g/( molh)) 0.0427 0.0008 Qcal ( mol/g) 24.1546 1000.0000 R2 0.9990 0.9990 q (%) 13.026 12.891

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25

4. Conclusions The present study shows that noroxacin can be effectively removed by low-cost adsorbents iron-doped activated alumina (Al2 O3 /Fe) and lotus stalk-based activated carbon (LAC). The maximum sorption capacity occurred near the pHpzc of the sorbents. Adsorption isotherms on LAC t well to the Langmuir equation, while both Langmuir and Freundlich models correlated the isotherm data on Al2 O3 /Fe quite well. The sorption kinetics of both sorbents followed the pseudo-second order model. While complexation and cation bridging appears dominant mechanisms for noroxacin sorption on Al2 O3 /Fe, hydrophobic interaction, cation exchange and -electron-donoracceptor interaction were likely important mechanisms for the sorption on LAC.
0 5 10 15 20

20

Qt (umol/g)

15

10

t (h)

b
1000

Acknowledgements The work was supported by the National Water Special Project (No. 2009ZX07210-009-04), the National Natural Science Foundation of China (No. 21007032) and the Independent Innovation Foundation of Shandong University (No. 2009JQ009). Appendix A. Supplementary data

800

Qt (umol/g)

600 400 200 0

Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.cej.2011.03.099. References
0 5 10 15 20 25 30

t (h)
Fig. 6. Sorption kinetics of noroxacin onto Al2 O3 /Fe (a) and LAC (b) and modeling using the pseudo-rst-order (dashed lines) and pseudo-second-order (solid lines) equations (C0 = 100 mol/L, I = 0.01 M NaCl, pH 6.6, sorbent dose = 4 g/L for Al2 O3 /Fe and 0.1 g/L for LAC).

To determine the validity of each model for the adsorption system, the correlation coefcients (R2 ), together with a normalized standard deviation q (%) were employed. q is dened as q(%) = 100 [(Qexp Qcal )/Qexp ] N1
2

(6)

where Qexp and Qcal ( mol/g) are the experimental and modelcalculated NOR uptake amounts; N is the number of measurements made. It is clear that a smaller q value means little deviation between the experimental data and that calculated from the model and vice versa. Adsorption kinetics of noroxacin on Al2 O3 /Fe and LAC along with the correlated results using the rst and second order models are presented in Fig. 6, and the as tted parameters are summarized in Table 3. For both sorbents, the pseudo-second-order model correlates the kinetic data quite well with high correlation coefcients (R2 0.999) and good agreements between Qcal and Qexp ( q < 15%). The pseudo-second-order model assumes that the sorption rate is controlled by chemical interaction and the sorption capacity is proportional to the number of active sites on the sorbent [29]. This result is in keeping with the sorption mechanisms proposed above for Al2 O3 /Fe and LAC. It can also be seen from Fig. 6 and Table 3 that the equilibrium NOR sorption amounts on LAC was about 40 times of that on Al2 O3 /Fe, which may be largely attributed to the much higher specic surface area of the former that can provide more contacting area and specic sorption sites for NOR. Note that Al2 O3 /Fe is still an effective adsorbent for noroxacin due to its advantages such as abundance and low cost.

[1] R. Hirsch, T.A. Ternes, K. Haberer, K.L. Kratz, Occurrence of antibiotics in the environment, Sci. Total Environ. 225 (1999) 109118. [2] E.M. Golet, A.C. Alder, W. Giger, Environmental exposure and risk assessment of uoroquinolone antibacterial agents in wastewater and river water of the Gatt Valley watershed, Switzerland, Environ. Sci. Technol. 36 (2002) 36453651. [3] O. Lorphensri, J. Intravijit, D.A. Sabatini, T.C.G. Kibbey, K. Osathaphan, C. Saiwan, Sorption of acetaminophen, 17-ethynyl estradiol, nalidixic acid, and noroxacin to silica, alumina, and a hydrophobic medium, Water Res. 40 (2006) 14811491. [4] T. Paul, P.L. Miller, T.J. Strathman, Visible-light-mediated TiO2 photocatalysis of uoroquinolone antibacterial agents, Environ. Sci. Technol. 41 (2007) 47204727. [5] M.C. Dodd, A.D. Shah, U.V. Gunten, C. Huang, Interactions of uoroquinolone antibacterial agents with aqueous chlorine: reaction kinetics, mechanisms, and transformation pathways, Environ. Sci. Technol. 39 (2005) 70657076. [6] R.A. Figueroa-Diva, D. Vasudevan, A.A. MacKay, Trends in soil sorption coefcients within common antimicrobial families, Chemosphere 79 (2010) 786793. [7] Z. Wang, X. Yu, B. Pan, B. Xing, Noroxacin sorption and its thermodynamics on surface-modied carbon nanotubes, Environ. Sci. Technol. 44 (2010) 978984. [8] A.K. Khattak, K. Mahmood, M. Afzal, M. Saleem, R. Qadeer, Thermodynamic studies of methanol adsorption on metal impregnated -alumina samples, Colloids Surf. A 236 (2004) 103110. [9] S.S. Tripathy, J.L. Bersillon, K. Gopal, Removal of uoride from drinking water by adsorption onto alum-impregnated activated alumina, Sep. Purif. Technol. 50 (2006) 310317. [10] D.L. Ross, C.M. Riley, Aqueous solubilities of some various substituted quinolone antimicrobials, Int. J. Pharm. 63 (1990) 237250. [11] K. Takacs-Novk, M. Jzan, I. Hermecz, G. Szsz, Lipophilicity of antibacterial uoroquinolones, Int. J. Pharm. 79 (1992) 8996. [12] L. Huang, Y. Sun, T. Yang, L. Li, Adsorption behavior of Ni (II) on lotus stalks derived active carbon by phosphoric acid activation, Desalination 268 (2011) 1219. [13] H.P. Boehm, Some aspects of the surface chemistry of carbon blacks and other carbons, Carbon 32 (1994) 759769. [14] B.M. Babic, S.K. Milonjic, M.J. Polovina, B.V. Kaludierovic, Point of zero charge and intrinsic equilibrium constants of activated carbon cloth, Carbon 37 (1999) 477481. [15] E.K. Putra, R. Pranowo, J. Sunarso, N. Indraswati, S. Ismadji, Performance of activated carbon and bentonite for adsorption of amoxicillin from wastewater: mechanisms, isotherms and kinetics, Water Res. 43 (2009) 24192430. [16] S. Kubilay, R. Grkan, A. Savran, T. Sahan, Removal of Cu(II), Zn(II) and Co(II) ions from aqueous solutions by adsorption onto natural bentonite, Adsorption 13 (2007) 4151. [17] E. Finocchio, G. Busca, Characterization and hydrocarbon oxidation activity of coprecipitated mixed oxides Mn3 O4 /Al2 O3 , Catal. Today 70 (2001) 213225.

438

W. Liu et al. / Chemical Engineering Journal 171 (2011) 431438 [24] E. Molis, O. Barrs, H. Marchand, E. Sauzat, B. Humbert, F. Thoms, Initial steps of ligand promoted dissolution of gibbsite, Colloids Surf. A 163 (2000) 283292. [25] I. Turel, The interactions of metal ions with quinolone antibacterial agents, Coord. Chem. Rev. 232 (2002) 2747. [26] E.D. Lavrinenko-Ometsinskaya, K.A. Kazdobin, V.V. Strelko, Quantum-chemical evaluation of electrondonor properties of ordinary and modied carbon sorbents, Theor. Exp. Chem. 25 (1989) 666670. [27] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and platinum, J. Am. Chem. Soc. 40 (1918) 13611403. [28] H. Freundlich, W. Heller, The Adsorption of cis- and trans-Azobenzene, J. Am. Chem. Soc. 61 (1939) 22282230. [29] Y.S. Ho, J.C.Y. Ng, G. McKay, Kinetics of pollutant sorption by biosorbents: review, Sep. Purif. Rev. 29 (2000) 189232.

[18] A.A. MacKay, D.E. Seremet, Probe compounds to quantify cation exchange and complexation interactions of ciprooxacin with soils, Environ. Sci. Technol. 42 (2008) 82708276. [19] C. Gu, K.G. Karthikeyan, Sorption of the antimicrobial ciprooxacin to aluminum and iron hydrous oxides, Environ. Sci. Technol. 39 (2005) 91669173. [20] A. Nowara, J. Burhenne, M. Spiteller, Binding of uoroquinolone carboxylic acid derivatives to clay minerals, J. Agric. Food. Chem. 45 (1997) 14591463. [21] J. Al-Mustafa, B. Tashtoush, Iron(II) and iron(III) perchlorate complexes of ciprooxacin and noroxacin, J. Coord. Chem. 56 (2003) 113124. [22] P.T. Djurdjevic, M. Jelikic-Stankov, D. Stankov, Fluorescence reaction and complexation equilibria between noroxacin and aluminium(III) ion in chloride medium, Anal. Chim. Acta 300 (1995) 253259. [23] A.I. Drakopoulos, P.C. Ioannou, Spectrouorimetric study of the acidbase equilibria and complexation behavior of the uoroquinolone antibiotics ooxacin, noroxacin, ciprooxacin and peoxacin in aqueous solution, Anal. Chim. Acta 354 (1997) 197204.