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Journal of Environmental Management 92 (2011) 2304e2347
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Journal of Environmental Management

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Review
Degradation and removal methods of antibiotics from aqueous

matrices e A review
Vera Homem, Lúcia Santos*
LEPÆ, Departamento de Engenharia Química, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
a r t i c l e i n f o a b s t r a c t
Article history: Over the past few years, antibiotics have been considered emerging pollutants due to their continuous
Received 1 November 2010 input and persistence in the aquatic ecosystem even at low concentrations. They have been detected
Received in revised form worldwide in environmental matrices, indicating their ineffective removal from water and wastewater
2 May 2011
using conventional treatment methods. To prevent this contamination, several processes to degrade/
Accepted 18 May 2011
Available online 16 June 2011
remove antibiotics have been studied. This review addresses the current state of knowledge concerning
the input sources, occurrence and mainly the degradation and removal processes applied to a specific
class of micropollutants, the antibiotics. In this paper, different remediation techniques were evaluated
Keywords:
Antibiotics
and compared, such as conventional techniques (biological processes, filtration, coagulation, flocculation
Emergent pollutants and sedimentation), advanced oxidation processes (AOPs), adsorption, membrane processes and
Degradation/removal processes combined methods. In this study, it was found that ozonation, Fenton/photo-Fenton and semiconductor
photocatalysis were the most tested methodologies. Combined processes seem to be the best solution for
the treatment of effluents containing antibiotics, especially those using renewable energy and by-
products materials.
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction Review articles about the input, occurrence and effects of anti-
biotics in the environment (Kemper, 2008; Kümmerer, 2009) and
The presence of pharmaceutical compounds, namely antibiotics, about the analytical methodologies for determination of these
in the ecosystem has been known for almost 30 years. However, it kinds of compounds in aqueous matrices (Petrovi c et al., 2005; Hao
was only in mid-1990s, when the use of these compounds was et al., 2007) have been recently published. To prevent environ-
widespread and new analytical technologies were developed, that mental matrices contamination, several processes to degrade/
their presence became an emerging concern (Lissemore et al., 2006; remove antibiotics have been studied. According to the authors’
Hernando et al., 2006; Bound and Voulvoulis, 2006). Residues of knowledge, four review articles on the oxidation technologies for
human and veterinary antibiotics were detected in a multiplicity of the removal of several pharmaceuticals were published (Ikehata
matrices (Ternes, 1998; Hirsch et al., 1999; Lindsey et al., 2001; et al., 2006; Esplugas et al., 2007; Sharma, 2008; Klavarioti et al.,
Sacher et al., 2001; Díaz-Cruz et al., 2003; Jacobsen et al., 2004; 2009), as well as a general review of antibiotics in the aquatic
Batt et al., 2006; Brown et al., 2006; Cha et al., 2006; Kim and environment, which refers possible disposal methodologies
Carlson, 2006; Díaz-Cruz and Barceló, 2007; Bailón-Pérez et al., (Kümmerer, 2009). However, the authors did not find a review
2008; Feitosa-Felizzola and Chiron, 2009; Minh et al., 2009; Mom- article concerning different types of methodologies to the antibi-
pelat et al., 2009). The introduction of these compounds into the otics removal. Therefore, the aim of this work is to review, evaluate
environmental through anthropogenic sources can constitute and compare different developed processes for the degradation and
a potential risk for aquatic and terrestrial organisms. Although removal of antibiotics in aqueous matrices.
present at vestigial levels, antibiotics may cause resistance in
bacterial populations, making them, in the near future, ineffective in
the treatment of several diseases (Schwartz et al., 2003, 2006; 2. Background
Baquero et al., 2008; Rosenblatt-Farrel, 2009; Martínez, 2009).
2.1. Antibiotics classification
* Corresponding author. Traditionally antibiotics are defined as chemical compounds

E-mail address: lsantos@fe.up.pt (L. Santos). that eradicate or inhibit the growth of other microorganisms
0301-4797/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2011.05.023
V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347 2305
Table 1
Principal classes of antibiotics.
Class Core structure
OH
HO NHCH 3
OH NH 2
H 2C O O
Consists of 2 or more amino sugars joined by HO OH H
a glycoside linkage to a hexose nucleus of HO N
Aminoglycosides HO O NH
the drug. The structure of these antibiotics is
R OH
derived from the these two molecules: H2N NH2 O
R H 3C HO
NH
HO
H 2N
R2 O R3 R4 NH
R5
Anthracyclines They are structurally glycosylated tetracyclines. R6
b-Lactams
R1 O OH R7
COOR2
They are structurally very similar to the penicillins, O
O N CH3
Carbapenems but the sulphur atom of the structure has been
CH3
replaced by a carbon atom.
R1 N
H
COOR2
They possess a cephem nucleus to which 2 side O R3
Cephalosporins chains are linked: one esterifies the carbamate O N
group (R1) and the other is linked to the nucleus (R3).
R1 N S
H
O
In these compounds, the b-lactam ring is alone and
NR5
Monobactams R1
not fused to another ring.
N R R R4
H 2 3
COOR2
O
Consists of a thiazolidine ring connected to a O N CH3
Penicillins
b-lactam ring, to which a side chain is attached. CH3
R1 N S
H
OR 1 R2
O O
R 3O R5
R4
O O O R6
They are composed for carbohydrate moieties H H
N N N
Glycopeptides (glycans) covalently attached to the N N N R7
O H H H
side chains of an amino acid. O NH O O
R 12
R 8O
R 11 R 13O O R 16
R R 14 OR 15
HO OR 9 10
They are heterocyclic compounds of 5 member R1

di-unsaturated ring structure with 2 nitrogen N
Imidazoles H3 C R2
atoms at nonadjacent positions. If R2]NO2
than it is a nitroimidazole compound. N
R3 CH3
CH3 O
R4
They are a small family of antibiotics that have N O SR4
Lincosamides N
carbohydrate-type structures. H
R1 HO OH (continued on next page)
OH
2306 V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347
Table 1 (continued ).
O
CH3
Macrolides They are highly substituted monocyclic lactone
with 1 or more saccharides glycosidically R1
CH3
attached to hydroxyl groups. The lactone rings H3C O CH3
are usually 12, 14 or 16-membered. O
R2 HC O O
CH3 CH3
HO N(CH3)2
HO CH 3
R1
O
R 1O O CH 3 OH H3C CH3
H 3C HO
R2 R3
H3C CH3 CH3
R 2O O H 2C CH 3 CH 3 OH
O O
H3C
CH 3 CH 2 O H3CH2C O O
O O
H 3C O
O O HO N(CH3)2
HO O CH 2CH 3
R 3O OH CH2R4
O
N(CH 3)2 R5O
H3C CH3
OH
H3C CH3
H3C OH
O
OH
H3CH2C O
They are characterized by multiple tetrahydrofuran
and tetrahydropyran rings connected by O
Polyethers aliphatic bridges, direct CeC linkages, or spiro linkages. Other
features include a free carboxyl function, many CH3
HOOC
lower alkyl groups, and a variety of functional oxygen groups. O H3C
O CH3
O CH
3
CH3
Polypeptides They are polymers formed from the linkage HO
of a-amino acids.
R5 O O
Their structure contains 2 fused rings with a R4
OH
Quinolones carboxylic acid and a ketone group.
If R4]F, then it is a fluoroquinolone compound. R3 N
R2 R1
O-
Quinoxaline Their structure contains a benzene ring
N+ R
derivative and a pyrazine derivative ring.
N+
O-
O O
S R
They are characterized by sulfonyl group connected N 1
Sulfonamides H
to an amine group. H
N
R2
H3C CH3
R1R R3 R4 N
2
These antibiotics contain an octrahydronaphtacene OH
Tetracyclines
ring skeleton, consisting of 4 fused rings.
CONHR5
Other antibiotics OH
OH O OH O
OH Cl
It contains a nitrobenzene moiety connected to H
N
Chloramphenicol a propanol group as well as an amino group O2N Cl
binding a derivative of dichloroacetic acid.
O
HO
O
NH2
They have a unique chemical structure, in O O
which 3 different functional groups e aziridine,
Mitomycins R1 R2
carbamate and quinone e are arranged around
a pyrro[1,2-a]indole nucleus.
H3C N R3
O
NH2
OCH3
It is a diaminopyrimidine, a structural analogue N
Trimethoprim
of the pteridine moiety of folic acid.
H2N N OCH3
OCH3
(Marzo and Bo, 1998). However, the term “antibiotic” has been environment through excretion (urine and faeces), entering in the
expanded for antibacterial, antiviral, antifungal and antitumour sewer network and reaching the wastewater treatment plants
compounds. Most of these substances have a microbial origin, but (WWTPs). Most of WWTPs are not designed to remove highly polar
they may be also semi-synthetic or totally synthetic. Antibiotics can micropollutants like antibiotics (Xu et al., 2007). Therefore, they can
be divided into several classes, according to different criteria: be transported to surface waters and reach groundwater after
spectrum, mechanism of action or chemical structure. In Table 1 are leaching. Ultimately, the contaminated surface waters can enter in
presented the principal classes of antibiotics, according to their the drinking water treatment plants (DWTPs), which are also not
chemical structure (Marzo and Bo, 1998; Bannister, 2000; Lindner prepared to remove these compounds, reaching the water distri-
et al., 2000; McGregor, 2000; Ponsford, 2000; Roberts, 2000; bution systems. The sludge produced in WWTPs is applied in the
Southgate and Osborne, 2000; Cavalleri and Parenti, 2001; Kirst, soil fertilization and may cause the same problems as the use of
2001; Mor, 2001; Kadow et al., 2002; Brimble, 2003; Weidner- manure, as explained above. Another important contamination
Wells and Macielag, 2003; Sum, 2004; Ohno et al., 2010). This source is the direct release of veterinary antibiotics through the
classification will be used later in the efficiency comparison of the application in aquaculture. Improper disposal of unused/expired
removal/degradation methodologies. drugs, which are directly discharged in the sewage network or
deposited in landfills, waste effluents from manufacture or acci-
dental spills during manufacturing or distribution can also be
2.2. Sources of antibiotics in the environment considered as significant points of contamination (Mompelat et al.,
2009; Díaz-Cruz et al., 2003).
In these last years, the use of antibiotics in veterinary and
human medicine was widespread (annual consumption of 100
000e200 000 tons) and consequently, the possibility of water 2.3. Occurrence in the environment
contamination with such compounds increased (Xu et al., 2007). As
mentioned above, human and veterinary antibiotics have been In the last years, the presence of antibiotics in environmental
detected in different matrices. These pollutants are continually matrices has been investigated. Actually, the first reported case of
discharged into the natural environment as parent compounds, water contamination (surface water) by antibiotics was in England
metabolites/degradation products or both forms by a diversity of in 1982, when Watts et al. detected macrolides, tetracyclines and
input sources as shown in Fig. 1. sulphonamides in a river at concentrations of 1 mg/L (Sarmah et al.,
When dispersed in the fields as fertilizer, manure can contam- 2006). After this case, several studies about the occurrence of
inate soil and consequently surface and groundwater through run- antibiotic residues in aquatic ecosystems have been reported:
off or leaching (Kemper, 2008; Farré et al., 2008; Díaz-Cruz et al., surface waters (Constanzo et al., 2005; Ferdig et al., 2005; Brown
2003). Similarly, human antibiotics are introduced into the et al., 2006; Cha et al., 2006; Kim and Carlson, 2006; Xu et al.,
Fig. 1. Origin and principal contamination routes of human and veterinary antibiotics.
2007; Smith et al., 2007; Tamtam et al., 2008; Feitosa-Felizzola and in treating pathologies and imbalance of microbial ecosystems
Chiron, 2009; Watkinson et al., 2009), groundwaters (Sacher et al., (Bailón-Pérez et al., 2008).
2001; Batt et al., 2006; Xu et al., 2007), sea waters (Xu et al., 2007; So far, legal limits have been established for antibiotics in food
Minh et al., 2009), drinking water (Watkinson et al., 2009; Yiruhan (4e1500 mg/kg for milk and 25e6000 mg/kg for the other food stuffs
et al., 2010), WWTPs effluents (McArdell et al., 2003; Ferdig et al., of animal origin (European Union, 1990)), but there is no legislation
2005; Brown et al., 2006; Cha et al., 2006; Seifrtová et al., 2008; applied to environmental matrices.
Watkinson et al., 2009; Minh et al., 2009) and hospital wastewa-
ters (Kümmerer, 2001; Lindberg et al., 2004; Ferdig et al., 2005; 3. Remediation processes e an overview
Brown et al., 2006; Batt et al., 2007; Seifrtová et al., 2008;
Watkinson et al., 2009). Antibiotics have also been detected in As mentioned above, most conventional WWTPs or DWTPs are
terrestrial matrices and biosolids (Jacobsen et al., 2004; Ferdig et al., not designed for the treatment of wastewaters containing highly
2005; Pei et al., 2006; Kim and Carlson, 2006; Kinney et al., 2006; polar contaminants (Xu et al., 2007). Therefore, practical and
Jones-Lepp and Stevens, 2007; Feitosa-Felizzola and Chiron, 2009). economical solutions must be achieved in order to reduce the daily
Usually, antibiotics are detected in the higher mg/L range in amounts of antibiotics discharged into the environment.
hospital effluents, lower mg/L range in municipal wastewater and A wide range of chemical and physical methodologies for
ng/L in surface, sea and groundwater. Moreover, it has been verified organic compounds removal can be employed, for example,
that sediments from agriculture-influenced rivers have higher chemical oxidation and biodegradation (destructive methods),
antibiotic concentrations than the overlying water matrix or than adsorption, liquid extraction and membrane techniques (non-
other sediments from rivers located far from agricultural areas. This destructive processes). Depending on the pollutant concentration
indicates the possibility of run-off contamination from farmland in the effluent and the cost of the process, different methods can be
(Kümmerer, 2009). chosen.
Soil analyses have also revealed the presence of measurable An overview of the works published in international journals
antibiotic residues in this matrix for several months, following the between 2000 and 2010 in this area is presented in Table 2.
application of manure or sludge as fertilizers. Positive findings of
these residues have also been reported in vegetables and cereals 3.1. Conventional treatments
such as carrots, lettuces, green onions, cabbages, cucumbers and
corn (Migliore et al., 2003; Kumar et al., 2005; Boxall et al., 2006; The biological processes, filtration and coagulation/flocculation/
Grote et al., 2007; Dolliver et al., 2007; Shenker et al., 2011). sedimentation are the most used in conventional wastewater
The accumulation and persistence of antibiotics in the envi- treatment plants (Adams et al., 2002; Göbel et al., 2007;
ronment can produce harmful effects, either in aquatic or terres- Stackelberg et al., 2007; Vieno et al., 2007; Arikan, 2008).
trial ecosystems, even in the low concentrations levels, in which In the biological systems, activated sludge technology is widely
they are detected (ng/L to mg/L for water matrices and low- used, especially in industrial effluent treatments. The method
medium mg/kg for sediments). The extensive and indiscriminate consists of the organic compounds degradation in activated sludge
use of these compounds in human and veterinary medicine and tanks, with aerobic or anaerobic systems, by monitoring continu-
their continual introduction into the environmental matrices may ously temperature and the chemical oxygen demand (COD). The
explain such bioaccumulation and pseudo-persistence. The highly high toxicity of many contaminants prevents the application of this
polarity and non-volatile nature of most antibiotics prevent their process in effluents with high pollutants concentration, since they
escape from these matrices (Hernando et al., 2006). The physico- are recalcitrant and toxic to the microorganisms (Britto and Rangel,
chemical properties of each antibiotic (e.g., molecular structure, 2008). However, this methodology can be applied to large effluent
size and shape, solubility and hydrophobicity) will define their flow rates. (Eckenfelder, 2000).
distribution in the environmental matrices (solids or water) The filtration is the removal of the solids, specially suspended
(Kemper, 2008). In addition to these facts, they are suspected to be matter, by passing the wastewater through a granular media (sand,
responsible for the production of resistant microorganisms, coal, diatomaceous earth, granular activated carbon). Particles may
causing serious problems of public health, namely difficulties be removed by interstitial straining, but smaller particles must be
Table 2
Summary of the removal/degradation processes applied in treatment of environmental matrices contaminated with antibiotics.
Antibiotic Concentration Matrix Treatment Operating conditions Analytical methods Results and comments References
1. Aminoglycosides
Spectinomycin 1 mM Distilled water Ozonation 0.06e0.10 mM O3 Absorbance at 260 nm - 2nd order reaction rates Qiang
pH ¼ 2e9 increased with et al. (2004)
increasing pH.
- Fast degradation around
neutral pH.
- In 10 s, a total
degradation was
achieved.
2. Anthracyclines
Epirubicin 17.9 mg/L Distilled water Electrochemical Two Pt/Ir electrodes HPLC-UV, microbiological - Electrolysis main Hirose
oxidation NaCl as electrolyte assay with S. aureus, degraded epirubicin and et al. (2005)
V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

100 mA current cytoxicity and mutagenic eliminated its cytotoxicity,
assays mutagenicity and
microbiological activity
after 360 min.
3. b-Lactams
Amoxicillin 5.0 104 M Deionised water Ozonation 1.6 104 M O3 TOC, HPLC-DAD - 90% removal after 4 min Andreozzi
pH ¼ 2.5e7.2 and 18% mineralisation et al. (2005)
after 20 min.
- Low degree of mineralisation,
even for long treatment times.
Amoxicillin COD ¼ 80 103 mg/L Industry plant Combination of Fenton: BOD5, COD, TOC - After liquideliquid extraction Zhang
TOC ¼ 18,925 mg/L wastewater Fenton oxidation 10 g/L H2O2 with dichloromethane to et al. (2006)
with two-stage 0.74 g/L Fe2þ remove solvents and other
reverse osmosis organic compounds, the TOC
Reverse osmosis:
and COD removal efficiency
Polyamide membr
were around 50%.
ane cells
- Fenton oxidation improves
Area ¼ 155 cm2
the degradation of organic
compounds before the
two-stage reverse osmosis
system (TOC removal of 38%).
- After reverse osmosis 11% TOC
removal was achieved and
biodegradability was enhanced
(COD:BOD5 ¼ 4:1).
- After the combined treatment
the overall TOC removal
efficiency was 99.7%.
Amoxicillin 42 mg/L Spiked STP Photo-Fenton Black light at 365 nm TOC, DOC, HPLC-DAD - Amoxicillin degradation was Trovó
effluent and solar irradiation not influenced by the type of et al. (2008)
1.0e2.0 mM H2O2 irradiation or by the matrix.
0.20 mM ferrioxalate Its degradation was enhanced
or Fe(NO3)3 in the presence of ferrioxalate.
pH ¼ 2.5 - The increase of the H2O2
concentration improved the
efficiency of oxidation.
- After 10 min of irradiation
a total degradation was
achieved.
(continued on next page)
2309
2310
Amoxicillin 500 mg/L Simulated Photo-Fenton UV light (6 W) HPLC-DAD, COD, - The maximum Elmolla and
COD ¼ 790 mg/L wastewater at 365 nm BOD5, DO biodegradability ratio Chaudhuri
H2O2/Fe2þ molar (>0.40) was achieved at (2009)
ratio ¼ 10e100 H2O2/COD molar ratio ¼ 2,
pH ¼ 2e4 H2O2/Fe2þ molar ratio ¼ 50 and
pH ¼ 3e3.5, after 30e45 min
of reaction. Under these
conditions, complete degradation
was achieved in 1 min
(TOC removal ¼ 71%).
- The study indicated that
photo-Fenton can be used as
a pre-treatment for improvement
of amoxicillin biodegradability.

Amoxicillin 300 mg/L Distilled water Adsorption on pH ¼ 2e7 UV at 230 nm - The amoxicillin solution in Putra
Wastewater activated carbon and 0.1e3.5 g adsorbent distilled water was used to et al. (2009)
bentonite T ¼ 30 C model the adsorption process.
- Both Langmuir and Freundlich
models well fit the data.
- The kinetic were fitted
by pseudo 2nd order model.
- In real wastewater matrices,
both activated carbon (95%)
and bentonite (88%) have
high removal efficiencies.
Amoxicillin 1e100 mg/L Distilled water Semiconductor pH ¼ 3e9 COD - Amoxicillin degradation Klauson
photocatalysis LP UV at 365 nm under solar radiation et al. (2010)
and solar radiation proceeded about 3 times
0.1e0.7 g/L TiO2 or faster than under artificial UV.
TiO2 doped with - The maximum photocatalytic
C and Fe degradation was achieved in
neutral pH with 37% C
doped catalyst (85% removal).
- By-products determined
by LCeMS.
Amoxicillin 20 mg/L Distilled water Removal using ZVI or Fe LCeMS - Kinetic studies demonstrated Ghauch
Ampicillin metallic iron (metallic iron) that this process followed et al. (2009)
0.5e2 g/L iron 1st order decay.
- Antibiotics removal was
attributed to the rupture
of the b-lactam ring,
adsorption onto iron
corrosion products and
co-precipitation with iron
corrosion products.
- Complete removal after
3 h of contact with ZVI.
- By-products determined
by LCeMS.
Amoxicillin 104 mg/L Distilled water Fenton pH ¼ 2e4 HPLC-DAD, COD, - Under the optimal Elmolla and
Ampicillin 105 mg/L H2O2/COD molar BOD5, TOC, DOC conditions (H2O2/Fe2þ Chaudhuri
Cloxacillin 103 mg/L ratio ¼ 1.0e3.5 molar ratio ¼ 10, pH ¼ 3) it (2009)
H2O2/Fe2þ molar was achieved the complete
ratio ¼ 2e150 degradation of the
antibiotics in 2 min.
- The biodegradability was
improved from 0 to 0.37
in 10 min and COD and DOC
degradation were 81.4%
and 54.3%, respectively
in 60 min.
- Fenton process was effective
in the treatment of solutions
containing these antibiotics.
Amoxicillin 104 mg/L Distilled water Photo-Fenton pH ¼ 2e4 HPLC-DAD, COD, - Under the optimal conditions Elmolla and
Ampicillin 105 mg/L H2O2/COD molar BOD5, TOC, DO (H2O2/COD ¼ 1.5, H2O2/Fe2þ Chaudhuri

Cloxacillin 103 mg/L ratio ¼ 1.0e2.5 molar ratio ¼ 20, pH ¼ 3) it (2009)
H2O2/Fe2þ molar was achieved that the
ratio ¼ 10e150 complete degradation of
UV light (6 W) the antibiotics in 2 min.
at 365 nm - The biodegradability was
improved from 0 to 0.4
and COD and DOC
degradation were 80.8%
and 58.4%, respectively
in 50 min.
- Mineralisation of organic
carbon occurred.
Amoxicillin 104 mg/L Distilled water Semiconductor UV light (6 W) at 365 nm HPLC-DAD, COD, - The optimal conditions for Elmolla and
Ampicillin 105 mg/L photocatalysis 0.2e2.0 g/L ZnO BOD5, TOC, DO complete degradation of Chaudhuri
Cloxacillin 103 mg/L pH ¼ 5e11 antibiotics were 0.5 g/L (2010)
ZnO, irradiation time
180 min and pH ¼ 11.
- Under these conditions,
complete degradation
occurred and COD and
DOC removal were 23.9
and 9.7%, respectively.
Amoxicillin 104 mg/L Distilled water Semiconductor UV light (6 W) at 365 nm HPLC-DAD, COD, - No significant degradation Elmolla and
Ampicillin 105 mg/L photocatalysis 0.5e2.0 g/L TiO2 BOD5, TOC, DO occurred by 300 min Chaudhuri
Cloxacillin 103 mg/L 50e300 mg/L H2O2 of UV irradiation. (2010)
pH ¼ 3e11 - At pH ¼ 5 and 1.0 g/L
TiO2, 50% degradation
was achieved for all
compounds (81%
DOC removal).
- Addition of 100 mg/L
H2O2 at pH ¼ 5 and
1.0 g/L TiO2 resulted in
complete degradation
after 30 min and 40%
mineralisation after 24 h.
2311
2312
Amoxicillin 1.60 mg/L Distilled water Chlorination ClO2/antibiotic molar HPLCeMS - ClO2 reacts with penicillin, Navalon
Cefadroxil 1.89 mg/L ratio ¼ 0.25e2.00 amoxicillin and cefadroxil. et al. (2008)
Penicillin 25 mg/L - It is possible to achieve total
degradation of penicillin
after 2 h of reaction
(ClO2/penicillin > 1.00)
and amoxicillin and cefadroxil
after 1 min of reaction
(ClO2/antibiotic > 1.50).
- It was detected degradation
metabolites.
Ampicillin 20 mg/L Distilled water Fenton pH ¼ 2.3e5.7 HPLC-UV, TOC, COD - Under the optimized Rozas
Photo-Fenton 230e570 mM H2O2 conditions (pH ¼ 3.7, 87 et al. (2010)
53e87 mM Fe2þ mM Fe2þ, 373 mM H2O2

UV light (20 W) for Fenton and pH ¼ 3.5, 87
at 365 nm mM Fe2þ, 454 mM H2O2 for
photo-Fenton) a complete
degradation was reached.
- It was achieved a higher
mineralisation (50% TOC
removal) with photo-Fenton
than Fenton (20% TOC
removal).
- The degradation products
not present in antibacterial
activity.
Ceftriaxone COD ¼ 250e1400 Formulation Ozonation 3 g/(h L) O3 BOD5, COD, TOC, - COD removal was increased Balciog
lu
mg/L wastewater pH ¼ 3e11 Absorbance with increasing pH from and Ötker
0e100 mM H2O2 at 254 nm 3 to 7. The addition of H2O2 (2003)
had no advantage for COD
removal kinetics over the
direct ozonation.
- Biodegradability represented
in terms of BOD5/COD
was increased.
- After 60 min, 95% degradation
was achieved (45%
TOC removal).
Penicillin COD ¼ 830 mg/L Formulation Ozonation Ozonation: BOD5, COD, - Degradation increased with Arslan-Alaton
effluent 2500 mg/(L h) O3 absorbance at the increase of pH and in et al. (2004)
pH ¼ 2.5e12.0 344 and 274 nm the presence of H2O2
up to 20 mM.
Perozonation:
- Removal efficiencies varied
2500 mg/(L h) O3
between 10 and 56% for
pH ¼ 10.5
ozonation and 30 and
2e40 mM H2O2
83% for perozonation.
- Both processes followed
1st order kinetics with
respect to COD
removal rates.
- Biodegradability ratio,
BOD5/COD, increased by a
factor of 6 and 23 for
ozonation and perozonation,
respectively for 20 min.

- Treated effluent was
subjected to biological
activated sludge treatment.
Biological COD removal
rates and efficiencies were
appreciably improved, in
particular with perozonation.
Penicillin COD ¼ 1555 mg/L Formulation Ozonation Ozonation: BOD5, COD, TOC, - Ozonation was pH-dependent Arslan-Alaton
effluent Direct and indirect 2760 mg/(L h) O3 HPLC-DAD and the highest COD and and Dogruel
photolysis pH ¼ 3e11.5 TOC removals occurred in (2004)
Fenton and alkaline conditions
Photolysis:
Fenton-like (after 60 min of treatment,
LP UV at 254 nm
Photo-Fenton and the maximum COD
pH ¼ 7
photo-Fenton-like removal was 49%).
0e40 mM H2O2
- Photolysis proved to be a
Photo- and less effective method.
Fenton: - Comparison between
LP UV at 254 nm Fenton and Fenton-like
pH ¼ 3 processes.
20 mM H2O2 - Relatively higher COD
1 mM Fe2þ or Fe3þ and TOC removal rates
were obtained with Fe2þ/H2O2
when compared with Fe3þ/H2O2
(61% and 46% COD removal,
respectively).
- The presence of UV light only
slightly improved the treatment
performance.
- Poor improvement of
biodegradability.
Penicillin COD ¼ 710 mg/L Formulation Ozonation 2760 mg/(L h) O3 BOD5, COD, TOC, - Degradation increased with Cokgor
effluent pH ¼ 3e11 respirometric the increase of pH (6% at et al. (2004)
experiments pH ¼ 3 to 34% at pH ¼ 11).
- Biodegradability ratio,
BOD5/COD, increased upon
ozonation for 40 min.
TOC abatement remained low.
- Biological treatability
studies shown the poor
biodegradability of this effluent.
2313
2314
Penicillin COD ¼ 49,913 Pharmaceutical Microwave Microwave BOD5, COD, TOC, - Operating parameters were Yang
mg/L wastewater enhanced power ¼ 100e500 W HPLC-UV, absorbance investigated and the optimal et al. (2009)
Fenton-like pH ¼ 1e11 at 254 nm condition were: microwave
Radiation power 300 W, radiation
time ¼ 2e10 min time 6 min, initial pH 4.42,
3200e19,000 H2O2 dosage 1300 mg/L
mg/L H2O2 and Fe2(SO4)3 4900 mg/L.
2000e8000 - Within the present conditions,
mg/L Fe2(SO4)3 the COD removal was 57.53%,
TOC removal >40%, 55.06%
degradation.
- Microwave enhanced
Fenton-like reaction had
superior treatment efficiency.

Penicillin G COD ¼ 600 mg/L Formulation Photo-Fenton-like Black light (125 W) BOD5, COD, TOC - In optimal conditions (1.5 mM Arslan-Alaton
effluent Fenton-like 5e40 mM H2O2 Fe3þ, 25 mM H2O2), it was and Gurses
0.1e5 mM Fe3þ obtained 56% COD and 42% (2004)
pH ¼ 3 TOC removal after 30 min
for photo-Fenton-like
and 44% COD and 35% TOC
removal for Fenton-like.
- Both processes followed
1st order kinetics with
respect to COD removal rates.
- Photo-Fenton-like process
over dark-Fenton-like was
more effective in terms
of their effect on
biodegradability
improvement.
Penicillin G COD ¼ 200e600 Formulation Ozonation 600e2600 COD, TOC - Ozonation followed 1st Arslan-Alaton
mg/L effluent mg/L O3 order kinetics. and Coglayan
pH ¼ 3e12 - COD removal was increased (2005)
with increasing pH and ozone
dose and with the decrease
of initial COD value.
- At pH ¼ 7, 1800 mg/L O3
and after 1 h, a TOC removal
of 36% and a COD removal
of 37% were achieved.
Penicillin G COD ¼ 600 mg/L Formulation Ozonation Ozonation: BOD5, COD, toxicity - COD removal was increased Arslan-Alaton
effluent 1800 mg/(h L) O3 to D. magna, with increasing pH and in and Coglayan
pH ¼ 7e12 activated sludge the presence of H2O2. (2006)
inhibition test - Biodegradability was
Perozonation:
improved by perozonation
1800 mg/(h L) O3
at pH ¼ 7, but this
pH ¼ 7e12
pre-treatment did not
10 mM H2O2
completely remove the
ecotoxicity, leading to
serious inhibition the
treatment of activated
sludge.
- The COD removal efficiency
increased from 37% after
1 h at pH ¼ 7 for ozonation
to 76% to perozonation.
Penicillin V COD ¼ 250e1400 mg/L Formulation Ozonation Ozonation: BOD5, COD, TOC, - COD removal was increased Balciog
lu
wastewater 3 g/(h L) O3 Absorbance at 254 nm with increasing pH from and Ötker
pH ¼ 3e11 3 to 7. The addition of H2O2 (2003)
had no advantage for COD
Perozonation:
removal kinetics over the
3 g/(h L) O3
direct ozonation.
pH ¼ 7
0e100 mM H2O2
in terms of BOD5/COD was
increased.
- After 60 min, 40% degradation
was achieved (40%
TOC removal).
4. Glicopeptides
Bleomycin 44.6 mg/L Distilled water Electrochemical Two Pt/Ir electrodes HPLC-UV, - Electrolysis slightly degraded Hirose
oxidation NaCl as electrolyte microbiological and eliminated cytotoxicity, et al. (2005)
100 mA current assay with S. aureus, mutagenicity and

cytoxicity and microbiological activity of
mutagenic assays this antibiotic.
5. Imidazoles
Dimetridazole 10e30 mg/L Distilled water, Simultaneous pH ¼ 2e9 HPLC-DAD, TOC, - The ozonation degradations Sánches-Polo
Metronidazole natural waters application 0.25e0.50 g/L Toxicity tests were higher than 90% and et al. (2008)
Ronidazole and wastewater of ozonation and activated carbon with V. fischeri 10e20% of TOC removal.
Tinidazole adsorption - Ozonation generates highly
toxic oxidation by-products.
- The presence of activated
carbon during the
ozonation produces an
increase in the removal
rate, a reduction in the
toxicity of oxidation
by-products and a
reduction of around
30% in the TOC.
Dimetridazole 100e600 mg/L Distilled water, Adsorption/ T ¼ 25 C Absorbance - The pH of the medium Rivera-Utrilla
Metronidazole natural bioadsorption pH ¼ 2e11 at 320 nm and the electrolyte et al. (2009)
Ronidazole waters and on activated 0e0.1 M NaCl concentration did not
Tinidazole wastewater carbon 1 g/L activated carbon influence the adsorption
removal.
- Antibiotics were not
degraded by the
microorganisms used
in the biological treatment.
- The presence of these
microorganisms during
the adsorption increases
their adsorption/
bioadsorption on the
activated carbon.
Dimetridazole 150 mg/L Distilled water Adsorption on T ¼ 25 C Absorbance at - 90% removal was achieved Méndez-Díaz
Metronidazole activated carbons 0.2e1 g/L activated 320, 308 and 317 nm with 1 g/L of activated et al. (2010)
Ronidazole carbon carbon.
Tinidazole pH ¼ 7 - 2nd order kinetic fits
suitably the
experimental data.
2315
2316
Levamisole 10 mg/L Pharmaceutical Reverse osmosis Reverse osmosis: HPLC-DAD - The removal of the antibiotic Kosutic
wastewater Nanofiltration XLE and HR95PP by reverse osmosis and the et al. (2007)
membranes tight nanofiltration
membrane is acceptably high
Nanofiltration:
(rejection factors > 0.9).
NF90 and HL
Desal membranes
Metronidazole 1 mg/L Deionised water Direct and indirect Photolysis: HPLC-PDAD, absorbance - photo-degradation exhibited Shemer
photolysis LP UV at 254 nm at 220e230 nm pseudo 1st order kinetics. et al. (2006)
Fenton MP UV at - MP irradiation was more
Photo-Fenton 200e400 nm effective than LP.
pH ¼ 6 - Direct photolysis (6e12%
0e50 mg/L removal) was less effective
H2O2 than UV/H2O2 oxidation
(58e67% removal).

Photo- and Fenton:
- Fenton oxidation followed
LP UV at 254 nm
2nd order kinetics and the
pH ¼ 3.5
rate was increased with
29.4 mM H2O2
high Fe2þ concentrations.
2.94e11.76
- An increase in the removal
mM Fe2þ
efficiency and in the reaction
rate occurred when
photo-Fenton (74e94%
removal) is compared to
Fenton oxidation (53e76%
removal).
6. Lincosamides
Lincomycin 1 mM Distilled water Ozonation 0.06e0.10 mM O3 Absorbance - 2nd order reaction rates Qiang
pH ¼ 2e9 at 260 nm increased with increasing pH. et al. (2004)
- Total degradation was
achieved after 1 s.
- Fast degradation around
neutral pH.
Lincomycin 10e75 mM Distilled water Semiconductor TiO2 catalyst TOC, HPLC-UV - The photo-oxidation Augugliaro
photocatalysis 0.2 g/L catalyst followed 1st order kinetics. et al. (2005)
coupled with Membrane - Lincomycin was successfully
nanofiltration DL2540C and oxidized by photocatalysis.
DK2540C - Filtration allowed the
separation of the
photocatalyst particles from
lincomycin and its
degradation products from
permeate.
Lincomycin 10e50 mg/L Distilled water Semiconductor MP UV (125 W) HPLC-UV, TOC, - Degradation followed Addamo
photocatalysis pH ¼ 6.0 Absorbance at pseudo 1st order kinetic rate. et al. (2005)
TiO2 (100% anatase 200e500 nm - After 5 h, 20% of lincomycin
or anatase/ was photolytic degraded. In
rutile ¼ 4/1) the presence of TiO2 more
1 and 0.4 g/L of than 98% of drug was
catalyst, oxidized within about 2 h.
respectively - Using TiO2 (anatase/rutile)
as catalyst, 60% TOC removal
was achieved, but a less
significant mineralisation
was observed using
100% anatase.
Lincomycin 25e50 mg/L Distilled water Electrochemical - stainless Absorbance at - Lincomycin was hardly Jara et al.
oxidation steel cathode 200e400 nm, oxidized (COD (2007)
- Ti/Pt, graphite, COD, iodometric removal ¼ 30%) with
Ti/IrO2/Ta2O5 titration, slow overall kinetics
or 3D GAC as voltammetric due to difficult
anode analyses deprotonation, a
- Na2SO4 or NaCl prerequisite for the
as electrolyte following electron
transfer step.
- The electro-oxidation
was found to occur
with first order kinetics.
- Different anodes
had been tested.
Lincomycin 25 mg/L Distilled water Photo-Fenton Black light TOC, DOC, - The degradation was Bautitz and
and wastewater (lmax ¼ 365 nm) HPLC-DAD improved when Nogueira
and solar radiation ferrioxalate was (2010)

pH ¼ 2.5 employed in comparison
0.20 mM ferrioxalate, to Fe(NO3)3 and FeSO4.
FeSO4, Fe(NO3)3 - After 8 min of irradiation
1.0e10 mM H2O2 the antibiotic was totally
removed in the presence
of ferrioxalate, while
when using Fe(NO3)3,
20 min were necessary
to achieve the same
degradation.
- 94% TOC removal was
observed after 60 min
irradiation when using
ferrioxalate, while 21%
TOC removal was
achieved using Fe(NO3)3.
7. Macrolides
Avilamycin COD ¼ 7000 mg/L Pharmaceutical Anaerobic process Up-flow anaerobic HPLC-UV, COD - The staged design Chelliapan
Tylosin wastewater reactor facilitated efficient et al. (2006)
pH ¼ 6.5e7.8 treatment of this
V ¼ 11 L divided antibiotic wastewater.
into four 2.75 - COD reduction was
L stages 70e75%.
Retention - An average of 95%
time ¼ 2e4 days tylosin reduction was
achieved, indicating that
this antibiotic could be
degraded efficiently in
the anaerobic reactor
system.
2317
2318
Azithromycin COD ¼ 360 or Two different Primary treatment: Activated sludge LCeMS - In treatment plant 1, a Göbel
Clarithromycin 590 mg/L WWTP effluents Screening treatment with pre-treatment with et al. (2007)
Erythromycin Aerated grit removal V ¼ 5600 m3, activated sludge
Roxithromycin Clarifier t ¼ 15 h was studied.
Membrane reactor - Bioreactor consisted of a
Secondary treatment:
with V ¼ 16 m3, stirred anaerobic
Activated sludge
t ¼ 13 h compartment and a
Membrane reactor
Sand filter with denitrification and
(1) or fixed-bed
V ¼ 288 m3, nitrification cascade.
reactor (2)
t ¼ 25 min - Similar eliminations
Clarifier
Activated sludge were observed
Sand filtration
treatment with in the secondary
V ¼ 9100 m3, treatment of
t ¼ 31 h two conventional

Fixed-bed reactor activated sludge
with V ¼ 1500 m3, systems and a
t¼1h fixed-bed reactor.
Sand filter with - Varying results were
V ¼ 360 m3, obtained for the
t ¼ 6e8 h investigated macrolides.
Azithromycin 2 mg/L Spiked WWTP Ozonation 2 columns LCeMS - Degradation followed Huber
Clarithromycin effluent operating in series 2nd order kinetics. et al. (2005)
Roxithromycin 0.5e5 mg/L O3 - 90e99% of degradation
pH ¼ 7 for O3 doses >2 mg/L.
- Suspended solids have
revealed a minor effect
on the removal efficiency.
Clarithromycin 0.2e0.6 mg/L Spiked STP Ozonation 5e15 mg/L O3 LCeMS - Ozonation revealed Ternes
Erythromycin effluent appropriate to oxidize et al. (2003)
Roxithromycin these compounds and
inactivate relevant
microorganisms
(degradation between 76
and 92%).
Clarithromycin 1 104 M Distilled water Ozonation 1 105 M O3 LCeMS, absorbance - Ozonation followed a 2nd Lange
pH ¼ 3.2e4.4 at 260 nm inhibition order reaction rate and the et al. (2006)
to P. putida rate was increased with
increasing pH.
- Reaction by-products were
determined and they were
less inhibitory than the
parent drug.
Erythromycin 10 ng/L DWTP effluent Clarification Clarification: LCeMS - Clarification decreased the Stackelberg
Chlorination 2 clarification tanks concentration of this et al. (2007)
GAC filtration operating in parallel antibiotic with a 47%
FeCl3 as coagulant removal. The moderate
pH ¼ 4.5e5.5 removal of this hydrophilic
Microsand injection compound from the water
Contact time ¼ 15e20 min phase during clarification
may be explained by
Chlorination:
ferric chloride coagulation,
Addition of NaClO
which results in base or
Time ¼ 200e300 min
acid hydrolysis.
GAC filtration: - After clarification, the
8 filter banks operating water samples were
simultaneously submitted to a
Contact time ¼ 1.5e3 min disinfection process. In
this process 92% removal
was achieved.

- Finally, chlorinated water
from disinfection process
was passed through GAC
filters. A total removal
was obtained.
Erythromycin 40 mg/L Spiked distilled Ozonation pH ¼ 3e11 LCeMS - The addition of H2O2 Lin et al.
Tylosin water H2O2/O3 molar accelerated the degradation (2009)
Pharmaceutical ratio ¼ 0.5e18 (optimum molar ratio
wastewater H2O2/O3 of 5).
- The wastewater ozonation
resulted in 97% removal
after 10 min and complete
degradation in 20 min for
all the compounds.
Roxithromycin 0.5 mM Spiked lake, river Ozonation 0.1e2 mg/L O3 HPLC-UV - Oxidation followed 2nd Huber
and well water pH ¼ 8 order kinetics. et al. (2003)
- Water matrix affects
ozone stability, radical
formation and scavenging.
- % Removal efficiencies > 90%.
8. Quinolones
Ciprofloxacin 0.15 mM Ultrapure water Photo-Fenton using HP UV at 280 TOC, COD, HPLC-DAD - The degradation was Bobu
a heterogeneous and 260 nm improved with the increase et al. (2008)
catalyst pH ¼ 3e10 of the H2O2 concentration
0e60 mM H2O2 and catalyst loading. An
Fe-Lap-RD catalyst optimum pH of 3 was
0e1.5 g/L catalyst achieved.
- At optimal conditions a
complete conversion and
57% of mineralisation was
achieved within 30 min.
- photo-Fenton followed
pseudo 1st order kinetics.
2319
2320
Ciprofloxacin 23e136 mM Deionised water Ozonation Ozonation: HPLC-UV - Ciprofloxacin ozonation and De Witte
660e3680 mg/L O3 perozonation could be well et al. (2009)
pH ¼ 3e10 described by 1st order
T ¼ 6.0e62.0 C kinetics.
- Highest degradation rate
Perozonation:
was obtained at the highest
2500 mg/L O3
ozone concentration and the
pH ¼ 3e10
lowest drug concentration
T ¼ 27.5 C
(95% degradation reached
2e990 mM H2O2
between 60 and 75 min).
No effect of temperature
was found.
- In the perozonation
experiments, the addition

of small amounts of H2O2
(2e50 mM) increased the
ciprofloxacin degradation.
- Reaction by-products were
determined.
Ciprofloxacin 30 ng/L Surface river Coagulation/ Coagulation: LCeMS - Coagulation had not been Vieno
Norfloxacin water Flocculation/ Fe2(SO4)3 found to affect the removal et al. (2007)
Ofloxacin Sedimentation 94e200 g/m3 of norfloxacin and ofloxacin.
Sand filtration coagulant 30% of ciprofloxacin was
Ozonation pH ¼ 5.0 removed from the effluent.
Granular activated - Rapid sand filtration and
Sand filtration:
carbon filtration granular activated carbon
Surface
Direct photolysis filtration didn’t remove
load ¼ 12 m/h
significantly these
pH ¼ 7.3
pharmaceuticals (w10%).
Ozonation: Drugs concentration was
3 columns not affected by direct
in series photolysis.
1 mg/L O3 - Ozonation was an
Contact time ¼ 30 min efficient technique for the
pH ¼ 7.3 elimination of most of the
GAC filtration: studied compounds.
2 step process Ciprofloxacin was only
Chemviron Filtrasorb carbon reduced by an
Contact time ¼ 36 min average of 16%.
Direct photolysis:
UV dose of 250 J/m2
Enrofloxacin COD ¼ 250e1400 Formulation Ozonation Ozonation: BOD5, COD, TOC, - COD removal was Balciog
lu
mg/L wastewater 3 g/(h L) O3 Absorbance at 254 nm increased with increasing and Ötker
pH ¼ 3e11Perozonation: pH from 3 to 7. The (2003)
pH ¼ 7 addition of H2O2 had no
0e100 mM H2O2 advantage for COD removal
kinetics over the direct
ozonation.
in terms of BOD5/COD was
increased.
- After 60 min, 95% removal
(45% TOC) was achieved.
Enrofloxacin 50e200 mg/L Distilled/deionised Adsorption pH ¼ 5e10 Absorbance at 271, - Enrofloxacin removal was Ötker and
water coupled with T ¼ 28e50 C 272 and 275 nm increased by decreasing pH Akmehmet-
ozonation Zeolite as adsorbent and increasing temperature. Balciog
lu
0.75 g adsorbent - Adsorption equilibrium data (2005)
Contact time ¼ 24 h were fitted by Langmuir
1430 mg/h O3 isotherm model. 80% of
Contact time ¼ 10e30 min enrofloxacin was adsorbed
on zeolite.
- Ozone at sufficient
concentration was able to
decompose totally
enrofloxacin adsorbed on
zeolite, but it caused the
change of zeolite pore
structure.
Enrofloxacin 10 mg/L Pharmaceutical Reverse osmosis Reverse osmosis: HPLC-DAD - The removal of the Kosutic
wastewater Nanofiltration antibiotic by reverse et al. (2007)

XLE and HR95PP
membranes osmosis and the tight
nanofiltration membrane
Nanofiltration:
is acceptably high
NF90 and HL Desal
(rejection factors > 0.972).
membranes
Enrofloxacin 1580 mg/L Synthetic Conductive-diamond Conductive-diamond COD, TOC - The three processes can Guinea
wastewater electrochemical reduce the organic content et al. (2009)
electrochemical
oxidation of synthetic wastewater
Ozonation oxidation: polluted with enrofloxacin.
Fenton oxidation Si-boron doped - Conductive-diamond
diamond as anode electrochemical oxidation
Stainless steel as cathode is the more efficient
T ¼ 35 C technology in terms of
Ozonation: mineralisation, but not on
0.5 L/min O3 flow rate COD removal, which is more
T ¼ 25 CFenton efficiently achieved by
oxidation: ozonation.
pH ¼ 3 - The high efficiency in
FeSO4.7H2O as catalyst terms of oxidant-use
obtained by Fenton
oxidation during the initial
stages indicates that this
process is very efficient
in the removal of the
antibiotic, but it rapidly
leads to the formation
of refractory compounds.
2321
2322
Enrofloxacin 158e790 mg/L Ultrapure water Anodic oxidation with Pt or boron-doped TOC, HPLC-DAD - All procedures are less Guinea
electrogenerated H2O2 diamond (BDD) as anode potent using Pt as anode. et al. (2010)
Electro-Fenton Carbon-PTFE cathode - In the stirred tank reactor
Photoelectron-Fenton 12 ml/min O2 using BDD as anode, it
Solar UVA light was achieved:
photoelectron-Fenton with lmax ¼ 360 nm (i) 67% TOC removal in
0.05 M Na2SO4 anodic oxidation with
0.1e0.5 mM Fe2þ electrogenerated H2O2
pH ¼ 3.0 (ii) 78% TOC removal in
T ¼ 35 C Electro-Fenton
(iii) 96% TOC removal in
photoelectron-Fenton
(iv) 97% TOC removal in solar

- In the batch recirculation flow
reactor using BDD as anode, it
was achieved:
(i) 28% TOC removal in anodic
oxidation with electrogenerated
H2O2
(ii) 45% TOC removal in
Electro-Fenton
(iii) 86% dolar
Flumequine 19.1e95.7 mM Distilled water Semiconductor UV lamp (20 W) Absorbance at - Under optimized conditions Palominos
photocatalysis pH ¼ 3e10 331 nm, HPLC, (pH ¼ 6, absence of H2O2 and et al. (2008)
0.5e1.5 g/L TiO2 TOC, GCeMS, low titania load), the time
0.17e0.83 mM H2O2 antibacterial required to completely eliminate
test with E. coli flumequine was 30 min.
- Mineralisation after 60 min
irradiation was around 80%.
- The oxidation products are
not biologically active.
- The method has the advantage
that after short period of
treatment, the by-products
could be treated by conventional
biological systems.
Nalidixic acid 45 mg/L Distilled water Solar photo-Fenton Solar photo-Fenton: HPLC-UV, TOC, - After 200 min, the total Sirtori
combined with - pH ¼ 2.6e2.8 DOC, toxicity degradation of the antibiotic et al. (2009)
biological treatment - 20 mg/L Fe2þ tests with was achieved.
- 200e400 mg/L H2O2 V. fischeri - 90% of mineralisation was
- solar UV power achieved after 400 min.
- Photo-Fenton successfully
Biological treatment:
enhanced the biodegradability.
- activated sludge
- The global efficiency in the
- 500 L/h operation flux
combined solar photo-Fenton
and immobilized biomass reactor
system operated in batch mode
was 95% of DOC elimination, of
which 33% was accomplished by
the solar photo-Fenton treatment
and 62% by the biological
treatment.
Ofloxacin 5e10 mg/L Ultrapure water Semiconductor LP UV (125 W) Absorbance at - Degradation followed 1st order Molinari
photocatalysis TiO2 catalyst 230e280 nm kinetics. et al. (2006)
coupled with 1 g/L catalyst - At pH ¼ 6, 54% of the antibiotic
nanofiltration Membrane NTR7410, was adsorbed on the catalyst.
PAN GKSS HV3IT, - 66% degradation was achieved
N30F and NF PES 10 by photocatalysis.
- Filtration separated the
catalyst particles, but not
the reaction by-products
from the permeate.
Ofloxacin 25e50 mg/L Distilled water Electrochemical Electrolytic cell: Absorbance at - Different anodes had been Jara et al.
oxidation - stainless steel 200e400 nm, tested. (2007)
plate as cathode COD, iodometric - Ofloxacin was efficiently
- Ti/Pt, graphite, titration, oxidized (99.995%) over all
Ti/IrO2/Ta2O5 or voltammetric tested anodes.
3D GAC as anode analyses - The electro-oxidation was
found to occur with

- Na2SO4 or NaCl as
electrolyte 1st order kinetics.
- 1.5e400 A/m2 current
9. Quinoloxaline
Derivative
Carbadox 50 mg/L Spiked deionised/ Coagulation/ Coagulation: HPLC-UV - Coagulation/Flocculation/ Adams
distilled water Flocculation/ Al2(SO4)3, Fe2(SO4)3 Sedimentation, excess lime/ et al. (2002)
and surface river Sedimentation 0e170 mg/L coagulant soda ash softening, direct
water Excess lime/ Treatment time ¼ 3 h21 photolysis and ion exchange
soda ash were all relatively ineffective
Excess lime/soda
softening methods of antibiotic removal.
Powdered ash softening: - The percent removal of this
activated carbon Lime ¼ 232 mg/L antibiotic was greater than
sorption as CaCO3 90% for PAC dosage
Chlorination Soda ash ¼ 191 of 50 mg/L.
Ozonation mg/L as CaCO3 - Oxidation with both ozone
Direct pH ¼ 11.3 and chlorine at typical doses
photolysis Sorption: was effective in the removal
Ion exchange Calgon WPH Pulv of the studied
Reverse PAC adsorbent antibiotics (>90%)
osmosis 0e50 mg/L PAC - Reverse osmosis was effective
Contact time ¼ 4 h at the removal of the
Chlorination: studied compound with
1.0 mg/L Cl2 rejection levels greater than
(pH ¼ 7.5) 90%. However, this process is
Ozonation: usually not economical.
7.1 mg/L O3 (pH ¼ 7.5)
Direct photolysis:
LP UV at 254 nm
(pH ¼ 7.5)
Ion exchange:
0.66 g strong-acid cation
and strong-base anion
resins (pH ¼ 7)
Reverse osmosis:
Cellulose acetate
membrane
2323
2324
10. Sulfonamide
Sulfacetamide 0.1 mM Distilled water Semiconductor UV at 366 nm HPLC-UV, BOD5, - All drugs were completely Baran
Sulfadiazine photocatalysis TiO2 catalyst TOC, microbiological degraded after 300 min of et al. (2006)
Sulfamethoxazole 2.5 g/L catalyst assay with C. vulgaris irradiation.
Sulfathiazole - TOC removal varied between
30 and 70%.
- Intermediate products are
more biodegradables and less
toxic than the parent
compounds.
Sulfachloropyridazine 10 mg/L Deionised water Ion exchange Self-decomposition: HPLC-DAD - Self-decomposition was slow Choi
Sulfadimethoxine and spiked STP pH ¼ 7.0 and considerable amounts of et al. (2007)
Sulfamerazine effluent T ¼ 25 C antibiotics (4.1e7.3 mg/L) still
Sulfamethazine Treatment time ¼ 15 days remained after 15 days.

Sulfamethoxazole - MIEXÒ treatment was effective
MIEXÒ resin treatment:
Sulfamonomethoxine for removal of these drugs
pH ¼ 7.0
Sulfathiazole through ion exchange
T ¼ 25 C
(w90% removal), but organic
0.5e5.0 mL/L resin
interference was observed.
Treatment time ¼ 24 h
This treatment was ineffective
for removal of sulfamerazine
and sulfamethazine.
- Compounds with stronger
electronegativity were more
easily removed by MIEXÒ
treatment.
Sulfachloropyridazine 50 mg/L Spiked deionised/ Coagulation/ Coagulation: HPLC-UV - Coagulation/Flocculation/ Adams
Sulfadimethoxine distilled water Flocculation/ Al2(SO4)3, Fe2(SO4)3 Sedimentation, excess lime/ et al. (2002)
Sulfamerazine and surface river Sedimentation 0e170 mg/L coagulant soda ash softening, direct
Sulfamethazine water Excess lime/ Treatment time ¼ 3 h21 photolysis and ion exchange
Sulfathiazole soda ash were all relatively ineffective
Excess lime/soda ash
softening methods of antibiotic removal.
Powdered softening: - The percent removal of this
activated Lime ¼ 232 mg/L antibiotic was greater than
carbon sorption as CaCO3 90% for PAC dosage
Chlorination Soda ash ¼ 191 mg/L of 50 mg/L.
Ozonation as CaCO3 - Oxidation with both ozone
Direct photolysis pH ¼ 11.3 and chlorine at typical doses
Ion exchange Sorption: was effective in the removal
Reverse osmosis Calgon WPH Pulv of the studied
PAC adsorbent antibiotics (>90%)
0e50 mg/L PAC - Reverse osmosis was
Contact time ¼ 4 h effective at the removal of
Chlorination: the studied compound with
1.0 mg/L Cl2 (pH ¼ 7.5) rejection levels greater than
Ozonation: 90%. However, this process is
7.1 mg/L O3 (pH ¼ 7.5) usually not economical.
Direct photolysis:
LP UV at 254 nm
(pH ¼ 7.5)
Ion exchange:
resins (pH ¼ 7)
Reverse osmosis:
Cellulose acetate membrane
Sulfachloropyridazine 10 mg/L Distilled water Nanofiltration NF 200 membranes LCeMS - The sulphonamide Koyuncu
Sulfadimethoxine spiked with (14.6 cm2 area) antibiotic group et al. (2008)
Sulfamerazine calcium chloride, pH ¼ 7 showed slow
Sulfamethazine humic acid T ¼ 20 C adsorption kinetic and
Sulfamethizole and NaCl relatively little mass
Sulfamethoxazole adsorption, rising to only
Sulfathiazole 11e20% after 90 min.
- The organic matter, salinity
and kind of antibiotic affected
membranes rejection.
Sulfadiazine 2 mg/L Spiked WWTP Ozonation 2 columns operating LCeMS - Degradation followed 2nd Huber
Sulfamethozaxole effluent in series order kinetics. et al. (2005)
Sulfapyridine 0.5e5 mg/L O3 - 90e99% of degradation for
Sulfathiazole pH ¼ 7 O3 doses > 2 mg/L.
- Suspended solids have
revealed a minor effect on the
removal efficiency.

Sulfadiazine 15 mg/L Distilled water Semiconductor UV at 340e400 nm LC-conductimeter, - After 30 min of irradiation, Calza
Sulfadimethoxine photocatalysis TiO2 catalyst LCeMS sulfadimethoxine and et al. (2004)
Sulfamerazine 200 mg/L catalyst sulfathiazole were completely
Sulfathiazole T ¼ 50 C degraded. 80 and 90% removal
efficiencies were achieved for
sulfadiazine and sulfamerazine,
respectively.
- LC/MS was used to identify
the intermediates products
and the reaction mechanism.
Sulfadiazine 10 mg/L Pharmaceutical Reverse osmosis Reverse osmosis: HPLC-DAD - The removal of the antibiotic Kosutic
Sulfaguanidine wastewater Nanofiltration XLE and HR95PP by reverse osmosis and the et al. (2007)
Sulfamethazine membranes tight nanofiltration membrane
is acceptably high (rejection
Nanofiltration:
factor> 0.989).
NF90 and HL Desal
membranes
Sulfadimethoxine 40 mg/L Spiked distilled Ozonation pH ¼ 3e11 LCeMS - The addition of H2O2 Lin
Sulfamethazine water and H2O2/O3 molar accelerated the degradation et al. (2009)
Sulfamethoxazole pharmaceutical ratio ¼ 0.5e18 (optimum molar ratio
wastewater H2O2/O3 of 5).
- The ozonation of the
pharmaceutical wastewater
resulted in complete
degradation in 20 min for
all the compounds.
Sulfamethazine 10e70 mg/L Distilled water Semiconductor UV at 350e400 nm Absorbance at - Degradation followed pseudo 1 Kaniou
photocatalysis pH ¼ 4.8 260 nm, TOC, DOC st order kinetic rate. et al. (2005)
0e800 mg/L H2O2 - The increase in the catalyst
TiO2 (anatase/rutile ¼ 3.6/1 quantity and the presence of
or 100% anatase), H2O2 enhanced the
TiO2Na or ZnO catalyst degradation rate.
0e4 g/L catalyst - TiO2 is more effective than ZnO
for drug removal and
mineralisation.
- With 1 g/L TiO2 it was achieved
95% degradation (120 min)
and 85% DOC removal
(350 min).
- With 1 g/L ZnO it was achieved
total degradation (120 min) and
30% DOC removal (350 min).
2325
2326
Sulfamethazine 50 mg/L Deionised Photo-Fenton Sunlight lamp (400e580 nm) HPLC-DAD, TOC, - To achieve maximum TOC Pérez-Moya
water pH ¼ 3 bacterial tests removal (60%) and total et al. (2010)
176e1024 mg/L H2O2 degradation it was necessary
12e68 mg/L Fe2þ to use 600 mg/L H2O2,
50 mg/L Fe2þ.
- After 2 min, total degradation
of sulfamethazine
was achieved.
- It has been established that
toxicity increases during its
1st reaction stages.
Sulfamethizole 100 mM Distilled water Direct photolysis Direct photolysis: HPLC-UV, LCeMS - Direct photolysis was found Boreen
Sulfamethoxazole and spiked Fenton Natural sunlight irradiation to be highly pH-dependent. et al. (2004)
Sufamoxole river water or MP UV (175 W) - Sulfamethoxazole and

Sulfathiazole pH ¼ 2.5e11 sulfisoxazole were
Sulfisoxazole photodegraded most readily
Fenton:
in acidic media, whereas
pH ¼ 3
sulfamethizole and
30% H2O2
sulfathiazole were degraded
40 mM Fe2þ
in basic. Sulfamoxole was
degraded nonphotochemically
in aqueous solutions at all
pH values.
- Sulfonamides drugs were
all degraded by Fenton
reagent.
Sulfamethoxazole 0.5 mM Spiked lake, Ozonation 0.1e2 mg/L O3 HPLC-UV - Oxidation followed 2nd Huber
river and well pH ¼ 8 order kinetics. et al. (2003)
water - Water matrix affects ozone
stability and radical formation.
- % Removal efficiencies > 90%.
Sulfamethoxazole 0.2e0.6 mg/L Spiked STP Ozonation 5e15 mg/L O3 LCeMS - Ozonation revealed Ternes
effluent appropriate to oxidize this et al. (2003)
compound and inactivate
relevant microorganisms
(92% degradation).
Sulfamethoxazole 5e500 mM Deionised water Semiconductor UV at 324e400 nm HPLC-PDA, DOC - Sulfamethoxazole degradation Hu et al.
spiked with photocatalysis pH ¼ 3e11 was influenced by the initial (2007)
natural organic TiO2 (anatase/rutile ¼ 9/1 drug concentration, catalyst
matter and or 100% anatase, 100% phase and concentration, pH
bicarbonates rutile) catalyst and water matrix.
0.01e1 g/L catalyst - Degradation followed pseudo
1st order kinetic rate.
- A mixed phase was more
reactive than pure rutile
or anatase.
- A total degradation was
achieved after 60 min.
Sulfamethoxazole 25e200 mg/L Distilled water Semiconductor UV at 240e310 nm HPLC-PDA, DOC, - Degradation and mineralisation Abellán
photocatalysis pH ¼ 2e11 BOD5, COD, TOC were increased, increasing the et al. (2007)
TiO2 catalyst catalyst dose (360 min, 2.0 g/L
0e2 g/L catalyst TiO2, pH ¼ 5, 90% degradation
and 40% TOC removal).
- pH didn’t influenced
significantly the drug
removal, but TOC removal
suffered an enhancement
with pH increase.
- Low biodegradability
of the effluent.
Sulfamethoxazole 200 mg/L Distilled water Photo-Fenton Black light e 365 nm BOD5, COD, TOC, - Drug degradation, González
50e1000 mg/L H2O2 HPLC-UV, toxicity mineralisation and et al. (2007)

10 mg/L Fe2þ test to V. fischeri, biodegradability were
pH ¼ 2.8 oxygen uptake improved with the increase
of H2O2 concentration.
- Using H2O2 < 400 mg/L, the
process produced
intermediates with enough
acute detoxicity and no
inhibition effects.
- With 400 mg/L, a TOC removal
of 50% was achieved, as
well as a COD removal of 75%.
Sulfamethoxazole 30 ng/L DWTP effluent Clarification Clarification: LCeMS - Clarification decreased the Stackelberg
Chlorination 2 clarification tanks average concentration of this et al. (2007)
GAC filtration operating in parallel antibiotic with a 33% removal.
FeCl3 as coagulant - After clarification, the water
pH ¼ 4.5e5.5 samples were submitted to a
Microsand injection disinfection process. With this
Contact time ¼ 15e20 min process 100% removal
was achieved.
Chlorination:
Addition of sodium
hypochlorite
Contact time ¼ 200e300 min
GAC filtration:
8 filter banks operating
simultaneously
Contact time ¼ 1.5e3 min
2327
2328
Sulfamethoxazole COD ¼ 360 Two different Primary treatment: Treatment plant 1: LCeMS - In treatment plant 1, a Göbel
Sulfapyridine or 590 mg/L WWTP effluents Screening Activated sludge treatment pre-treatment with activated et al. (2007)
Aerated grit removal with V ¼ 5600 m3, t ¼ 15 h sludge was studied.
Clarifier Membrane reactor - Bioreactor consisted of a
with V ¼ 16 m3, t ¼ 13 h stirred anaerobic compartment
Secondary treatment:
Sand filter with V ¼ 288 m3, and a denitrification and
Activated sludge
t ¼ 25 min nitrification cascade.
Membrane reactor (1)
- Similar eliminations were
or fixed-bed reactor (2) Treatment plant 2:
observed in the secondary
Clarifier Activated sludge treatment
treatment of two conventional
Sand filtration with V ¼ 9100 m3, t ¼ 31 h
activated sludge systems and
Fixed-bed reactor
a fixed-bed reactor.
with V ¼ 1500 m3, t ¼ 1 h
- Varying results were obtained
Sand filter with
for the investigated
V ¼ 360 m3, t ¼ 6e8 h

sulfonamides. These
compounds were detected in
secondary effluents.
Sulfamethoxazole 200 mg/L Distilled water Ozonation 0.15e1.5 g/L O3 HPLC-UV, TOC, COD, - Ozonation followed 2nd Dantas
pH ¼ 3e11 BOD5, absorbance order kinetics. et al. (2008)
at 254 nm, toxicity - Process performance
to V. fischeri increased with increasing
pH. Temperature had no
significant effect on
degradation.
- After 60 min of ozonation
with 1.5 g/L O3, it was
achieved a complete drug
degradation with an increase
in biodegradability, and low
mineralisation (TOC
removal w18%). Ecotoxicity
remained practically
unchanged.
- By-products were identified
by means of LCeMS.
Sulfamethoxazole 50 ng/L Spiked Nanofiltration and Polyamide thin-film HPLCeMS - Excellent overall performance Radjenovi c
groundwater reverse osmosis composite membranes of both nanofiltration and reverse et al. (2008)
Reverse osmosis: osmosis was noted, with high
486 m3/h feed flow rejection percentages (>95%).
356 m3/h permeate flow
Two parallel stages (240 þ 120
membranes)
Nanofiltration:
360 m3/h feed flow
234 m3/h permeate flow
Two parallel stages
(186 þ 90 membranes)
Sulfamethoxazole 10 mg/L Distilled water Photolysis Solar simulator (l < 290 nm) HPLC-UV, LCeMS, - The presence of nitrate in Trovó
Distilled DOC, toxicity test distilled water did not et al. (2009)
water þ nitrate to V. fischeri and affect the degradation rate.
(10 and 20 mg/L) D. magna - 98% of the initial
Seawater concentration in distilled
water was removed after
30 h of irradiation.
- No DOC variation was
observed, demonstrating
the formation of
intermediates.
- In the seawater solutions,
a slower kinetic was
observed, where only
a slight reduction in the
antibiotic concentration
(14%) occurred after 7 h.

and the reaction
mechanism.
- High toxicity of the
photo-transformation
products generated.
Sulfamethoxazole 50 mg/L Distilled water Solar photo-Fenton Lamp at 290 nm HPLC-UV, HPLCeMS, - Degradation and Trovó
Seawater pH ¼ 2.5e9.0 DOC, toxicity tests mineralisation were et al. (2009)
30e210 mg/L H2O2 strongly hindered in
2.6e10.4 mg/L Fe2þ seawater compared to
distilled water.
- The increase in iron
concentration showed
a slight improvement
on the pollutant degradation
and mineralisation rate.
- The increase of H2O2
concentration up to 120 mg/L
in distilled water reduced the
sample toxicity.
- The DOC removal obtained
was about 80% for distilled
water and 50% for seawater.
2329
2330
11. Tetracyclines
Chlortetracycline 10 mg/L Deionised water Ion exchange Self-decomposition: HPLC-DAD - Self-decomposition was slow Choi et al.
Democycline and spiked STP pH ¼ 7.0 and considerable amounts (2007)
Doxycycline effluent T ¼ 25 C of antibiotics (6.1e7.8 mg/L)
Meclocycline Treatment time ¼ 15 days still remained after 15 days.
Minocycline An exception was minocycline
MIEXÒ resin treatment:
Oxytetracycline and oxytetracycline, which
pH ¼ 7.0
Tetracycline were reduced to 0.7
T ¼ 25 C
and 2.2 mg/L, respectively.
0.5e5.0 mL/L resin
- MIEXÒ treatment was
Treatment time ¼ 24 h
effective for removal of
these drugs through ion
exchange (removal > 80%),
but organic interference

was observed.
- Compounds with stronger
electronegativity were more
easily removed by
MIEXÒ treatment.
Chlortetracycline COD ¼ 52,240e49, Manure slurry Anaerobic pH ¼ 7.5 LCeMS - Drug concentration decreased Arikan
100 mg/L digestion T ¼ 35 C approximately 75%. (2008)
Treatment time ¼ 33 days
Chlorotetracycline 10 mg/L Distilled water Nanofiltration NF 200 membranes LCeMS - After 90 min, the degradation Koyuncu
Doxycycline spiked with (14.6 cm2 area) of the tetracyclines ranged et al. (2008)
Oxytetracycline calcium chloride, pH ¼ 7 between 50 and 80%.
Tetracycline humic acid T ¼ 20 C - The organic matter, salinity
and NaCl and kind of antibiotic affected
membranes rejection.
Chlortetracycline 10 mg/L (adsorption Spiked synthetic Coagulation Coagulation: LCeMS, DOC - In coagulation, the removal Choi et al.
Demeclocycline studies) and river water Adsorption with PACl (5e60 mg/L) efficiency was improved with (2008)
Doxycycline 100 mg/L activated carbon Contact time ¼ 5 min the increasing of PACl.
Meclocycline (coagulation) - Coagulation could remove
GAC filtration:
Minocycline 43e94% of the drugs from
Calgon F400 and
Oxytetracycline the synthetic water (40 mg/L
Coconut-based carbon
Tetracycline coagulant), but in the river
water the removal efficiencies
were slightly deteriorated
(44e67%) due to organic
interference.
- With activated carbon, more
than 68% of tetracyclines
were removed.
Chlortetracycline 20e110 mM Distilled water Adsorption with 0.8e3.5 g/L Al2O3 HPLC-DAD, LCeMS - Rapid adsorption occurs in Chen and
Oxytetracycline aluminium oxide the first 3 h (40 mM Huang
Tetracycline antibiotic, 1.78 g/L Al2O3, (2010)
pH ¼ 5, T ¼ 22 C).
- The %adsorption was 43%
tetracycline, 57%
chlortetracycline and 44%
oxytetracycline.
Oxytetracycline 1000 mg/L Pharmaceutical Reverse osmosis Reverse osmosis: Absorbance at 480 nm, - Using reverse osmosis Li et al.
(COD ¼ 10000 mg/L) wastewater Ultrafiltration - NTR-7450 membrane COD, TOC the organic content in (2004)
- NTR-7459 membrane the permeate was decreased
- Area ¼ 155 cm2 from COD ¼ 10000 mg/L to
- T ¼ 21e23 C less than 200 mg/L
- Operational (98% removal).
pressure ¼ 1.8 MPa - The oxytetracycline was
- Volume reduction ¼ 3.5 reduced from 1000 mg/L
to lower than 80 mg/L (87.5%
Ultrafiltration:
removal) and was concentrated
- Stirred cell
more than 3 times
- 3,10,30,50 K Da
in the retentate.
cut-off membranes
- With additional treatment
- Operational
of ultrafiltration by 3K
pressure ¼ 0.3 MPa
membranes, the antibiotic
- Volume reduction ¼ 10
recovery ratio was higher
than 60% and the purity

higher than 80%.
Oxytetracycline 10 mg/L Pharmaceutical Reverse osmosis Reverse osmosis: HPLC-DAD - The removal by reverse osmosis Kosutic
wastewater Nanofiltration XLE and HR95PP and the tight nanofiltration et al. (2007)
membranes membrane is acceptably high
(rejection factor> 0.990).
Nanofiltration:
NF90 and HL Desal
membranes
Oxytetracycline 10e40 mg/L Ultrapure water Direct photolysis MP UV at 365 nm HPLC-UV, TOC, toxicity - Oxytetracycline photolysis Shaojun
pH ¼ 4e9 to P. phosphoreum followed 1st order et al. (2008)
model kinetics.
- After 240 min of irradiation,
an inhibition rate of 47%
was achieved with 90%
degradation and 14%
TOC removal.
Oxytetracycline 100e200 mg/L Ultrapure water Ozonation 11 mg/L O3 HPLC-DAD, COD, BOD5, - Performance increased Li et al.
pH ¼ 3e11 toxicity to V. fischeri with increasing pH (100% (2008)
degradation after 20 min).
BOD5/COD was higher
than 0.3-biodegradable
effluent.
- The toxicity results
indicated that by-products
(5e30 min) were more
toxic than the parent
compound.
Tetracycline 10e50 mg/L Distilled water Semiconductor MP UV (125 W) HPLC-UV, TOC, - Degradation followed Addamo
photocatalysis pH ¼ 6.0 Absorbance at pseudo 1st order et al. (2005)
TiO2 (100% anatase or 200e500 nm kinetic rate.
anatase/rutile ¼ 4/1) - After 5 h, 70% of tetracycline
1 and 0.4 g/L of catalyst, was photolytic degraded. In
respectively the presence of TiO2 more
than 98% of drug was
oxidized within about 2 h.
- Using TiO2 (anatase/rutile)
as catalyst, tetracycline was
totally mineralised, whereas
only 50% was observed using
100% anatase.
2331
2332
Tetracycline 40 mg/L Deionised water Semiconductor UV at 254, 365 nm and HPLC-UV, BOD5, COD, - Degradation followed 1st Reyes
photocatalysis solarium device at TOC, microbiological order kinetics. et al. (2006)
300e400 nm assay with S. aureus - Degradation and TOC
TiO2 catalyst removal were influenced
0.5e1 g/L catalyst by the light source
(UV 254 nm>solarium>
UV 365 nm).
- With 0.5 g/L TiO2 and
after 120 min it
was achieved:
UV 254 nm: 100%
degradation, 90%
TOC removal
Solarium: 100% degradation,

70% TOC removal
UV 365 nm: 50% degradation,
10% TOC removal
- By-products did not show
antibacterial and were more
biodegradable than the
parent compound.
Tetracycline 24 mg/L Spiked STP Photo-Fenton Black light (15 W) TOC, HPLC-UV - photo-Fenton under Bautitz and
effluent, surface and solar irradiation artificial or solar irradiation Nogueira
and deionised 1e10 mM H2O2 was very efficient, achieving (2007)
water 0.20 mM ferrioxalate total degradation after
or Fe(NO3)3 approximately 1 min
pH ¼ 2.5 irradiation.
- Under black light irradiation,
higher efficiency was
obtained using iron nitrate,
while solar degradation
is favoured by the use
of ferrioxalate.
Tetracycline 10e40 mg/L Ultrapure water Direct photolysis ML UV at 365 nm HPLC-UV, TOC, - Photolysis followed 1st Jiao et al.
pH ¼ 6 toxicity to V. fischeri order kinetics. (2008)
- Upon 300 min of irradiation,
only 15% reduction of TOC
occurred in spite of quick
conversion of 73% of
tetracycline, suggesting
that a majority of this drug
transformed into intermediate
products without complete
mineralisation.
- Toxicity increased with
irradiation. Reaction
by-products were studied.
Tetracycline 20 mg/L Distilled water Semiconductor Xe lamp (300e800 nm) Absorbance at - The optimal conditions Palominos
photocatalysis TiO2 and ZnO as catalyst 360 nm and 380 nm, found were 1.5 g/L and et al. (2009)
0.5e1.5 g/L TiO2 TOC, antibacterial pH ¼ 8.7 for TiO2 and 1.0 g/L
0.2e1.5 g/L ZnO test with S. aureus and pH ¼ 11 for ZnO.
pH ¼ 3e10 (TiO2) or - After 15 min irradiation, in
pH ¼ 6e11 (ZnO) the absence of catalyst, 80%
degradation was achieved.
After 15 min of irradiation,
the antibiotic was completely
removed with TiO2 and more
than 50% was mineralised
(total removal of the
antibacterial activity).
In the presence of ZnO,
degradation was achieved
after 10 min. and
mineralisation after 60 min.

12. Other antibiotics
Chloramphenicol 10e80 mg/L Deionised water Semiconductor UV at 320e400 nm Absorbance at - Pseudo 1st order kinetic rate Chatzitakis
photocatalysis pH ¼ 5 276.5 nm, TOC, increased with increasing drug (2008)
0e600 mg/L H2O2 antimicrobial concentration, catalyst loading
TiO2 (anatase/rutile ¼ 3.6/1 activity to E. coli and H2O2 concentration.
or 100% anatase), TiO2Na - Temperature slightly affected
(100% anatase) or ZnO the photo-degradation process.
catalyst - TiO2 (anatase/rutile ¼ 3.6/1)
0e4 g/L catalyst and ZnO catalysts seem to be
T ¼ 3e57 C the most efficient.
- It was achieved a complete
elimination of the antibiotic
activity after 90 min, with
70% of mineralisation.
Mitomycin C 17.9 mg/mL Distilled water Electrochemical Two Pt/Ir electrodes HPLC-UV, - Electrolysis slightly degraded Hirose
oxidation NaCl as electrolyte microbiological and eliminated cytotoxicity, et al. (2005)
100 mA current assay with S. aureus, mutagenicity and
cytoxicity and microbiological activity of
mutagenic assays this antibiotic.
2333
2334
Trimethoprim 50 mg/L Spiked deionised/ Coagulation/ Coagulation: HPLC-UV - Coagulation/Flocculation/ Adams
distilled water Flocculation/ Al2(SO4)3, Fe2(SO4)3 Sedimentation, excess et al. (2002)
and surface Sedimentation 0e170 mg/L coagulant lime/soda ash softening,
river water Excess lime/ Treatment time ¼ 3 h21 direct photolysis and ion
soda ash exchange were all
Excess lime/soda
softening relatively ineffective
Powdered ash softening: methods of antibiotic
activated Lime ¼ 232 mg/L removal.
carbon sorption as CaCO3 - The percent removal of
Chlorination Soda ash ¼ 191 mg/L this antibiotic was
Ozonation as CaCO3 greater than 90% for
Direct pH ¼ 11.3 PAC dosage of 50 mg/L.
photolysis Sorption: - Oxidation with both
Ion exchange Calgon WPH Pulv ozone and chlorine at

Reverse osmosis PAC adsorbent typical doses was
0e50 mg/L PAC effective in the removal
Contact time ¼ 4 h of the studied
Chlorination: antibiotics (>90%)
1.0 mg/L Cl2 (pH ¼ 7.5) - Reverse osmosis was
Ozonation: effective at the removal
7.1 mg/L O3 (pH ¼ 7.5) of the studied compound
with rejection levels
Direct photolysis:
greater than 90%.
LP UV at 254 nm
However, this process
(pH ¼ 7.5)
is usually not economical.
Ion exchange:
resins (pH ¼ 7)
Reverse osmosis:
Cellulose acetate
membrane
Trimethoprim 0.2e0.6 mg/L Spiked STP effluent Ozonation 5e15 mg/L O3 LCeMS - Ozonation revealed Ternes
appropriate to oxidize et al. (2003)
this compound and
inactivate relevant
microorganisms
(85% degradation).
Trimethoprim 10 mg/L Pharmaceutical Reverse osmosis Reverse osmosis: HPLC-DAD - The removal of the Kosutic
wastewater Nanofiltration XLE and HR95PP antibiotic by reverse et al. (2007)
membranes osmosis and the tight
nanofiltration membrane
Nanofiltration:
is acceptably high
NF90 and HL Desal
(rejection factor > 0.888).
membranes
Trimethoprim COD ¼ 360 Two different Primary Treatment plant 1: LCeMS - In treatment plant 1, a Göbel
or 590 mg/L WWTP effluents Activated sludge pre-treatment with et al. (2007)
treatment:
treatment with activated sludge
Screening
V ¼ 5600 m3, t ¼ 15 h was studied.
Aerated grit
Membrane reactor - Bioreactor consisted
removal
with V ¼ 16 m3, of a stirred anaerobic
Clarifier
t ¼ 13 h compartment and a
Secondary treatment: denitrification and
Sand filter with
Activated sludge nitrification cascade.
V ¼ 288 m3,
Membrane - Similar eliminations
t ¼ 25 min
reactor were observed in the
(1) or fixed-bed Treatment plant 2:
secondary treatment
reactor (2) Activated sludge
of two conventional
Clarifier treatment with
activated sludge
Sand filtration V ¼ 9100 m3, t ¼ 31 h
systems and a
Fixed-bed reactor
fixed-bed reactor.
with V ¼ 1500 m3, t ¼ 1 h
- Slight elimination

Sand filter with
of up to 20% was
V ¼ 360 m3, t ¼ 6e8 h
observed in conventional
activated sludge
treatment and the
fixed-bed reactor.
Trimethoprim 50 mg/L Distilled water Adsorption on pH ¼ 4e10 UV at 278 nm - The adsorption isotherm Kim
powered and T ¼ 25 C on both activated carbons et al. (2010)
granular 0e3 g/L adsorbent could be fitted with
activated Toth equation.
carbon - The powered activated
carbon was more
efficient than granular
activated carbon to
remove the trimethoprim.
However the separation
from aqueous solution
was not easy, so that
granular activated
carbon was used instead
(% removal > 90% after
30 min at pH ¼ 4 and
2.0 g/L adsorbent).
2335
transported to the surfaces of the media, where an attachment compounds, some of them with potentially dangerous carcinogenic
mechanism such as electrostatic attraction, chemical bond or activity (trihalomethanes and haloacetic acids) (Acero et al., 2010;
adsorption retains the particles (Eckenfelder, 2007). This process Navalon et al., 2008).
has the disadvantage of not degrading the contaminant, but Chlorine dioxide has been used as an alternative to other chlo-
concentrating it in the solid phase, generating a new waste. rine species because in its reaction with organic compounds it does
Coagulation/flocculation/sedimentation employs chemicals to not form trihalomethanes. Besides that, it is more selective than the
enhance the solids sedimentation, pollutants precipitation and other oxidants and reacts with micropollutants through a one-
colloids formation and subsequent settle out. The most used electron exchange reaction e radical reaction (Navalon et al.,
chemicals are lime, alum, iron salts and polymers (Eckenfelder, 2008). It is a free stable radical that does not react with aromatic,
2007). These techniques require a subsequent treatment to hydrocarbons, carbohydrates and molecules containing primary
remove the pollutants (in a coagulated form) from the effluents. and secondary amines, aldehydes and ketones. Nonetheless, it
Over the last ten years, several conventional techniques have reacts with molecules containing phenolic and tertiary amino
been tested in antibiotics removal from environmental matrices. groups (Huber et al., 2005a,b; Sharma, 2008).
When the pollutants toxicity against the microorganisms used in Few articles of antibiotics degradation using this technique
the biological systems is very low, this method continues to be the were found. Navalon et al. (2008) studied the oxidation of three
best approach. Chelliapan et al. (2006) and Arikan (2008) studied b-lactams (amoxicillin, cefadroxil and penicillin G) with chlorine
the application of anaerobic processes in the removal of macro- dioxide. They concluded that penicillin reacted sluggishly with
lides and tetracyclines, respectively. In these two cases, a reduc- ClO2, whereas amoxicillin and cefadroxil were highly reactive
tion of 90% for macrolides and 75% for tetracyclines was achieved. (both have a phenolic group). The authors also studied the influ-
As mentioned above, this removal does not always occur. Göbel ence of ClO2 dose and pH on the process. They concluded that the
et al. (2007) tested the traditional primary and secondary treat- ClO2 reacted stoichiometrically with these antibiotics and the
ments used in the WWTPs in matrices containing macrolides, influence of pH was directly related to the compound structure
sulphonamides and trimethoprim. In this case slight eliminations (e.g. the reactivity of chlorine dioxide towards penicillin was
(z20%) were verified. Adams et al. (2002), Stackelberg et al. enhanced with the pH decrease, while for amoxicillin and cefa-
(2007) and Vieno et al. (2007) investigated the efficiency of droxil an opposite situation occurred). A total degradation was
some physicochemical methods, such as clarification, coagulation/ achieved after 2 h for penicillin and 1 min for the other
flocculation/sedimentation and filtration. They were applied to compounds. Although, degradation metabolites were detected,
macrolides, sulphonamides, quinolones, quinoxaline derivatives their toxicity was not discussed.
and trimethoprim, resulting in low removals (maximum removal Adams et al. (2002) also studied the degradation of sulfon-
of about 30%). amides, trimethoprim and carbadox at a concentration level of
Due to the low efficiencies of these methodologies and some- 50 mg L1 with 1.0 mg L1 of Cl2. They also concluded that oxidation
times the inability of their use, new alternatives have emerged. with chlorine was effective in the removal of the studied antibiotics
(>90%). However, they verified that natural organic matter influ-
3.2. Oxidation processes enced the oxidation process, comparing the reaction rates in river
and distilled water. The slower reaction rates in river water sug-
3.2.1. Chlorination gested that organic matter may complex or otherwise interact with
Due to its low cost, chlorine gas or hypochlorite have been the studied compounds, reducing reactivity. The authors also
frequently applied in the disinfection of drinking water treatment detected the formation of chlorinated by-products, which should
plants. They are currently used as a post-treatment, in order to have higher toxicity than the original compounds. A similar
maintain a disinfectant residual level in the distribution systems conclusion was obtained by Stackelberg et al. (2007), which studied
(Acero et al., 2010). However, some studies also refer the chemical the degradation of macrolides and sulphonamides, using NaClO.
oxidation using chlorinated species in wastewater treatments. The From the bibliographic research done, the authors conclude that
application of this technique for treating water containing phar- this technique seems to be efficient in the degradation of antibiotics
maceuticals before the application of biological treatments has present in matrices with low loads of organic matter, such as
been employed in order to oxidize them to readily biodegradable drinking water. In addition, the degradation rates are also influ-
and less toxic compounds. enced by pH. This technique has been replaced by advanced
From the chlorinated species, hypochlorite has the highest oxidation processes in order to avoid the formation of halogenated
standard oxidation potential (E0 ¼ 1.48 V), followed by chlorine gas species, which are potentially carcinogenic.
(E0 ¼ 1.36 V) and chlorine dioxide (E0 ¼ 0.95 V) (Sharma, 2008).
Chlorine gas hydrolyses in water according to the reaction: 3.2.2. Advanced oxidation processes
The recalcitrant nature of the effluents containing antibiotics
Cl2 þ H2O / HOCl þ Cl þ Hþ (1) residues interferes in the elimination of these compounds by
traditional biological treatments. In these cases, one alternative is
Hypochlorous acid (HOCl) is a weak acid that dissociates in to apply advanced oxidation processes (AOPs).
aqueous solutions in hypochlorite (ClO) and Hþ. For pH > 4, AOPs are oxidative methods based on the generation of inter-

Cl2 hydrolysis is almost complete and consequently hypochlorous mediate radicals, the hydroxyl radicals (OH ), which are extremely
acid and hypoclorite are the main chlorine species (Acero et al., reactive and less selective than other oxidants (e.g. chlorine,
2010). However, among the different aqueous chlorine species, molecular ozone,.). Its standard oxidation potential (E0 ¼ 2.8 V) is
hypochlorous acid is the major reactive form during water treat- greater than the conventional oxidants, making them extremely
ment. Due to its oxidizing power and its chemical structure, effective in the oxidation of a great variety of organic compounds
hypochlorous acid can react with organic compounds through (Hernandez et al., 2002; Bautitz and Nogueira, 2007). These radicals
oxidation reactions, addition reactions to unsaturated bonds or are produced from oxidizing agents such as ozone (O3) or hydrogen
electrophilic substitution reaction (Deborde and von Gunten, peroxide (H2O2), often combined with metallic or semiconductor
2008). In fact, this species reacts with aromatic rings, neutral catalysts and/or UV radiation. In these processes, it is expected that
amines and double bonds, producing halogenated organic organic compounds are oxidized to less refractory intermediate
species (less toxic and more biodegradables) or even mineralised to improving the mass transfer rates. This is a critical point in the
CO2 and H2O. Sometimes, the produced metabolites are potentially ozonation process. If the pH value is not well controlled, a decrease
more dangerous than the parent compound (Dantas et al., 2008). of pH during the process will occur due to the accumulation of
Examples of AOPs include ozonation, Fenton, photo-Fenton, carboxylic acids. These will affect the reaction rate and its mecha-
photolysis, semiconductor photocatalysis and electrochemical nism and also the absorption rates of ozone.
processes. The same study was performed for other antibiotic classes, such
as lincosamides (Qiang et al., 2004), macrolides (Ternes et al., 2003;
3.2.2.1. Ozonation. The ozone is a strong oxidant (E0 ¼ 2.07 V) Huber et al., 2003, 2005a,b; Lange et al., 2006; Lin et al., 2009),
capable to act direct or indirectly. For a direct oxidation with quinolones (Balciog lu and Ötker, 2003; De Witte et al.,
molecular ozone (in this case, this is not a AOP method), it is 2009), sulfonamides (Huber et al., 2003, 2005a,b; Ternes et al.,
required that the study-compounds have carbonecarbon double 2003; Dantas et al., 2008; Lin et al., 2009) and tetracyclines (Li
bonds, aromatic bonds or nitrogen, phosphorous, oxygen or et al., 2008), as can be seen in Table 2. Overall, it was found that
sulphur atoms (Ikehata et al., 2006) since it only reacts selectively for all these classes studied degradation above 76% occurred,
with nucleophilic molecules (Stockinger et al., 1995). Otherwise, accompanied by low total organic carbon removal and a slight
the decomposition of ozone in water to form hydroxyl radicals increase in the effluents biodegradability. Lower degradations were
occurs through the following mechanism (Andreozzi et al., 1999), achieved for the b-lactam antibiotics. The results from the ecotox-
where hydroxide ions initiate the reaction: icity of treated effluents are not consensual. Some authors suggest
that the metabolites produced are less inhibitory than the parent
O3 þ OH / O2 þ HO2 (2) compound (Lange et al., 2006), others find that ecotoxicity remains
practically unchanged (Dantas et al., 2008) and there are still
O3 þ HO2 / HO2 þ O3

(3) authors who verified an increase in the effluent toxicity (Li et al.,
2008). Therefore, this is an issue that cannot be generalised and
HO2 / Hþ þ O2

(4) depends on the compound to be oxidized.
In order to improve the performance of this kind of treatment it
O2 þ O3 / O2 þ O3

(5) is possible to combine ozone with UV irradiation, hydrogen
peroxide or catalysts. In the first case, the photolysis of ozone
O3 þ Hþ / HO3

(6) within aqueous solutions produces directly hydrogen peroxide,
which initiates the further decomposition of residual ozone into
HO3 / OH þ O2

(7) hydroxyl radicals by the following mechanism (Hernandez et al.,
2002):
According to reactions (2) and (3) the initiation of ozone
decomposition can be artificially accelerated by increasing the hn
O3 þ H2 O/O2 þ H2 O2 (9)
pH value.
Side reaction (8) is a fast process and plays an important role in
waters with low dissolved organic carbon and alkalinity (Gunten,
H2O2 / HO2 þ Hþ (10)
2003), since it can reduce the oxidation capacity of the system:
O3 þ HO2 / O3 þ HO2

(11)
OH þ O3 / HO2 þ O2

(8)
O3 þ Hþ / O2 þ HO

This technique has the advantage of being applied when the (12)
flow rate and/or composition of the effluents are fluctuating.
The homolytic cleavage of the hydrogen peroxide by UV light
However, the high cost of equipment and maintenance, as well as
produces also hydroxyl radicals:
energy required to supply the process, constitutes some of the
disadvantages. Mass transfer limitations are also a relevant factor to hn
be considered in the oxidation process with ozone. These systems H2 O2 /2HO$ (13)
require the transfer of ozone molecules from gas phase to liquid
The UV light used in this process can degrade some compounds by
phase, where the attack on the organic molecules occurs. In many
direct photolysis or can excite the micropollutants molecules
cases, the ozone consumption rate per unit of volume can be so
making them more susceptible for hydroxyl radical attack.
high that the mass transfer is the limiting step, reducing the process
Other possibility to enhance the ozonation performance is
efficiency and increasing the operating costs (Britto and Rangel,
combining the O3 with H2O2 e perozonation. The mechanism for
2008). In addition, the ozonation performance is affected by the
the formation of hydroxyl radicals is similar to those presented for
presence of organic matter, suspended solids, carbonate, bicar-
UV/O3, but in this case, hydrogen peroxide is added from an
bonate and chlorine ions and also by pH and temperature
external source. The reaction mechanism is described by
(Andreozzi et al., 1999; Gunten, 2003).
Hernandez et al. (2002):
Several studies have been developed about the ozonation
applied to waters contaminated with antibiotics. For example,
Andreozzi et al. (2005), Balcioglu and Ötker (2003), Arslan-Alaton H2 O2 þ H2 O%H3 Oþ þ HO
2 (14)
et al. (2004), Cokgor et al. (2004) and Arslan-Alaton and Caglayan
(2005, 2006) studied the degradation of b-lactams using this
O3 þ HO / HO2 þ O2 (15)
technique. They concluded that although high removal efficiencies
were achieved (COD removals > 50%), the degree of mineralisation
O3 þ HO2 / HO þ O2 þ O2

was low (z20%), even for long treatment times. All the authors (16)
studied the pH influence on the process. They all concluded that
degradation rates increased with increasing pH, as a consequence The production of hydroxyl radicals by perozonation can also
of enhanced ozone decomposition rates into free radicals, occur through reactions (17) and (18):
O3 þ O2 / O3 þ O2

(17) The production of hydroxyl radicals via direct H2O2/UV photol-
ysis (slow reaction) is also possible. The use of solar radiation
O3 þ H2O / HO þ HO þ O2

(18) constitutes an advantage since it decreases significantly the overall
costs of treatment.
This process can be used in turbid effluents, which do not occur The performance of these processes is affected mainly by pH,
with the previous system. This technique has been investigated temperature, catalyst, hydrogen peroxide and target-compound
over the past ten years. Balciog lu and Ötker (2003) studied the concentration. In fact, the pH value is an extremely important
degradation by perozonation of beta-lactams and quinolones variable in the efficiency of Fenton and photo-Fenton processes. For
antibiotics, concluding that perozonation brought no advantage pH values below 3, the Fenton’s reaction (Eq. (19)) is severely
over the ozonation. However, other authors verified that the affected, causing the reduction of hydroxyl radicals in solution.
addition of small amounts of hydrogen peroxide increased the Hydrogen peroxide is more stable at low pH, due to the formation
removal efficiency (up to 15%) and the effluents biodegradability of oxonium ions (H3O2þ), which improves its stability and,
(Arslan-Alaton and Caglayan, 2006; De Witte et al., 2009), but the presumably, greatly reduces its reactivity with ferrous ions (Elmolla
ecotoxicity was not totally removed. However, the addition of high and Chaudhuri, 2009a,b). Some authors also suggest that at low pH
concentrations of H2O2 will not improve the process efficiency, values the amount of soluble iron Fe3þ decreases, inhibiting the

since it may act as a free radical scavenger. radical OH formation. On the other hand, at pH 1e2 an inhibition of
Ozonation could be applied to fluctuating flow rates and the hydroxyl radical formation exists, due to Hþ ions scavenging
compositions. However, this process is limited by mass transfer (Lucas and Peres, 2006):
issues. So, in comparison with other oxidative methods, it requires
HO þ Hþ þ e / H2O

a greater amount of oxidant to treat the same pollutant load. The (26)
results obtained in different studies show that although high
degradation efficiencies are achieved, the mineralisation degree is For pH values above 4, the precipitation of oxyhydroxides
low and the ecotoxicity of effluents remains or even increase. In occurs, inhibiting both the regeneration of the active species Fe2þ
addition, this methodology is extremely pH-dependent, requiring and the formation of hydroxyl radicals (El-Desoky et al., 2010).
a control over the work range. For these reasons and due to the high Besides that, an excessive pH elevation promotes the HO2 ions

cost of equipment and the energy required to supply the process, formation and the scavenging of OH radicals by carbonate and
this methodology does not seem to be adequate for the contami- bicarbonate ions. This narrow pH range of operation constitutes
nated water treatment. one disadvantage, as well as, the common necessity to recover the
dissolved catalyst. The heterogeneous system fills these gaps, since
3.2.2.2. Fenton and photo-Fenton. In the 1890s, Henry John Horst- the catalyst is immobilized in a heterogeneous matrix, allowing to
man Fenton developed the Fenton’s reagent, a solution of hydrogen work in all pH range and to recover the catalyst from the treated
peroxide and ferrous ions, which has strong oxidizing properties effluent (Bobu et al., 2008).
(Gan et al., 2009). The Fenton’s oxidation can occur in homoge- Usually the increase in temperature affects positively the Fenton
neous or heterogeneous systems, although the first one has been, and photo-Fenton processes because an increase of kinetic energy
until now, the most used. occurs and consequently, the reaction rate also increases. However,
In the homogeneous oxidation, the Fenton’s reagent consists of it is also possible to occur acceleration in the hydrogen peroxide
a hydrogen peroxide solution and an iron salt catalyst (ferrous or decomposition process (Eq. (27)), decreasing the amount available
ferric ions) in acidic medium. From this reagent, hydroxyl radicals for reaction.
are formed through a radical mechanism. The main steps of the
reaction mechanism are (Andreozzi et al., 1999; Arslan-Alaton and 2H2O2 / 2H2O þ O2 (27)
Gurses, 2004; Britto and Rangel, 2008):
A decrease in the process efficiency can also take place if an
Fe2þ þ H2O2 / Fe3þ þ OH þ OH

(19) excess of hydrogen peroxide is used. The recombination of hydroxyl
radicals (Eqs. (28) and (29)) and the reaction between them and the
Fe3þ þ H2 O2 %Hþ þ FeðHO2 Þ2þ (20) hydrogen peroxide (Eq. (30)) may explain this fact.
HO þ HO / H2O2

(28)
Fe(HO2)2þ / Fe2þ þ HO2

(21)
FeOH2þ þ H2O2 / Fe(OH)(HO2)þ þ Hþ HO þ HO2 / H2O þ O2

(22) (29)
Fe(OH)(HO2)þ / Fe2þ þ HO2 þ OH

(23)
HO þ H2O2 / HO2 þ H2O

(30)
OH þ organic substance / H2O þ degradation

This kind of system is attractive because it uses low-cost

products / CO2 þ H2O (24)
reagents, iron is abundant and a non toxic element and hydrogen
peroxide is easy to handle and environmentally safe.
One way to increase the oxidation process efficiency is its
As shown in Table 2, several studies have been conducted on the
conjugation with UV radiation e photo-Fenton (González et al.,
applicability of these two techniques to different antibiotic classes:
2007; Trovó et al., 2008, 2009; Elmolla and Chaudhuri, 2009a,b;
b-lactams (Arslan-Alaton and Dogruel, 2004; Arslan-Alaton and
Bautitz and Nogueira, 2010). The use of radiation can increase the
Gurses, 2004; Trovó et al., 2008; Elmolla and Chaudhuri, 2009a,b;
efficiency of this process mainly due to the regeneration of ferrous
Rozas et al., 2010), imidazoles (Shemer et al., 2006), lincosamides
ion and the extra production of hydroxyl radicals by the photolysis
(Bautitz and Nogueira, 2007), quinolones (Bobu et al., 2008; Guinea
of ferric complexes (Eq. (25)):
et al., 2009), sulphonamides (González et al., 2007; Trovó et al.,
hn 2009; Pérez-Moya et al., 2010), tetracyclines (Bautitz and
FeOH2þ /Fe2þ þ HO (25)
Nogueira, 2007).
In all these research papers, it can be seen that although Fenton (imidazole) and they concluded that 6e12% removal was achieved.
produces good results (degradation efficiency above 53%, COD As expected, they conclude that using UV/H2O2 the removal
removal > 44%, TOC removal > 20% and a slightly increase in biode- increased for 58e67%. Shaojun et al. (2008) and Jiao et al. (2008)
gradability), the photo-Fenton seems to be more efficient (degrada- studied the degradation of tetracyclines, an antibiotic group very
tion efficiency above 74%, COD removal > 56%, TOC removal > 50%). light sensitive. They obtained high removals (about 80%), but very
Comparing at the same conditions the dark-Fenton process with low TOC removal (14%), which prove the production of intermediate
photo-Fenton, it is clear that the latter method conducts to high compounds. In their study, they also found that the toxicity of the
degradation rates, with an improvement on biodegradability and on treated effluent was higher than the original one. Shaojun et al.
mineralisation levels. Pérez-Moya et al. (2010) also concluded in their (2008) tested the influence of dissolved organic matter, particularly
tests with photo-Fenton, that toxicity increased during the first humic acids in photolysis treatment. They proved that photolysis was
reaction stages, gradually decreasing over the time. The opposite enhanced by low concentrations of these compounds. However, for
conclusion was drawn by Guinea et al. (2009), who studied the relatively high concentrations there was an inhibitory effect, since
enrofloxacin (quinolone) degradation by Fenton oxidation. They humic acids behaved as irradiation filters. Other authors studied the
concluded that the initial stages of the process were very efficient, degradation of different antibiotics belonging to other classes, such as
but the process quickly led to the formation of refractory compounds, quinolones and sulphonamides, achieving very low removals (Adams
increasing the effluent toxicity. et al., 2002; Arslan-Alaton and Dogruel, 2004) or very long reaction
Overall, the presence of UV light in the Fenton process (photo- times to obtain a high degradation (Trovó et al., 2009).
Fenton) seems to improve the treatment performance. However, Comparing this method with the others described so far, this is
photo-Fenton is generally inapplicable to wastewaters with high relatively ineffective in treating aqueous matrices contaminated
organic matter content (high concentrations of COD, such as with antibiotics. This technology is only applicable to wastewater
municipal, hospital and antibiotics manufacturing wastewaters), containing photo-sensitive compounds and waters with low COD
since the turbidity prevents the penetration of UV radiation. concentrations (e.g. river, drinking waters).
Although Fenton process produces lower removal efficiencies and
mineralisation, it seems potentially applicable to treat these 3.2.2.4. Semiconductor photocatalysis. The semiconductor photo-
matrices. Nevertheless, Fenton and photo-Fenton are both appli- catalysis started after the discovery of the photo-induced splitting
cable to matrices with low COD concentrations, but waters with of water on TiO2 electrodes. Later, researchers found that illumi-
high ions concentration (e.g. seawater) cannot be treated by these nated semiconductor particles could catalyse a wide range of redox
methods because Cl, NO3, CO32 and HCO3 are OH scavengers.

reactions of organic and inorganic substrates (Fujishima et al.,
As mentioned above, in both cases, it is important to control the pH 2007).
operation range in order to prevent the sludge formation (oxy- In semiconductor photocatalysis, the reactions of oxidative
hydroxides precipitates). degradation require the presence of three basic components:
a catalytic photo-sensitive surface (typically an inorganic semi-
3.2.2.3. Photolysis. The photolysis is the decomposition or disso- conductor, such as titanium dioxide), a source of photon energy and
ciation of chemical compounds caused by natural or artificial light. a suitable oxidizing agent (Calza et al., 2004; Addamo et al., 2005;
Two photo-induced processes are commonly applied: direct and Baran et al., 2006; Reyes et al., 2006; Hu et al., 2007; Abellán et al.,
indirect photolysis. In the first case, the organic compounds absorb 2007; Palominos et al., 2008; Klauson et al., 2010; Elmolla and
UV light and may react with the constituents of the water matrix or Chaudhuri, 2010a,b,c). The principle of this methodology involves
suffer self-decomposition (Boreen et al., 2004; Giokas and Vlessidis, the activation of a semiconductor (typically TiO2 due to its high
2007; Shaojun et al., 2008; Jiao et al., 2008; Trovó et al., 2009). stability, good performance and low cost) by artificial or sunlight.
Indirect photolysis involves the photo-degradation by photo- A semiconductor is characterized by valence and conduction bands,
sensitizers like oxygen and hydroxyl or peroxyl radicals (Arslan- and the area between them is the band gap. The absorption of
Alaton and Dogruel, 2004; Giokas and Vlessidis, 2007). These photons with energy higher than the band gap energy results in the
oxidants should be produced by photolysis of humic and inorganic promotion of an electron from the valence to the conduction band,
substances present in the water matrices or by external addition of with a concomitant hole generation in the valence band (Andreozzi
hydrogen peroxide (homolytic cleavage of hydrogen peroxide, et al., 1999; Melo et al., 2009).
producing the hydroxyl radicals) or even ozone. Although both
direct and indirect processes can occur simultaneously, indirect hn

photolysis plays the most important role in the half-life of the TiO2 /TiO2 e þ hþ (31)
contaminants (Giokas and Vlessidis, 2007).
The photolysis performance depends on the absorption spec- These holes have a very high oxidation potential, which is
trum of the target-compound, radiation intensity and frequency, enough to generate hydroxyl radicals from the water molecules or
H2O2 and O3 concentration (if used) and type of matrix (Kümmerer, hydroxide ions adsorbed on the semiconductor surface (Andreozzi
2009). Natural waters have different substances that may either et al., 1999):
inhibit or enhance the process by scavenging (organic matter) or
generating oxidant species (humic and inorganic substances like
TiO2(hþ) þ H2Oads / TiO2 þ HO ads þ H
þ

(32)
dissolved metals). This technique has proved to be less effective
that the other ones, in which radiation is combined with hydrogen
peroxide, ozone or catalysts. Photolysis under solar irradiation, TiO2(hþ) þ HO / TiO2 þ HO

(33)
ads
instead of using mercury vapour lamps (l < 280 nm), has been
considered one promising method to degrade antibiotics in natural The formed electrons can reduce the dissolved oxygen, creating
aquatic environment (Jiao et al., 2008). a superoxide radical ion (O2), which subsequently in converted
From the results summarised in Table 2, it seems that this process into H2O2 (Eq. (34)e(36)):
is extremely dependent on the chemical structure of the compound.
Only the photo-sensitive compounds are easily degraded. Shemer
TiO2(e) þ O2 / TiO2 þ O2

et al. (2006) studied the photo-degradation of metronidazole (34)
O2 þ H2O / HO2 þ HO

(35) In terms of removal efficiency, this methodology seems to be
promising for the treatment of effluents with low loads of organic
2HO2 / H2O2 þ O2

(36) matter (river, groundwater and drinking water). Although semi-
conductor photocatalysis has been studied for decades and
The hydrogen peroxide also acts as an electron receptor, numerous papers have been published, this technology has never
generating extra hydroxyl radicals, as follows: been practically applied to water/wastewater treatment due to its
very low value of electrical energy per order.
TiO2(e) þ H2O2 / TiO2 þ HO þ HO

(37)
3.2.2.5. Electrochemical processes. The electrochemical treatments
The adsorbed substrate (RXads) may be directly oxidized by are interesting processes to remove toxic organic compounds,
electron transfer: applying an effective, versatile, cost-effective, ease and clean tech-
nology (Hirose et al., 2005; Jara et al., 2007; Panizza and Cerisola,
TiO2(hþ) þ RXads / TiO2 þ RXads þ

(38) 2009). In the electrochemical processes, the oxidation occurs over
anodes (graphite, TiO2, Ti-based alloys, Ru or Ir oxides, boron-doped
Overall, the mechanism of semiconductor photocatalysis can be diamond) in the presence of an electrolyte. Pollutants can be
divided into five main steps: (1) transfer of reactants in the fluid destroyed electrochemically by a direct anodic oxidation, where
phase to the surface; (2) adsorption of the reactants; (3) reaction in pollutants are first adsorbed on the anode surface and then
the adsorbed phase; (4) desorption of the products and (5) removal destroyed through the anodic electron exchange. On the other hand,
of products from the interface region. if the molecules are degraded in the liquid bulk with mediation of
Recent studies have shown that the degradation mechanism electroactive species (such as metallic redox couples e Ag(II), Fe(III),
does not occur exclusively by means of hydroxyl radicals, but also Ce (IV), Mn (III) or strong oxidants as H2O2, O3, persulfate, percar-
through other radical species derived from oxygen. The process bonate, perphosphate and chlorinated species), which act as
performance is affected by catalyst concentration, wavelength, intermediaries for electrons transference between the electrode and
radiation intensity, pH and water matrix. This method has the the organic compounds, the reaction is classified as indirect (Chiang
advantage of being applied at ambient conditions, with an energy et al., 1995; Panizza and Cerisola, 2009). The process selection
gain when the sunlight is used as irradiation source. However, the depends on the nature and structure of the electrode material,
industrial applicability of this technology has been widely dis- experimental conditions and electrolyte composition. Usually this
cussed due to the difficulty of radiation penetration in an aqueous kind of system is used to prevent electrode fouling.
solution containing a suspension of opaque fine particles and the The efficiency of the direct oxidation depends on the electrode
difficulty to remove the catalyst at the end of the process (Britto and catalytic activity, diffusion rates of the compounds towards the
Rangel, 2008). This phase separation process can be time active sites of the anode and the applied current, while the indirect
consuming and costly. As a result, filtration and re-suspension of oxidation strongly depends on the diffusion rate of secondary
photocatalyst powder should be avoided. To overcome these oxidants into the solution, temperature and pH (Saracco et al.,
problems, studies on semiconductors immobilization have been 2000; Jara et al., 2007).
performed. Diverse materials have been studied as a TiO2 support. According to the authors’ best knowledge, only two papers were
From the practical point of view, the ideal support should have written on the applicability of electrochemical oxidation to anti-
strong adherence to the catalyst, a high specific surface area, strong biotics. Hirose et al. (2005) studied the epirubicin (anthracycline),
adsorption affinity towards the contaminants and the attachment bleomycin (glycopeptides) and mitomycin C degradation and
process should not affect the catalyst reactivity (Shan et al., 2010). concluded that only epirubicin was mostly removed. The other
Studies about the attachment of photocatalyst particles onto study was developed by Jara et al. (2007), who tested the linco-
supports that are easily removable, such as glass, silica gel, metal, mycin (lincosamide) and ofloxacin (quinolone) degradation. The
ceramics, polymer, zeolite, alumina clays, activated carbon have first compound was hardly oxidized (30%), while the other one was
been developed. The semiconductors immobilized systems have totally removed (>99%). As in the previous case, no studies were
the disadvantage of suffering from mass transfer limitation due to developed about effluent mineralisation.
the reduction in specific surface when compared with the tradi- These kinds of processes seem suitable to treat toxic wastewa-
tional systems (Shan et al., 2010). ters with high concentrations of both antibiotics and COD (such as
Diverse authors studied the application of this method to manufacturing wastewaters). However, the applicability of this
different antibiotic classes and they concluded that semiconductor technology is limited to small flow rates. Moreover, the high
photocatalysis was very efficient. Klauson et al. (2010) and Elmolla operating cost of the reactor is also a drawback.
and Chaudhuri (2010a,b,c) studied the application of this tech-
nique to b-lactam antibiotics, concluding that degradations above 3.3. Adsorption processes
50% occur, associated with high removal dissolved organic carbon
(z80%). The sulfonamides degradation was also studied by several Adsorption processes are widely used in industry to remove
authors (Calza et al., 2004; Kaniou et al., 2005; Baran et al., 2006; organic contaminants. The term adsorption is commonly used to
Abellán et al., 2007; Hu et al., 2007). They concluded that high describe the tendency of the molecules in fluid phase have to adhere
removals can be achieved using this methodology (>80%) and they to a solid surface. The force field creates a region near the solid surface,
are often accompanied by important mineralisation levels (40e70% whose potential energy is low, resulting in the molecular density
TOC removal). The produced intermediate compounds were less increase near the surface. The adsorption phenomenon involves the
toxic and more biodegradable than the parent compounds. Addamo following steps: (i) solute transport in the bulk e adsorbate move-
et al. (2005), Reyes et al. (2006) and Palominos et al. (2009) studied ment by the stagnant liquid film surrounding the adsorbent, (ii) film
the tetracycline degradation. As in the previous cases, the degra- diffusion e adsorbate transport along the film, (iii) pores diffusion e
dation rates were high (>98%), as well as mineralisation (>50%). The adsorbate diffusion through the porous structure to the active sites
same conclusions were withdrawn by Addamo et al. (2005), (molecular diffusion in the pore and/or in the adsorbent surface), (iv)
Palominos et al. (2008) and Chatzitakis et al. (2008), who studied adsorption e interaction between adsorbate and porous structure.
lincosamides, quinolones and chloramphenicol. Depending on the nature of the forces involved, the process can be
divided in chemical adsorption or physical adsorption. In the last one, adsorption with low-cost alternative materials and continuous
the forces are relatively weak, involving mainly van der Waals inter- systems (packed columns) exists.
actions. In the cases of chemical adsorption, the electron transfer and
chemical bonds formation between adsorbate and solid surface 3.4. Membrane processes
occurs. These interactions are strong and more specific than those
existent in physical adsorption and they are obviously limited to the The membrane processes are increasingly used as separation
monolayer coverage (Ruthven, 2000). processes. However, this technology does not enable the removal or
This technique has the advantage of removing the analytes degradation of the contaminant, but only its transference to
instead of producing potentially more dangerous metabolites a new phase (the membrane), where it is present in a more
(Putra et al., 2009; Rivera-Utrilla et al., 2009). However, this process concentrated form.
does not enable the effective removal of the contaminants, but only
its transference to a new phase, where they are more concentrated. 3.4.1. Reverse osmosis, nano and ultrafiltration
The adsorption efficiency is related with the adsorbent proper- The reverse osmosis constitutes one of the membrane processes
ties, namely surface area, porosity and pore diameter (Estevinho (Li et al., 2004; Kosutic et al., 2007; Radjenovic et al., 2008). This
et al., 2007). It is also important to notice that the process effec- diffusion method is usually applied to remove large molecules and
tiveness is dependent not only on the trace compounds of concern ions from liquid effluents, applying pressure to the solution on one
or even the adsorbent materials, but also on dissolved naturally side of a selective semipermeable membrane. The contaminants
occurring organic matter present in any natural water. A major are retained in the pressurized side of the membrane and the clean
effect of the organic matter is its direct competition for the avail- effluent passes to the other side. In reverse osmosis the flow occurs
able adsorption surface/sites (Qui et al., 2007). against the concentration gradient. This technology is efficient to
The most used adsorbents are granular activated carbons (GACs), reduce high levels of dissolved salts, but has limitations in the
but their high cost and difficulty of regeneration are disadvantages removal of organic compounds.
(Crisafully et al., 2008). Therefore, the interest for alternative Reverse osmosis membrane separations are mostly governed by
adsorbents grows up with the purpose of finding new low-cost the properties of the membrane used in the process, which depend
adsorbents, as by-products or waste materials from industrial or on its chemical nature and physical structure (porosity, mechanical
agricultural processes. Hazelnuts (Pehlivan and Altun, 2008; Bulut resistance, etc.). Therefore, these membranes should be resistant to
and Tez, 2007; Kazemipour et al., 2008), coconut (Crisafully et al., chemical and microbial attack, mechanical and structural stable
2008), walnut (Kazemipour et al., 2008), almond shells (Pehlivan over long operating periods (Meyer et al., 2003). So, polymeric
and Altun, 2008; Bulut and Tez, 2007; Estevinho et al., 2008; membranes are chosen.
Ardejani et al., 2008; Kazemipour et al., 2008) and others have This kind of process does not require thermal energy, but only
been used for this purpose applied to different contaminants. Some an electrically driven feed pump; they are simple and have high
of these adsorbents require a previous activation treatment (such as energy efficiency. However, reverse osmosis has disadvantages. The
chemical or thermal activation) in order to increase their surface membranes can be easily fouled or damaged and they are suscep-
areas and consequently, the adsorption efficiency. Batch systems tible to be attacked by oxidizing agents. As mentioned above, the
remain the most studied processes. However, only continuous small pores in the membrane block large molecules, but small
processes (packed columns) should be more similar to those chemicals can pass through the porous membrane. For this reason,
employed for treatments at industrial scale and will provide a real carbon filters are often used as a complimentary technique to
insight into the applicability of this technology. reverse osmosis (Binnie et al., 2002). Besides that, reverse osmosis
Although adsorption is a well-known process, in the past ten is a slow process when compared to other techniques.
years the study of this technology applied to antibiotics removal As reverse osmosis, nanofiltration and ultrafiltration are
has not been much extended. Adams et al. (2002) and Méndez-Díaz membrane processes (Li et al., 2004; Kosuti c et al., 2007; Koyuncu
et al. (2010) studied the batch adsorption on activated carbon of et al., 2008; Radjenovi c et al., 2008). They are cross-flow filtrations,
imidazoles and sulphonamides with trimethoprim, respectively. In in which the process takes place on a selective separation layer
these two studies about 90% removal was achieved. A similar study formed by an organic semipermeable membrane. Nano and ultrafil-
was developed by Kim et al. (2010), but they investigated whether tration membranes are usually charged (carboxylic groups, sulfonic
batch or continuous adsorption of trimethoprim, obtaining also groups) and, as a result, ion repulsion is the main factor in this process.
removals above 90%. Putra et al. (2009) compared the adsorption The driving force of the separation process, like in reverse osmosis, is
capacity of activated carbon and bentonite, using amoxicillin the pressure difference between the feed and the filtrate side at the
(a beta-lactam antibiotic). As in the previous cases, high removal separation layer of the membrane (Kosuti c et al., 2007). These tech-
efficiencies were achieved (95% for activated carbon and 88% for niques are able to remove smaller molecules. The size of the retained
bentonite). Chen and Huang (2010) analysed the adsorption of molecules represents the difference between these two processes.
three tetracyclines antibiotics on aluminium oxide. They concluded There are different studies about reverse osmosis, nano and
that these compounds were adsorbed (>50%) and besides that, ultrafiltration applied to the antibiotics removal. In most studies,
they suffer structural transformations along the process. Therefore, the percentage removal obtained for different membrane types was
aluminium oxide was capable to catalyse structural trans- higher than 90% for all the antibiotic classes studied (Adams et al.,
formations, phenomenon that was not recognized previously. 2002; Kosutic et al., 2007; Li et al., 2004; Radjenovi c et al., 2008).
These studies revealed that adsorption continues to be an Koyuncu et al. (2008) obtained the lowest values for the removal of
effective method to remove antibiotics from aqueous effluents. tetracyclines (50e80%) and sulphonamides (11e20%).
Unlike some of the processes mentioned so far, adsorption can be As in adsorption, these techniques produce a new solid residue
applied to waters containing either high levels of organic matter, or (membrane), where the contaminant is concentrated. So far, these
high antibiotic concentrations. However, in this process only occurs techniques have been mostly used in combination with other
the contaminant transference from the liquid to the solid phase, methodologies. Reverse osmosis, nano and ultrafiltration are
producing a new solid residue, where the contaminant is concen- sensitive processes to temperature (this parameter significantly
trated. This solid waste should be subsequently treated (e.g incin- affects feed pump pressure, the hydraulic flux balance between
eration). In the author’s opinion, a great publication lack on stages and solubility of the dissolved salts in the effluent), organic
Fig. 2. (A) Most studied antibiotic classes (results according to Table 2) and (B) most prescribed antibiotic classes in 2010.
material occurring naturally in the water matrices and the In the context of antibiotics removal, ion exchange is a technique
concentration of the dissolved salts. The occurrence of high rarely used. Besides ion exchange consists of a phase transfer
concentration levels of these compounds can cause membrane process (production of a new residue), this method is only effective
structure deterioration or fouling. if the antibiotics to be removed possess ionisable groups in its
structure.
3.4.2. Ion exchange
Ion exchange is a process in which cations or anions in a liquid 3.5. Combined processes
medium are exchanged with cations or anions on a solid sorbent. In
this process the cations are exchanged with other cations, anions Considering that treatment processes must be applied indus-
with other anions, and electroneutrality is maintained in both trially, it is necessary to study the process integration to maximize
phases (Choi et al., 2007). The exchange membranes can be clas- the treatment performance. Therefore, combined processes have
sified in anion or cation exchangers. The first one contains posi- been developed.
tively charged groups (eNH3þ, eNRH2þ, eNR2Hþ, eNR3þ) fixed to In some cases, the degradation or removal processes can/should
the membrane and allows the passage of anions, but reject cations. not be applied alone. This is the case of biodegradation because
The cation exchange membranes contain negatively charged most microorganisms are sensible to the toxic pollutants. Thus,
groups (eSO3, eCOO, ePO32) and allow the passage of cations, AOPs have been applied as a pre-treatment step, in which the
rejecting anions. Depending on their preparation, the membranes pollutants are oxidized to by-products that are easily biodegradable
could be classified into homogeneous or heterogeneous. If the and less toxic, preventing the death of microorganisms that are
charged groups are chemically bonded to the membrane matrix, present in the subsequent biological treatments (Tekin et al., 2006).
the membrane is homogeneous. On the other hand, if the charged The same situation occurs with the reverse osmosis, which is
groups are physically mixed with the membrane matrix, they are applied in combination with carbon filters. The use of adsorption as
heterogeneous (Xu, 2005). The most used membranes are the pre-treatment, with subsequent treatment by AOPs is also frequent
polymeric (styrenic and acrylic resins) because they usually have (Klavarioti et al., 2009).
both chemical and mechanical stability and great permselectivity Zhang et al. (2006) studied the combination of Fenton with
(Dickert, 2007). Ion exchange membranes can also be prepared reverse osmosis in the removal of amoxicillin. First of all, the authors
from inorganic materials such as zeolites, betonite or phosphate used a liquideliquid extraction to remove several organic
salts. However, these membranes are too expensive, have bad compounds (with this step 50% TOC removal was achieved). After
electrochemical properties and have frequently large pores (Xu, that, Fenton oxidation was performed, improving the degradation
2005; Nagarale et al., 2006). (TOC removal of 38%). Finally, the authors used a reverse osmosis
The ion exchange systems have been used to improve water system, reaching 11% TOC removal and an enhancement in the
quality. Nevertheless, this kind of technique has disadvantages such effluent biodegradability. The overall TOC removal was 99%.
as the necessity of backwashing and regeneration. Another problem is Sánchez-Polo et al. (2008) investigated the simultaneous application
the appearance of fouling, which constitutes most of times an irre- of ozonation and adsorption in the removal of imidazoles. With
versible fixation of organic materials to the resin (Üstün et al., 2007). a simple ozonation the authors achieved 90e100% degradation and
One advantage is that ion exchange is a reversible process, allowing 10e20% mineralisation and they also concluded that by-products
extended use of the adsorbent resin before replacement is necessary. generated were highly toxic. The presence of activated carbon
In this process, semi-continuous columns are often used instead of during the ozonation process besides increasing the removal rate
batch systems. As mentioned above, ion exchange systems have the also reduces the by-products toxicity and the TOC removal in about
disadvantage of requiring resin regeneration. For this reason, the 30%. This combined process enables the treatment of water matrices
systems are usually designed with multiple units in parallel to ensure with a high content of organic matter (municipal wastewater),
a continuous flow, when one or more columns require regeneration. which would not be possible if ozononation was applied alone.
The authors found only two papers using ion exchange as Ötker and Akmehmet-Balciog lu (2005) also studied the
a removal method of antibiotics. Adams et al. (2002) studied the combination of these two techniques for the removal of enro-
applicability of a polymeric resin to remove trimethoprim, carba- floxacin (quinolones). 80% of the compound was adsorbed and the
dox and sulphonamides, concluding that this methodology was ozonation was able to completely degrade enrofloxacin adsorbed
ineffective. On the other hand, Choi et al. (2007) also studied the on zeolite. Augugliaro et al. (2005) studied the removal of linco-
use of other polymeric resin for the removal of sulphonamides and mycin (lincosamide) by semiconductor photocatalysis coupled with
tetracyclines. They obtained high removal efficiencies (90% for nanofiltration. Lincomycin was successfully oxidized (100% degra-
sulphonamides and >80% for tetracyclines), but some organic dation) and the filtration allowed separation of the photocatalyst
interferences were detected. particles and the degradation products from permeate. A similar
Fig. 3. Comparison between the most studied methods (A) and the most applied methodology for each class (B) between the years 2000 and 2010.
study was performed by Molinari et al. (2006) with quinolones. 66% the most applied to the b-lactam class (the mainly prescribed
degradation was achieved by photocatalysis, while filtration only antibiotics).
separates the catalyst particles from the treated effluent. Sirtori
et al. (2009) studied the degradation of quinolones by solar
photo-Fenton combined with biological treatment. The global 5. Conclusions
efficiency of dissolved organic carbon removal was 95%, of which
33% for solar photo-Fenton and 62% for biological treatment. Total In the last years, the presence and fate of antibiotics in envi-
degradation of antibiotic was achieved, with 90% mineralisation. ronmental matrices have received a special attention by the
The application of photo-Fenton as a preliminary method allows scientific community. These compounds are persistent and resis-
increasing the effluent biodegradability, enabling the subsequent tant to biodegradation, accumulating in the environment. Even at
use of biological treatment. low concentration levels, in which they are detected, they can
Despite that combined methods are not a very common practice, produce harmful effects either in aquatic or terrestrial ecosystems.
they are one of the most powerful processes for the antibiotics For these reasons, several degradation/removal processes have
removal from the environment. been studied to solve environmental contamination issues.
Most conventional treatments applied in WWTPs and DWTPs
(such as coagulation, flocculation, sedimentation and filtration)
4. Assessment of the remediation techniques were unsuccessful in the removal of these compounds (Vieno et al.,
2007; Adams et al., 2002; Göbel et al., 2007), requiring the devel-
Remediation techniques are employed for the removal of opment of new efficient methodologies. Due to the recalcitrant
contaminants from environmental media, for the general protection nature of the effluents containing antibiotics residues, the appli-
of human health and ecosystems. As mentioned above, Table 2 cation of the advanced oxidation processes (AOPs) emerge as an
provides an overview of the works published in international jour- alternative. Actually, ozonation and Fenton’s oxidation are the most
nals in this area, illustrating the most studied antibiotic classes. tested methodologies. Although ozonation has the advantage of
Based on this research work, it was verified that b-lactams and being applied to fluctuating flow rates and compositions, the high
sulfonamides antibiotics classes were the most studied (Fig. 2A). cost of equipment and the energy required to supply the process
However, in accordance with the European Surveillance of constitutes major drawbacks. Several studies report that this
Antimicrobial Consumption (2010) and Muller et al. (2007) the technique is effective in the antibiotics removal. However, low rates
most prescribed antibiotics in Europe were the b-lactams, lincosa- of mineralisation are achieved even for long treatment times and
mides and macrolides (Fig. 2B). the ecotoxicity of the treated effluents remains practically
A similar study was conducted in order to ascertain which unchanged or even worse, indicating the production of metabolites
methods of degradation and removal were most studied and from that are more toxic than the parent compounds (Balciog lu and
these, which were more applied to each class of antibiotics (Fig. 3). Ötker, 2003; Cokgor et al., 2004; Andreozzi et al., 2005; Dantas
Ozonation, Fenton/photo-Fenton and semiconductor photo- et al., 2008; Li et al., 2008). This method has also been applied to
catalysis were the most methodologies tested so far. They were also the most prescribed class of antibiotics, obtaining the same
conclusions (Balciog lu and Ötker, 2003; Arslan-Alaton et al., 2004; Adams, C., Asce, M., Wang, Y., Loftin, K., Meyer, M., 2002. Removal of antibiotics
from surface and distilled water in conventional water treatment processes.
Cokgor et al., 2004; Andreozzi et al., 2005; Arslan-Alaton and
J. Environ. Eng. 128, 253e260.
Caglayan, 2005, 2006). As discussed above, besides ozonation, Addamo, M., Augugliaro, V., Di Paola, A., Gracía-López, E., Loddo, V., Marcí, G.,
Fenton’s oxidation is one of most studied AOPs. When applied as Palmisano, L., 2005. Removal of drugs in aqueous systems by photoassisted
a homogeneous process (more common case), the production of degradation. J. Appl. Electrochem. 35, 765e774.
Andreozzi, R., Caprio, V., Insola, A., Marotta, R., 1999. Advanced oxidation processes
oxyhydroxides precipitates (if the pH operation range is not well (AOP) for water purification and recovery. Catal. Today 53, 51e59.
controlled) and the necessity to recover the dissolved catalyst Andreozzi, R., Canterino, M., Marotta, R., Paxeus, N., 2005. Antibiotic removal from
constitute disadvantages. This is another process often applied to wastewaters: the ozonation of amoxicillin. J. Hazard. Mater. 122, 243e250.
Ardejani, F.D., Badii, K., Limaee, N.Y., Shafaei, S.Z., Mirhabibi, A.R., 2008. Adsorption
the group of beta-lactam antibiotics, especially when combined of direct red 80 dye from aqueous solution onto almond shells: effect of pH,
with UV irradiation (photo-Fenton). In these cases, a complete initial concentration and shell type. J. Hazard. Mater. 151, 730e737.
degradation was achieved, accompanied by an increase in the TOC Arikan, O.A., 2008. Degradation and metabolization of chlortetracycline during the
anaerobic digestion of manure from medicated calves. J. Hazard. Mater. 158,
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effluent biodegradability (Trovó et al., 2008; Elmolla and Arslan-Alaton, I., Caglayan, A.E., 2005. Ozonation of procaine penicillin G formula-
Chaudhuri, 2009a,b). Therefore, this seems to be a promising tion effluent. Part I: Process optimization and kinetics. Chemosphere 59, 31e39.
Arslan-Alaton, I., Caglayan, A.E., 2006. Toxicity and biodegradability assessment of
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Adsorption is another process that has been reported as an Environ. Saf. 63, 131e140.
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Arslan-Alaton, I., Gurses, F., 2004. Photo-Fenton-like and Fenton-like oxidation of
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Journal of Environmental Management 92 (2011) 2304e2347

Contents lists available at ScienceDirect

Journal of Environmental Management

Degradation and removal methods of antibiotics from aqueous

* Corresponding author. Traditionally antibiotics are deﬁned as chemical compounds

Class Core structure

They are heterocyclic compounds of 5 member R1

Class Core structure

Class Core structure

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

(continued on next page)

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

V. Homem, L. Santos / Journal of Environmental Management 92 (2011) 2304e2347

FeOH2þ þ H2O2 / Fe(OH)(HO2)þ þ Hþ HO þ HO2 / H2O þ O2

Fe(OH)(HO2)þ / Fe2þ þ HO2 þ OH

This kind of system is attractive because it uses low-cost

O2 þ H2O / HO2 þ HO

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