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<a href=Journal of Environmental Management 98 (2012) 168 e 174 Contents lists available at S c i V e r s e S c i e n c e D i r e c t Journal of Environmental Management journal homepage: www.els evier.com/locate/jenvman Degradation, mineralization and antibiotic inactivation of amoxicillin by UV-A/TiO photocatalysis Despina Dimitrakopoulou , Irene Rethemiotaki , Zacharias Frontistis , Nikolaos P. Xekoukoulotakis , Danae Venieri , Dionissios Mantzavinos * Department of Environmental Engineering, Technical University of Crete, Polytechneioupolis, GR-73100 Chania, Greece School of Science and Technology, The Hellenic Open University, 18 Parodos Aristotelous St., GR-26335 Patras, Greece article info Article history: Received 18 July 2011 Received in revised form 19 December 2011 Accepted 8 January 2012 Available online 24 January 2012 Keywords: Activity Kinetics Pharmaceuticals Removal Semiconductor Water abstract The UV-A/TiO photocatalytic decomposition of amoxicillin (AMX) in aqueous suspensions was inves- tigated. Experiments were performed at antibiotic concentrations between 2.5 and 30 mg/L, eight commercially available TiO catalysts at loadings between 100 and 750 mg/L, acidic or near-neutral conditions (pH 5 or 7.5) and two different matrices (ultrapure water and secondary treated ef fl uent) at a photon fl ux of 8 10 E/(L min). Of the various catalysts tested, Degussa P25 was highly active, i.e. complete AMX degradation and 93% mineralization could be achieved after 25 and 90 min of reaction, respectively at 10 mg/L AMX and 250 mg/L titania. In general, mineralization was slower than degra- dation due to the formation of stable transformation by-products. For the range of concentrations studied, initial degradation rates can be approached by a Langmuir e Hinshelwood kinetic model, while the reaction order with respect to AMX shifts from fi rst to zeroth as initial concentration increases from 2.5 to 5 mg/L to higher values. Degradation in treated ef fl uent was partly impeded compared to pure water due to the inherent presence of organic and inorganic constituents that compete for hydroxyl radicals. Although increasing solution pH from 5 to 7.5 had no effect on degradation, it retarded mineralization. The antibiotic activity of AMX prior to and after photocatalytic degradation was tested to three reference bacterial strains, namely Escherichia coli (ATCC 23716), Klebsiella pneumoniae (NCTC 5056) and Enterococcus faecalis (ATCC 14506). The fi rst two were found to be highly resistant at AMX concentrations up to 25 mg/L, while the latter could partly be inactivated at lower AMX concentrations (i.e. 10 mg/L) and/or in the presence of photocatalytic by-products. 2012 Elsevier Ltd. All rights reserved. 1. Introduction Pharmaceuticals constitute an emerging class of micro- pollutants, whose occurrence in the environment is due to point sources, like production ef fl uents and waste disposal, as well as diffuse sources, like run-off from fi elds and anthropogenic ef fl uents ( Kümmerer, 2009a ). A variety of pharmaceuticals have been detected in many environmental samples worldwide including wastewater treatment plant ef fl uents, surface water, seawater, groundwater, soils and sediments and this is closely related to their bioresistant nature ( Fatta-Kassinos et al., 2010 ). Among the various pharmaceutical compounds, antibiotics have been paid particular attention because of their potential role in the development of antibiotic-resistant bacteria ( Homem and Santos, * Corresponding author. Tel.: þ 302821037797; fax: þ 302821035852. E-mail address: mantzavi@mred.tuc.gr (D. Mantzavinos). 0301-4797/$ e see front matter 2012 Elsevier Ltd. All rights reserved. doi: 10.1016/j.jenvman.2012.01.010 2011 ). Antibiotics are used extensively in human and veterinary medicine, as well as in aquaculture to prevent or treat microbial infections. Most antibiotics tested to date are known to be bio- recalcitrant under aerobic conditions ( Kümmerer, 2009b ), thus escaping intact from conventional wastewater treatment plants. In this light, non-biological methods have been employed to treat antibiotics (and other pharmaceuticals too), such as advanced oxidation processes, membrane separation, adsorption, coagula- tion, as well as various combinations of them; two recent review articles ( Homem and Santos, 2011 ; Klavarioti et al., 2009 ) summarize the more representative studies in this fi eld. Amoxicillin (AMX) is a semi-synthetic b -lactam antibiotic used in human medicine to treat several diseases and in veterinary practice as growth promoter. As it is excreted by the body almost unmetabolized (e.g. excretion levels as much as 86 8% in human urine have been reported ( Garcia-Reiriz et al., 2007 )), AMX itself rather than a metabolite is likely to be found in environmental samples ( Morse and Jackson, 2004 ). AMX has been detected at the " id="pdf-obj-0-7" src="pdf-obj-0-7.jpg">

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Journal of Environmental Management

<a href=Journal of Environmental Management 98 (2012) 168 e 174 Contents lists available at S c i V e r s e S c i e n c e D i r e c t Journal of Environmental Management journal homepage: www.els evier.com/locate/jenvman Degradation, mineralization and antibiotic inactivation of amoxicillin by UV-A/TiO photocatalysis Despina Dimitrakopoulou , Irene Rethemiotaki , Zacharias Frontistis , Nikolaos P. Xekoukoulotakis , Danae Venieri , Dionissios Mantzavinos * Department of Environmental Engineering, Technical University of Crete, Polytechneioupolis, GR-73100 Chania, Greece School of Science and Technology, The Hellenic Open University, 18 Parodos Aristotelous St., GR-26335 Patras, Greece article info Article history: Received 18 July 2011 Received in revised form 19 December 2011 Accepted 8 January 2012 Available online 24 January 2012 Keywords: Activity Kinetics Pharmaceuticals Removal Semiconductor Water abstract The UV-A/TiO photocatalytic decomposition of amoxicillin (AMX) in aqueous suspensions was inves- tigated. Experiments were performed at antibiotic concentrations between 2.5 and 30 mg/L, eight commercially available TiO catalysts at loadings between 100 and 750 mg/L, acidic or near-neutral conditions (pH 5 or 7.5) and two different matrices (ultrapure water and secondary treated ef fl uent) at a photon fl ux of 8 10 E/(L min). Of the various catalysts tested, Degussa P25 was highly active, i.e. complete AMX degradation and 93% mineralization could be achieved after 25 and 90 min of reaction, respectively at 10 mg/L AMX and 250 mg/L titania. In general, mineralization was slower than degra- dation due to the formation of stable transformation by-products. For the range of concentrations studied, initial degradation rates can be approached by a Langmuir e Hinshelwood kinetic model, while the reaction order with respect to AMX shifts from fi rst to zeroth as initial concentration increases from 2.5 to 5 mg/L to higher values. Degradation in treated ef fl uent was partly impeded compared to pure water due to the inherent presence of organic and inorganic constituents that compete for hydroxyl radicals. Although increasing solution pH from 5 to 7.5 had no effect on degradation, it retarded mineralization. The antibiotic activity of AMX prior to and after photocatalytic degradation was tested to three reference bacterial strains, namely Escherichia coli (ATCC 23716), Klebsiella pneumoniae (NCTC 5056) and Enterococcus faecalis (ATCC 14506). The fi rst two were found to be highly resistant at AMX concentrations up to 25 mg/L, while the latter could partly be inactivated at lower AMX concentrations (i.e. 10 mg/L) and/or in the presence of photocatalytic by-products. 2012 Elsevier Ltd. All rights reserved. 1. Introduction Pharmaceuticals constitute an emerging class of micro- pollutants, whose occurrence in the environment is due to point sources, like production ef fl uents and waste disposal, as well as diffuse sources, like run-off from fi elds and anthropogenic ef fl uents ( Kümmerer, 2009a ). A variety of pharmaceuticals have been detected in many environmental samples worldwide including wastewater treatment plant ef fl uents, surface water, seawater, groundwater, soils and sediments and this is closely related to their bioresistant nature ( Fatta-Kassinos et al., 2010 ). Among the various pharmaceutical compounds, antibiotics have been paid particular attention because of their potential role in the development of antibiotic-resistant bacteria ( Homem and Santos, * Corresponding author. Tel.: þ 302821037797; fax: þ 302821035852. E-mail address: mantzavi@mred.tuc.gr (D. Mantzavinos). 0301-4797/$ e see front matter 2012 Elsevier Ltd. All rights reserved. doi: 10.1016/j.jenvman.2012.01.010 2011 ). Antibiotics are used extensively in human and veterinary medicine, as well as in aquaculture to prevent or treat microbial infections. Most antibiotics tested to date are known to be bio- recalcitrant under aerobic conditions ( Kümmerer, 2009b ), thus escaping intact from conventional wastewater treatment plants. In this light, non-biological methods have been employed to treat antibiotics (and other pharmaceuticals too), such as advanced oxidation processes, membrane separation, adsorption, coagula- tion, as well as various combinations of them; two recent review articles ( Homem and Santos, 2011 ; Klavarioti et al., 2009 ) summarize the more representative studies in this fi eld. Amoxicillin (AMX) is a semi-synthetic b -lactam antibiotic used in human medicine to treat several diseases and in veterinary practice as growth promoter. As it is excreted by the body almost unmetabolized (e.g. excretion levels as much as 86 8% in human urine have been reported ( Garcia-Reiriz et al., 2007 )), AMX itself rather than a metabolite is likely to be found in environmental samples ( Morse and Jackson, 2004 ). AMX has been detected at the " id="pdf-obj-0-38" src="pdf-obj-0-38.jpg">

Degradation, mineralization and antibiotic inactivation of amoxicillin by UV-A/TiO 2 photocatalysis

Despina Dimitrakopoulou a , Irene Rethemiotaki b , Zacharias Frontistis a , Nikolaos P. Xekoukoulotakis a , Danae Venieri a , Dionissios Mantzavinos a , *

a Department of Environmental Engineering, Technical University of Crete, Polytechneioupolis, GR-73100 Chania, Greece b School of Science and Technology, The Hellenic Open University, 18 Parodos Aristotelous St., GR-26335 Patras, Greece

article info

Article history:

Received 18 July 2011 Received in revised form 19 December 2011 Accepted 8 January 2012 Available online 24 January 2012

Keywords:

Activity

Kinetics

Pharmaceuticals

Removal

Semiconductor

Water

abstract

The UV-A/TiO 2 photocatalytic decomposition of amoxicillin (AMX) in aqueous suspensions was inves- tigated. Experiments were performed at antibiotic concentrations between 2.5 and 30 mg/L, eight commercially available TiO 2 catalysts at loadings between 100 and 750 mg/L, acidic or near-neutral conditions (pH 5 or 7.5) and two different matrices (ultrapure water and secondary treated efuent) at a photon ux of 8 10 4 E/(L min). Of the various catalysts tested, Degussa P25 was highly active, i.e. complete AMX degradation and 93% mineralization could be achieved after 25 and 90 min of reaction,

respectively at 10 mg/L AMX and 250 mg/L titania. In general, mineralization was slower than degra- dation due to the formation of stable transformation by-products. For the range of concentrations studied, initial degradation rates can be approached by a LangmuireHinshelwood kinetic model, while the reaction order with respect to AMX shifts from rst to zeroth as initial concentration increases from 2.5 to 5 mg/L to higher values. Degradation in treated efuent was partly impeded compared to pure water due to the inherent presence of organic and inorganic constituents that compete for hydroxyl radicals. Although increasing solution pH from 5 to 7.5 had no effect on degradation, it retarded mineralization. The antibiotic activity of AMX prior to and after photocatalytic degradation was tested to three reference bacterial strains, namely Escherichia coli (ATCC 23716), Klebsiella pneumoniae (NCTC 5056) and Enterococcus faecalis (ATCC 14506). The rst two were found to be highly resistant at AMX concentrations up to 25 mg/L, while the latter could partly be inactivated at lower AMX concentrations (i.e. 10 mg/L) and/or in the presence of photocatalytic by-products. 2012 Elsevier Ltd. All rights reserved.

1. Introduction

Pharmaceuticals constitute an emerging class of micro- pollutants, whose occurrence in the environment is due to point sources, like production efuents and waste disposal, as well as diffuse sources, like run-off from elds and anthropogenic efuents (Kümmerer, 2009a). A variety of pharmaceuticals have been detected in many environmental samples worldwide including wastewater treatment plant efuents, surface water, seawater, groundwater, soils and sediments and this is closely related to their bioresistant nature (Fatta-Kassinos et al., 2010). Among the various pharmaceutical compounds, antibiotics have been paid particular attention because of their potential role in the development of antibiotic-resistant bacteria (Homem and Santos,

* Corresponding author. Tel.: þ302821037797; fax: þ302821035852. E-mail address: mantzavi@mred.tuc.gr (D. Mantzavinos).

0301-4797/$ e see front matter 2012 Elsevier Ltd. All rights reserved.

2011). Antibiotics are used extensively in human and veterinary medicine, as well as in aquaculture to prevent or treat microbial infections. Most antibiotics tested to date are known to be bio- recalcitrant under aerobic conditions (Kümmerer, 2009b), thus escaping intact from conventional wastewater treatment plants. In this light, non-biological methods have been employed to treat antibiotics (and other pharmaceuticals too), such as advanced oxidation processes, membrane separation, adsorption, coagula- tion, as well as various combinations of them; two recent review articles (Homem and Santos, 2011; Klavarioti et al., 2009) summarize the more representative studies in this eld. Amoxicillin (AMX) is a semi-synthetic b-lactam antibiotic used in human medicine to treat several diseases and in veterinary practice as growth promoter. As it is excreted by the body almost unmetabolized (e.g. excretion levels as much as 86 8% in human urine have been reported (Garcia-Reiriz et al., 2007)), AMX itself rather than a metabolite is likely to be found in environmental samples (Morse and Jackson, 2004). AMX has been detected at the

D. Dimitrakopoulou et al. / Journal of Environmental Management 98 (2012) 168e174

169

mg/L level in environmental samples, like secondary treated efuents and surface water (Kasprzyk-Hordern et al., 2008; Schreiber and Szewzyk, 2008), while its presence in antibiotic manufacturing efuents may reach the mg/L level (Arslan-Alaton et al., 2004). Advanced oxidation processes to degrade AMX in water include ozonation ( Andreozzi et al., 2005 ), dark Fenton oxidation (Ay and Kargi, 2010 ), photo-Fenton oxidation (Mavronikola et al., 2009 ; Trovo et al., 2008 ) and semiconductor photocatalysis using undoped and doped titania samples under UV-A or solar irradia- tion ( Klauson et al., 2010 ). In other studies performed by a certain research group, the treatment of a synthetic antibiotic formulation wastewater cont aining amoxicillin, cloxacillin and ampicillin at a total concentration of about 300 mg/L was studied by means of UV-A/ZnO photocatalysis ( Elmolla and Chaudhuri, 2010a ), UV-A/TiO 2 photocatalysis ( Elmolla and Chaudhuri, 2010b) and Fenton oxidation with and without UV-A irradiation ( Elmolla and Chaudhuri, 2010c ). Since the literature concerning the heterogeneous photo- catalytic treatment of AMX in environmentally relevant systems and/or concentrations is scarce, we decided to study, in a system- atic way, the effect of various process parameters such as TiO 2 type and loading, initial antibiotic concentration, solution pH and the water matrix (i.e. ultrapure water and treated wastewater) on the kinetics of AMX degradation and mineralization, as well as on its antibiotic activity.

2. Materials and methods

2.1. Materials

AMX (C 16 H 19 N 3 O 5 S), whose structure is shown in Fig. 1, was purchased from Fluka (CAS 26787-78-0) and used as received. Most experiments were performed in ultrapure water taken from a water purication system (EASYpureRF-Barnstead/Thermolyne, USA); in an additional experiment, the secondary efuent of a municipal wastewater treatment plant was spiked with AMX to assess the effect of water matrix on degradation. Eight commercially available TiO 2 samples, whose main properties are summarized in Table 1, were employed for slurry photocatalytic experiments.

2.2. Experimental procedure

UV-A irradiation was provided by a 9 W lamp (Radium Ralutec, 9W/78) emitting predominantly at 350e 400 nm. The photon ux emitted from the lamp was determined actinometrically using

0.18 pK a2 =7.5 0.15 NH 2 H H N S 0.12 CH 3 O N
0.18
pK a2 =7.5
0.15
NH 2
H
H
N
S
0.12
CH
3
O
N
CH
HO
3
O
COOH
0.09
pK a3 =9.6
pK a1 =2.7
0.06
0.03
0
200
215
230
245
260
275
290
305
Absorbance, AU

Wavelength, nm

Fig. 1. The absorbance spectrum and molecular structure of AMX.

Table 1 TiO 2 catalysts used in this study. A: anatase; R: rutile.

Catalyst

Crystal

BET area, Particle

Supplier

form

m

2 /g

size, nm

Degussa P25

75%A:25%R 50

 

21

Degussa AG

Hombikat UV100

A > 99%

<250

5

Sachtleben Chemie

Millennium PC50

A > 97%

45e55

20e30

GmbH Millennium Inorganic

Millennium PC100

A > 95%

80e100

15e25

Chemicals Millennium Inorganic

Millennium PC105

A > 95%

75e95

15e25

Chemicals Millennium Inorganic

Millennium PC500

A > 75%

<300

5e10

Chemicals Millennium Inorganic Chemicals

Tronox AK1

A > 97%

90

20

Kerr McGee Chemicals

Aldrich Anatase AA A > 99%

190e290 15

Aldrich

the potassium ferrioxalate method and was found 8 10 4 E/ (L min). Experiments were conducted in an immersion well, batch type, laboratory scale photoreactor, purchased from Ace Glass (Vineland, NJ, USA) and described in detail elsewhere (Fotiadis et al., 2007). In a typical photocatalytic run, 0.35 L of the aqueous solution containing the desired concentration of AMX in the range 2.5e30 mg/L were loaded in the reaction vessel. These concentra- tions, although greater than those typically found in environmental samples, were chosen to allow (i) the assessment of process ef- ciency within a measurable time scale, and (ii) the accurate deter- mination of residual AMX and organic carbon with the analytical techniques employed in this work. The solution was slurried with the appropriate amount of catalyst and magnetically stirred for 30 min in the dark to ensure complete equilibration of adsorption/ desorption of AMX onto the TiO 2 surface. After that period, the UV- A lamp was turned on, while pure O 2 was continuously sparged in the reaction mixture under stirring. During photocatalytic experi- ments, temperature was maintained at 25 C with a temperature control unit. Most experiments were performed at inherent solu- tion pH which was left uncontrolled during the reaction; the inherent solution pH was about 5 (the exact value was dependent of AMX initial concentration and the type of catalyst) in experi- ments with ultrapure water and 7.5 in the experiment with the secondary efuent. For those runs with ultrapure water where the initial pH had to be adjusted to 7.5, this was done adding the appropriate amount of 0.5 N NaOH. All of the experiments were run in duplicate and mean values are quoted as results with the standard error not exceeding 5%. The only exception was the run in secondary efuent which was per- formed once.

2.3. Analytical techniques

Samples periodically taken from the reactor were centrifuged to

remove catalyst particles and then analyzed for (i) total organic

carbon (TOC) content on a Shimadzu 5050A TOC analyzer, whose

operation is based on the catalytic combustion/non-dispersive

infrared gas analysis, to assess the extent of mineralization that

had occurred, and (ii) residual AMX concentration. The latter

was followed by high performance liquid chromatography

(Waters 2690) equipped with a Luna C18 (2) column (5 mm,

4.6 mm 250 mm) and a security guard column (4 mm 3 mm)

both purchased from Phenomenex, and a diode array detector (Waters 996) set at 275 nm. The mobile phase consisted of 70% 0.025 M KH 2 PO 4 buffer solution in ultrapure water and 30% acetonitrile at a ow rate of 0.5 mL/min and inherent temperature.

  • 170 D. Dimitrakopoulou et al. / Journal of Environmental Management 98 (2012) 168e174

    • 2.4. Measurement of antibiotic activity

Antimicrobial susceptibility test was performed by determining the minimum inhibitory concentration (MIC) of AMX using Escherichia coli (ATCC 23716), Klebsiella pneumoniae (NCTC 5056) and Enterococcus faecalis (ATCC 14506) as reference strains. MICs were determined by the broth dilution method (microdilution), labeling 96-well sterile microtitre trays with the appropriate anti- biotic dilutions (Andrews, 2001; NCCLS, 2002). The range of the tested antibiotic concentrations was between 5 and 30 mg/L. Bacterial inocula were prepared using Mueller-Hinton broth (Merck) adjusted to 2 10 4 e10 5 CFU/mL, which is the appropriate inoculum size for standard MIC. Microtitre trays were incubated for 18e24 h at 37 C, followed by optical density measurement at 630 nm, using a microplate reader (Labtech LT-4000 Plate Reader). The same procedure was followed to test the antibiotic activity of the treated AMX.

3. Results and discussion

  • 3.1. Catalyst screening and activity

To assess the relative catalytic activity of various TiO 2 samples, preliminary experiments were conducted at 10 mg/L AMX initial concentration, 250 mg/L catalyst loading and inherent solution pH. Fig. 2 shows that Degussa P25 is highly active leading to complete

a 100 80 60 P25 UV100 AK1 PC50 PC100 PC105 40 PC500 AA No catalyst 20
a
100
80
60
P25
UV100
AK1
PC50
PC100
PC105
40
PC500
AA
No catalyst
20
0
0
15
30
45
60
75
90
Time, min
b
AMX reduction, %
100 P25 UV100 AK1 PC50 PC100 PC105 80 PC500 AA 60 40 20 0 0 15
100
P25
UV100
AK1
PC50
PC100
PC105
80
PC500
AA
60
40
20
0
0
15
30
45
60
75
90
TOC reduction, %

Time, min

Fig. 2. Relative activity of various TiO 2 samples (250 mg/L) for 10 mg/L AMX (a) degradation and (b) mineralization at inherent pH ¼ 5.

AMX disappearance after 25 min and over 90% mineralization after 90 min of reaction. To achieve similar AMX conversions with other TiO 2 samples, reaction times of at least 45 min are required, while mineralization does not exceed 75% after 90 min. It should be noted here that Degussa P25 is more active than the rest despite its lower surface area (although the relationship between surface area and photoactivity is debatable (Uyguner and Bekbolet, 2004)). The superiority of Degussa P25 is attributed (Emilio et al., 2006; Martin et al., 1994) to the slower electron/hole recombination taking place on the catalyst surface compared to other TiO 2 pho- tocatalysts; another explanation ascribes the higher activity of Degussa P25 to its structure which is a mixture of anatase and rutile; this mixture is more active than the individual pure crys- talline phases (Bickley et al., 1991). The results of Fig. 2 are not surprising since Degussa P25 has been reported to be an effective photocatalyst in numerous water/wastewater treatment applica- tions (Malato et al., 2009). According to the above ndings, all subsequent photocatalytic experiments were performed with Degussa P25 TiO 2 . To conrm that AMX degradation is due to the synergy between photonic energy and the catalyst surface rather than direct photolysis and/or photooxidation, an additional experiment was performed in the absence of catalyst leading to just 4% AMX conversion after 90 min (Fig. 2a); this is consistent with the fact that the absorbance spectrum of AMX (Fig. 1) fades out at about

  • 290 nm, i.e. well below the emission spectrum of the irradiation

source.

3.2. Effect of catalyst loading

The effect of catalyst loading on 10 mg/L AMX degradation

and mineralization was studied in the range 100 e750 mg/L and

inherent solution pH and the results are shown in Fig. 3 . As seen,

both AMX degradation and mineralization increase considerably

with increasing catalyst concentration from 100 to 250 mg/L

beyond which the effect is less pronounced. Nevertheless,

mineralization appears to be more sensitive to catalyst concen-

tration changes than AMX degradation. For instance, the 20 min-

TOC reduction is 43%, 60%, 65% and 70% at 100, 250, 500 and

  • 750 mg/L catalyst, respectively; on the other hand, the 20 min-

AMX conversion is 65% at 100 mg/L catalyst and complete at any

other concentration. This is so because mineralization comprises

a sequence of reactions involving the oxidation of AMX photo-

catalytic transformation by-products to CO 2 and water, which is more difcult to occur than the partial AMX oxidation. Elmolla and Chaudhuri (2010b) reported a 42% AMX conversion after

  • 300 min of UV-A irradiation at 500 mg/L pure anatase TiO 2 , which

increased to 57 2% at 1500 500 mg/L catalyst. Their ndings

are not directly comparable to ours since different experimental

conditions were employed including the type of catalyst (pure

anatase instead of Degussa P25), the photon ux (not explicitly

given), the composition and concentration of the solution

(mixture of AMX with two other antibiotics at 300 mg/L cumu-

lative concentration instead of 10 mg/L AMX) and the catalyst to

substrate concentration ratio (in the range 1.7 e6.7 in their work

and 10 e75 in ours).

The increase in photocatalytic activity with increasing catalyst

loading indicates a heterogeneous catalytic regime since the

fraction of incident light absorbed by the semiconductor

progressively increases in suspensions containing higher amounts

of TiO 2 (Abellan et al., 2009 ). The catalyst concentration above which conversion levels off depends on several factors (e.g. reactor geometry, substrate concentration, wavelength and intensity of light source) and corresponds to the point where all catalyst particles, i.e. all the surface exposed, are fully illuminated

D. Dimitrakopoulou et al. / Journal of Environmental Management 98 (2012) 168e174

171

a 100 80 60 40 100mg/L 250mg/L 20 500mg/L 750mg/L 0 0 15 30 45 60
a
100
80
60
40
100mg/L
250mg/L
20
500mg/L
750mg/L
0
0
15
30
45
60
75
90
Time, min
b
AMX reduction, %
100 80 60 40 100mg/L 250mg/L 20 500mg/L 750mg/L 0 0 15 30 45 60 75
100
80
60
40
100mg/L
250mg/L
20
500mg/L
750mg/L
0
0
15
30
45
60
75
90
TOC reduction, %

Time, min

Fig. 3. Effect of Degussa P25 loading on 10 mg/L AMX (a) degradation and (b) mineralization at inherent pH ¼ 5.

( Herrmann, 1999 ). At higher concentrations, a screening effect of excess particles may occur, thus masking part of the photosensi- tive surface and consequently hindering light penetration. At the conditions employed in this work, P25 TiO 2 in the range 250e750 mg/L appears to have no signicant effect on conversion, i.e. it can provide a sufcient amount of catalyst particles without impeding light penetration; therefore, all subsequent runs were performed at 500 mg/L catalyst.

3.3. Effect of AMX concentration

The effect of varying AMX initial concentration (C o ) was studied in the range 2.5e30 mg/L at 500 mg/L Degussa P25 loading and the results are shown in Fig. 4; regardless the initial concentration, complete degradation is always achieved in less than 45 min of reaction. Heterogeneous photocatalytic reactions can be described by a LangmuireHinshelwood (LeH) kinetic model, i.e.:

r o ¼ k r

KC eq

1

1

1

1

1 þ KC eq

r o

k r K

C

eq

k r

5

¼

þ

(1)

where r o is the initial reaction rate, C eq is the equilibrium concen- tration, K is the adsorption constant onto the catalyst surface and k r is the intrinsic reaction rate constant. Computing r o from the data of Fig. 4 for the rst 4 min of reaction and taking C eq z C o since the extent of dark adsorption is quite low (i.e. between 3.2% and 13.7%

30 2.5 2 25 1.5 20 1 0.5 15 0 0 0.1 0.2 0.3 0.4 10
30
2.5
2
25
1.5
20
1
0.5
15
0
0
0.1
0.2
0.3
0.4
10
1/C , L/mg
5
0
0
5
10
15
20
25
30
35
40
45
AMX concentration, mg/L
1/r , (L.min)/mg

Time, min

Fig. 4. Change of AMX concentration as a function of its initial concentration at

500 mg/L Degussa P25 and inherent pH ¼ 5. Inset graph: the LeH kinetic model for

AMX degradation.

for the lower and higher concentration, respectively), the experi-

mental data t the LeH model well (inset Fig. 4). From the intercept

and the slope of the resulting straight line, the values for k r and K

are 2.28 mg/(L min) and 0.09 L/mg, respectively.

The ability of semiconductor photocatalysis to oxidize organic

species is due to the valence band holes photogenerated onto the

titania surface, as well as the hydroxyl radicals produced from the

reaction of holes with surface-bound water and hydroxyl anions

(Turchi and Ollis, 1990). Hydroxyl radicals are considered as the

primary oxidizing agent acting not only on the surface but also in

the solution phase; in this respect, the LeH model (and the asso-

ciated kinetic constants) should be viewed cautiously since it may not take into account all possible photocatalytic mechanisms (Turchi and Ollis, 1989). When the extent of adsorption and/or substrate concentration is small, i.e. KC eq << 1, eqn. (1) is reduced to a rst-order kinetic expression as follows:

dC

dt

¼ k app C 5ln C o ¼ k app t 5ln 1 X ¼ k app t

C

(2)

where k app is an apparent rate constant and X is the conversion. Fig. 5 shows the data of Fig. 4 plotted in the form of eqn. (2), where k app values can be computed from the slopes of the resulting

3 2.5 2 1.5 30mg/L 1 20mg/L 10mg/L 0.5 5mg/L 2.5mg/L 0 0 5 10 15
3
2.5
2
1.5
30mg/L
1
20mg/L
10mg/L
0.5
5mg/L
2.5mg/L
0
0
5
10
15
20
25
30
Ln(C o /C)

Time, min

Fig. 5. Plot of eqn. (2) for the AMX concentrationetime proles of Fig. 4.

  • 172 D. Dimitrakopoulou et al. / Journal of Environmental Management 98 (2012) 168e174

straight lines. These values are given in Fig. 6 alongside AMX conversion after 4 min of reaction. (It should be noted that data tting to eqn. (2) was applied for AMX conversions up to 90% and the coefcient of linear regression (r 2 ) was always greater than 98.5%). The kinetics of AMX degradation in the range 2.5e5 mg/L are, indeed, rst order since the rate constant is independent of the initial concentration (and so is conversion). However, at higher concentrations both the rate constant and the conversion decrease, thus implying deviation from rst-order kinetics (although tting to eqn. (2) is still excellent). For example, if the reaction were zeroth order with respect to AMX concentration, conversion would decrease proportionately with increasing concentration, i.e.:

  • dC ¼ k app 5C o C ¼ k app t 5X ¼

dt

k app

  • C o

t

(3)

This is clearly demonstrated at the two higher concentrations, where a 50% increase (from 20 to 30 mg/L) results in an almost equal conversion decrease. For concentrations in the range 5e20 mg/L, the decrease in conversion is proportionately lower than the respective increase in concentration, thus implying kinetics between zeroth and rst order. This transition in kinetics can be explained as follows: the rate of photocatalytic formation of oxidizing species should be a function of the photon ux and the catalyst loading and, therefore, constant at xed operating conditions. In this respect, an increase in AMX concentration would increase the probability of hydroxyl radicals attack on AMX and, consequently, the reaction rate. This is partic- ularly true during the early stages of reaction when the concen- tration of competing transformation by-products is low. Fig. 7 shows their evolution depicted from the carbon balance between residual AMX and measured TOC. This increase is linear in the range 2.5e5 mg/L, e.g. r o is 0.41 and 0.81 mg/(L min) at 2.5 and 5 mg/L, respectively denoting rst-order kinetics. At higher concentrations, hydroxyl radicals become the limiting reactant and, consequently, lower order kinetics would occur. For the range of initial concen- trations examined, the photonic efciency, F, takes values between 0.14% and 0.57%. The efciency is computed as follows:

F ¼

r o V

I

100

(4)

where the initial reaction rate is expressed in M/min, I is the photon ux and V is the liquid volume. Klauson et al. (2010), who studied AMX degradation in the range 1e100 mg/L with 1000 mg/L Degussa P25 under UV-A radiation at 0.5 mW/cm 2 and pH ¼ 6, reported about 90% conversion after

172 D. Dimitrakopoulou et al. / Journal of Environmental Management 98 (2012) 168 e 174 straight

Fig. 6. Effect of initial AMX concentration on conversion (B) and the apparent rate constant (C) of eqn. (2) at 500 mg/L Degussa P25 and inherent pH ¼ 5.

7 6 5 4 3 30mg/L 2 20mg/L 5mg/L 1 2.5mg/L 0 0 5 10 15
7
6
5
4
3
30mg/L
2
20mg/L
5mg/L
1
2.5mg/L
0
0
5
10
15
20
25
30
35
40
45
Concentration of by-products, mg C/L

Time, min

Fig. 7. Accumulation of liquid-phase transformation by-products during AMX degra- dation at various initial concentrations, 500 mg/L Degussa P25 and inherent pH ¼ 5.

  • 360 min at 10 mg/L AMX concentration; this value consistently

decreased increasing AMX concentration and became about 30% at

  • 100 mg/L. This was explained considering a transition from the

kinetic control regime at lower concentrations to mass transfer limitations at higher concentrations. In the present study, complete conversion of 10 mg/L AMX was achieved after 25 min of reaction, i.e. an order of magnitude faster than that reported by Klauson et al. (2010); this may be due to a 10-fold greater irradiance employed in this study since other experimental conditions were comparable. Based on the kinetic analysis of this work, the photocatalytic degradation of AMX (and alike pharmaceuticals) in environmen- tally relevant matrices like surface water, groundwater, run-offs etc is likely to follow rst-order kinetics since its concentration will be several orders of magnitude lower than in this study; conversely, manufacturing efuents typically contain antibiotics at the mg/L level and, in this case, lower order kinetics may, indeed, apply.

3.4. Effects of initial solution pH and the water matrix

Fig. 8 shows the effect of initial pH in ultrapure water on 10 mg/L AMX degradation and mineralization. As clearly seen, increasing pH from acidic to near-neutral conditions has no effect on AMX degradation and this may be associated with the ionization states of both the substrate and the catalyst. As seen in Fig. 1, AMX has three pK a values at 2.7, 7.5 and 9.6 (Andreozzi et al., 2005). AMX is positively charged at pH ¼ 5 (Elmolla and Chaudhuri, 2010a) and so is the surface of Degussa P25, whose the point of zero charge is 6.7 (Fernandez-Ibanez et al., 2003). On the other hand, they are both negatively charged at near-neutral/slightly alkaline conditions. Therefore, neither pH appears to favor the electrostatic attraction between AMX and the catalyst surface (the degree of dark adsorption was measured 8 2% at either pH) and this may explain the nearly identical degradation rates. These results are in good agreement with those reported by Elmolla and Chaudhuri (2010b), who found that a pH change from 5 to 8 had practically no inuence on AMX degradation (e.g. the 300 min-conversion was 57 2%). Similarly, no striking differences were observed by Klauson et al. (2010) regarding the effect of pH in the range 6e9 on AMX degradation. On the other hand, mineralization is favored at acidic conditions with 93% TOC reduction occurring after 90 min, while the respec- tive value at pH ¼ 7.5 is only 75%. If certain transformation by- products were negatively charged at pH ¼ 5, their binding to the

D. Dimitrakopoulou et al. / Journal of Environmental Management 98 (2012) 168e174

173

100 80 60 40 AMX/pH=5 AMX/pH=7.5 TOC/pH=5 20 TOC/pH=7.5 AMX/pH=7.5 (SE) 0 0 15 30 45
100
80
60
40
AMX/pH=5
AMX/pH=7.5
TOC/pH=5
20
TOC/pH=7.5
AMX/pH=7.5 (SE)
0
0
15
30
45
60
75
90
AMX or TOC reduction, %
Growth inhibition, %

Time, min

40

 
40
40
 
40 30 20 10 0 0 5 10 15 20 25 30
40 30 20 10 0 0 5 10 15 20 25 30

30

30
30
30

20

 
20

10

 

0

0
0

0

5

10

15

20

25

30

AMX concentration, mg/L

Fig. 8. Effect of initial solution pH and water matrix on 10 mg/L AMX degradation and mineralization at 500 mg/L Degussa P25.

Fig. 9. Growth inhibition of E. faecalis as a function of (C) original AMX concen- tration in untreated solutions and (B) residual AMX concentration during oxidation of 30 mg/L AMX at 500 mg/L Degussa P25 and inherent pH ¼ 5.

catalyst surface would be enhanced and this could increase mineralization; nevertheless, this is speculative since identication of by-products was not possible with the analytical tools employed in this study. In addition, it is well known that TiO 2 particles tend to form agglomerates when dispersed in aqueous media, and such agglomeration strongly depends on parameters such as ionic strength and the pH of the suspension (French et al., 2009; Li et al., 2010). It has been reported (Li et al., 2010) that agglomeration of Degussa P25 particles in water decreases at acidic conditions compared to neutral conditions, thus increasing the effective surface area of the catalyst. This increase can also explain, in part, the increased photocatalytic mineralization observed at acidic conditions. If this is true, the fact that the transformation of AMX to by-products is not accelerated at acidic conditions may be explained by the fact that partial oxidation reactions are less difcult to happen than total oxidation (mineralization). To assess the role of water matrix, 10 mg/L AMX were spiked in secondary efuent (SE) and subject to photocatalytic treatment at inherent pH ¼ 7.5. As seen in Fig. 8, degradation in ultrapure water is considerably faster than in SE, i.e. to achieve complete AMX removal, the respective treatment times are 25 and 60 min. The SE inherently contains about 8 mg/L of organic matter (this is 1.3 times the organic carbon contained in 10 mg/L AMX) that would compete with AMX for hydroxyl radicals and other oxidizing species, thus reducing conversion. Furthermore, radical scavenging induced by the presence of about 180 mg/L bicarbonates and 220 mg/L chlo- rides in SE may also be responsible for decreased efciency. These results pinpoint the role of water matrix, which is likely to be more crucial in real applications considering that far lower AMX concentrations would typically exist in municipal wastewater inuents and discharges.

3.5. Antibiotic activity

Fig. 9 shows the antimicrobial activity of AMX against E. faecalis as a function of its concentration (lled symbols). Partial activity is developed in the range 10e30 mg/L AMX, with the extent of inactivation not exceeding 42% at the higher concentration tested. Similar tests with E. coli and K. pneumoniae revealed that both were resistant up to 25 mg/L AMX, while only at 30 mg/L was antimi- crobial activity partly developed, i.e. 52 1% inactivation (data not shown for brevity). MIC values obtained in this study are rather expected considering that all experiments have been conducted with bacterial reference strains. According to Andrews (2001) the

suggested ranges for MIC determinations regarding AMX are 0.25e128 mg/L for Enterobacteriaceae (E. coli and K. pneumoniae) and 0.12e128 mg/L for Enterococci (E. faecalis). However, these ranges may be different when dealing with environmental bacterial isolates, as they may develop resistance producing chromosomal beta-lactamases and inactivating the corresponding antibiotic compounds (Lateef et al., 2005). Fig. 9 also shows the effect of oxidation on the antimicrobial properties of 30 mg/L AMX, where activity is plotted against the residual, unreacted AMX concentration (open symbols) rather than the respective treatment time. It is evident that photocatalytic transformation by-products possess some activity to E. faecalis and this is more pronounced at <5 mg/L AMX concentrations, where activity seems to be exclusively due to by-products. The respective tests (not shown) with E. coli and K. pneumoniae resulted in complete removal of antibiotic activity as soon as the residual AMX concentration dropped below 25 mg/L (i.e. after 5 min); transformation by-products accumulating in the reaction mixture (i.e. 6.4 mg C/L after 30 min) appeared to have no antibiotic and/or toxic effect.

4. Conclusions

The conclusions drawn from the present study can be summa- rized as follows:

1) Semiconductor photocatalysis based on Degussa P25 TiO 2 and UV-A irradiation is an efcient method for the degradation of AMX in water. Nonetheless, mineralization is a slower process associated with the formation of persistent transformation by- products. Process performance is affected by several factors, namely irradiation time, photocatalyst type and loading, solu- tion pH and the water matrix. 2) The rate of AMX degradation depends on the substrate to oxidizing species concentration ratio. The order of reaction regarding the substrate is rst at low ratios and it decreases towards zeroth at higher ratios. This is consistent with the decreased conversions recorded in experiments with treated efuent compared to runs in pure water since reactive oxygen species are wasted in reactions with the efuent organic matter. 3) The antibiotic activity of AMX depends on its concentration and the test bacteria in question. In the case of E. coli and K. pneumoniae, inactivation is exclusively due to the presence of

  • 174 D. Dimitrakopoulou et al. / Journal of Environmental Management 98 (2012) 168e174

AMX at relatively high concentrations, i.e. over 25 mg/L, since below this value no antimicrobial activity occurs regardless the presence of transformation by-products in the reaction mixture. Conversely, E. faecalis is less resistant to AMX and it is also partially killed by its reaction by-products.

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