Arabian Journal of Chemistry (2014) xxx, xxx–xxx

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
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SPECIAL ISSUE: ENVIRONMENTAL CHEMISTRY

Photocatalysis of b-blockers – An overview

Marothu Vamsi Krishna a,*, Gorrepati Madhavi b, Nagi F. Idris c,
Salah Ali M. Idris d, Lella Ravi Kiran Chowdary e

a
Faculty of Pharmacy, Omar Al-Mukhtar University, Tobruk, Libya
b
University College of Pharmaceutical Sciences, Acharya Nagarjuna University, Nagarjuna Nagar, India
c
Faculty of Pharmacy, Omar Al-Mukhtar University, Al-Beida, Libya
d
Department of Chemistry, Faculty of Science, Omar Al-Mukhtar University, Tobruk, Libya
e
Alliance Institute of Advanced Pharmaceutical and Health Sciences, Hyderabad, India

Received 12 July 2013; accepted 29 October 2014

KEYWORDS Abstract Photocatalysis is one of the most effective advanced oxidation processes to remove resid-
Photocatalysis; ual pharmaceuticals from the aquatic environment. b-Blockers are the group of pharmaceuticals
b-Blockers; commonly found in the environment and are showing potential risk to the aquatic and terrestrial
Aquatic environment organisms. This paper provides an overview of different photocatalytic procedures found in the lit-
erature for the abatement of b-blockers.
ª 2014 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

1. Introduction metoprolol (Christensen et al., 2009; Fent et al., 2006; Maurer

et al., 2007).
Beta (b)-blockers are a class of drugs used to treat a variety of The presence of active pharmaceutical ingredients (APIs) in
cardiovascular diseases, such as hypertension, coronary artery the aquatic environments was reported as early in the 1980s
disease and cardiac arrhythmias, by blocking the action of (Richardson and Bowron, 1985). It is an emerging environ-
adrenaline and noradrenaline on the b-adrenergic receptors mental issue and provides a new challenge to drinking water,
in the body, primarily in the heart (Maurer et al., 2007). The wastewater and water reuse treatment systems (Ikehata et al.,
most commonly used b-blockers are atenolol, propranolol 2006). The most important sources of pharmaceutical com-
and metoprolol, and the structures of those are shown in pounds in the environment are APIs administered to the
Fig. 1. Propranolol was the first clinically successful b-blocker patient’s excreted either as metabolites or as the unchanged
developed (De la Cruz et al., 2013) and it has the highest acute parent compounds, hospitals, pharmaceutical industry waste,
and chronic toxicity within the class of b-blockers followed by and rejected drugs from households, waste water treatment
plants and intensive animal breeding farms (Fatta et al.,
* Corresponding author. Tel.: +218 944828805. 2007). Pharmaceutical residues have been detected in many
E-mail address: [email protected] (V.K. Marothu). environmental matrices worldwide at concentrations ranging
Peer review under responsibility of King Saud University. from ng/L to lg/L (Benner et al., 2009; Nicolaou et al.,
2007; Santos et al., 2009; Ternes and Joss, 2006).This is of
great concern in particular because of their potential impact
on terrestrial and aquatic ecosystems and public health
Production and hosting by Elsevier
(Bendz et al., 2005; Cleuvers, 2005; Sharma, 2008).
http://dx.doi.org/10.1016/j.arabjc.2014.10.044
1878-5352 ª 2014 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
Please cite this article in press as: Marothu, V.K. et al., Photocatalysis of b-blockers – An overview. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/
j.arabjc.2014.10.044
2 V.K. Marothu et al.

which oxidize and mineralize all the organic compounds.

Among AOPs, photocatalysis is an effective, low cost, environ-
mental friendly and sustainable treatment technique. This
process is based on the interaction of light and a semiconduc-
tor (catalyst). The most effective photocatalyst for this purpose
is titanium dioxide (TiO2) (Malato et al., 2002). A photon with
energy higher than TiO2 band gap (3.2 eV for anatase and
3.0 eV for rutile) arrives to the catalyst surface, an electron is
photo excited from the valence to the conduction band;
the wavelength range with energy higher than TiO2 band gap
is k < 390 nm. This mechanism generates electron–hole pairs
on the semiconductor surface which lead to a chain of redox
reactions related to organic contaminants degradation
(Fig. 2) (Chong et al., 2010). The photocatalytic oxidation of
an organic species often proceeds via adsorption of the
contaminant on the surface of the catalyst, followed by direct
subtraction of the contaminant’s electrons by positively
charged holes. Another possible way is oxidation with OH rad-
Figure 1 Chemical structures of (i) atenolol (ii) metoprolol (iii) icals, generated from water of the aqueous environment, which
propranolol. takes place at the catalyst surface or in its vicinity. Both
reactions may proceed simultaneously and which mechanism
dominates depends on the chemical and adsorption properties
The occurrence of b-blockers has been repeatedly reported of the contaminant. This review article provides an overview of
in recent years in the effluents of many wastewater treatment different photocatalytic procedures found in the literature for
plants around the world (Brun et al., 2006; Carlsson et al., the abatement of b-blockers in the aquatic environment.
2009; Conkle et al., 2008; Gabet-Giraud et al., 2010; Huggett
et al., 2003; Joakim Larsson and Fick, 2009; Liu and 2. Photocatalytic works on b-blockers
Williams, 2007; Nikolai et al., 2006; Sacher et al., 2001;
Ternes, 1998). These compounds are persistent against biolog- Yang et al. (2010) performed photocatalytic degradation kinet-
ical degradation and natural attenuation, and therefore, may ics of three b-blockers (atenolol, metoprolol and propranolol)
remain in the environment for a long time. Conventional in aqueous solution using Pyrex reactor. The light source used
wastewater treatment using activated sludge (Paxeus, 2004) is was high pressure mercury lamp and the photocatalyst was
not effective in removing these compounds completely. The Degussa P25 (commercial TiO2 powder). The three drugs were
promising technology for the treatment of wastewaters con- completely degraded within 40 min irradiation, using a TiO2
taining pharmaceuticals is advanced oxidation processes concentration of 2.0 g/L. The degradation of the three drugs
(AOPs) (Dantas et al., 2011; Klavarioti et al., 2009). These followed pseudo-first-order kinetics and degradation occurred
techniques are based on the generation of hydroxyl radicals, mainly on the surface of TiO2 by oxidation reactions with

Figure 2 Principles of photocatalysis using TiO2.

Please cite this article in press as: Marothu, V.K. et al., Photocatalysis of b-blockers – An overview. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/
j.arabjc.2014.10.044
Photocatalysis of b-blockers 3

i = the number of aromatic rings, and R = the substituted group on aromatic ring. atenolol: i = 1,
R = NH2COCH2-,; metoprolol: i = 1, R = CH3OCH2 CH2-,; propranolol: i = 2, R = H.

Figure 3 General scheme of degradation pathways for b-blockers (Yang et al., 2010).

photohole (h+) or OH radicals. Degradation intermediates benzaldehyde through ether chain cleavage, hydroxylation
were completely mineralized to CO2 and nitrogen (predomi- and loss of CONH2 from acetamide function group respectively.
nantly as NH3/NH+ 4 ) within 240 min. The major degradation Hydroxy radical (HO) was the predominant reactive species
pathways for the three b-blockers were cleavage of side chain involved in the photocatalytic degradation of atenolol. Possible
(–CH (OH) CH2 NH CH (CH3)2) and addition of –OH group photocatalytic degradation pathways of atenolol are shown in
to the parent compound. General scheme of degradation path- Fig. 4. Intermediates formed during the photocatalysis further
ways for b-blockers is shown in Fig. 3 (Yang et al., 2010). oxidized to five carboxylic acids namely oxalic, glyoxylic,
Ioannou et al. (2011) investigated decomposition of malonic, oxamic and formic acid. In the river water atenolol
b-blockers (atenolol and propranolol) by means of TiO2 degradation was slow due to the presence of inorganic ions
photocatalysis using solar simulator in water and wastewater. and natural radical scavengers (Cl , CO23 , HCO3 and dis-
Irradiation was provided by a 1 Kw Xe-OP lamp and photo- solved organic matter). Inorganic ions compete for the active
catalyst used was Degussa P25. Different commercially sites on the TiO2 surface or they form salt layer on the TiO2
available TiO2 catalysts (Degussa P25, Hombicat UV100, surface and reducing/blocking the accessibility of catalyst and
Aldrich, Tronox AK-1, Tronox TRHP-2, Tronox TR) were substrate (atenolol). Natural radical scavengers present in the
used in the study and found that Degussa P25 is showing river water reduce the HO concentration and thereby decreas-
higher photocatalytic activity. This is due to its structure which ing the photocatalytic efficiency.
is a mixture of anatase and rutile, and slower electron/hole Romero et al. (2011) investigated the degradation of meto-
recombination on the surface of Degussa P25. After 120 min prolol and propranolol by photocatalysis. Photocatalytic
of irradiation with Degussa P25 80% of the drug was decom- experiments were carried out with 0.4 g/L of TiO2 as catalyst,
posed. Degradation was favored in pure water compared with 50 mg/L of both drugs and xenon lamp as irradiation source.
the wastewater because the latter contains dissolved organic Metoprolol and propranolol were completely removed after
carbon (DOC) and radical scavengers which show detrimental 300 and 360 min of irradiation, respectively. Biodegradability
effect on conversions. and toxicity tests were performed to assess the suitability of
Toxicity of atenolol and propranolol before and after the the photocatalytic treatment. Untreated samples were not bio-
photocatalytic treatment was evaluated by using Daphnia degradable and treated samples were biodegradable through
magna. Toxicity increased during the early stages of photocat- oxidation promoted by hydroxyl radicals. Biodegradability
alytic treatment for either substrate and then gradually of the metoprolol was faster compared with the propranolol.
decreased on prolonged treatment due to elimination of the Acute toxicity of both compounds prior and after the treat-
substrate and its toxic reaction intermediates. ment was determined by measuring the inhibition of Vibrio
Ji et al. (2013) investigated photocatalytic degradation of fischeri bioluminescence. Toxicity of the metoprolol was
atenolol in pH 6.8 Milli-Q water and river water using TiO2 as reduced from the beginning of the treatment but for propran-
catalyst. Efficiency of the four different TiO2 catalysts (Hombi- olol more toxic intermediates than the primary compound
cat UV100, Millennium PC500, Aldrich rutile and Degussa P25) were formed in the early-stage of reaction, after 30 min of
was also investigated. Degussa P25 exhibited the highest photo- irradiation, the toxicity was decreased continuously.
catalytic activity. Complete degradation of atenolol was De la cruz et al. (2013) assessed the propranolol degrada-
obtained after 60 min and 180 min of irradiation in pH 6.8 tion by direct photolysis and TiO2 photocatalysis using solar
Milli-Q water and river water, respectively. Atenolol was and artificial (Xe-lamp) light. In this study photo-reactors
degraded to 3-(isopropylamino)propane-1,2-diol, p-hydroxyph- made with quartz and Duran were tested and found that
enylacetamide and 4-[2-hydroxy-3-(isopropylamino)propoxy] quartz reactor given significant propranolol degradation. In

Please cite this article in press as: Marothu, V.K. et al., Photocatalysis of b-blockers – An overview. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/
j.arabjc.2014.10.044
4 V.K. Marothu et al.

Figure 4 Photocatalytic degradation pathways for atenolol in aqueous TiO2 suspensions (Ji et al., 2013).

the direct photolysis, after 240 min of irradiation 77% and This study indicates that photocatalyst with highest BET sur-
71% of the drug was degraded by the solar plant and the lab- face area (T3) revealed the highest activity and lowest BET
oratory device (artificial light), respectively. Mineralization surface area (T2) revealed the lowest activity in metoprolol
observed was 7% in the solar plant and 2% in the laboratory photocatalytic oxidation.
device. Ji et al. (2012) investigated the nitrate-induced photolysis
In the photocatalysis treatment, concentration of TiO2 used behavior of atenolol and toxicity of its degradation products.
was 0.4 g/L and the degradation observed after 240 min of Photolysis experiments were conducted under simulated solar
irradiation was 81% for the solar plant and 94% for lab irradiation using 1000 W Xe arc lamp. Influence of pH, bicar-
device. Meanwhile mineralization reached was 30% and 41% bonate concentration and dissolved organic matter (DOM)
in solar plant and laboratory device, respectively. was also studied. Increase in the nitrate concentration
This study shown that photocatalysis is better than the pho- increases the rate of reaction due to generation of hydroxyl
tolysis in the propranolol degradation and mineralization. radicals upon irradiation of nitrate solution.
Mineralization was negligible in the photolysis compared with Increase in pH decreases the reaction rate of atenolol by
the photocatalysis because there are no other photosensitive decreasing the rate of generation of hydroxyl radicals during
compounds in water to generate hydroxyl radicals which are irradiation of nitrate. Increase in bicarbonate concentration
main reactive species for propranolol removal. decreases the photodegradation rate of atenolol due to increase
Rivas et al. (2010) investigated the efficiency of several in pH and hydroxyl radical scavenging effect.
UV-C radiation based methods for the mineralization of meto- The presence of DOM decreases the photolysis rate con-
prolol. Mineralization was performed by means of UV-C, stant; this is due to competition between DOM and nitrate
UV-C/H2O2, UV-C/percarbonate, UV-C/monopersulphate, ions for the photons. Less number of photons is available
UV-C/TiO2, UV-C/H2O2/TiO2 and photo-Fenton (Fe2+ and for exciting nitrate and thereby decreased the generation of
H2O2) reagent. Under UV-C radiation mineralization degree hydroxyl radicals. During the photocatalysis process atenolol
was negligible; addition of free radical promoters/photocata- and its degradation products were monitored by HPLC and
lysts significantly increases the degradation rate. Among the LC–MS. The major pathways of atenolol degradation were
tested systems photo-Fenton reagent showed maximum hydroxylation and side chain cleavage .The toxicity of the
efficiency (70% mineralization) due to three simultaneous phototransformation products was evaluated by using
actions in the process, direct photolysis, H2O2 photolysis and Daphnia magna and the results revealed that they are less toxic.
Fenton’s reagent. This study suggested that photodegradation was an important
Czech and Rubinowska (2013) investigated the photocata- pathway for atenolol toxicity reduction in natural water
lytic degradation of metoprolol in the tube reactor using four containing relatively high concentration of nitrate.
different commercially available TiO2 samples (TiO2-Tytanpol Rey et al. (2012) prepared and characterized a TiO2 mag-
(T1), TiO2-Sigma–Aldrich (T2), Hombikat-Sigma–Aldrich netic activated carbon catalyst to mineralize metoprolol tar-
(T3) and TiO2-S21-Sigma–Aldrich (T4)) differed in specific trate. The photocatalytic activity of the TiO2 magnetic
surface area, pore volume and rutile presence. Brunauer– activated carbon catalyst was tested by performing degrada-
Emmett–Teller (BET) surface areas (m2/g) of T1, T2, T3 and tion of metoprolol (Initial Concentration: 10 and 50 mg/L)
T4 were 12.08, 11.50, 61.03 and 55.33, respectively. Metoprolol under simulated solar photocatalytic ozonation. The results
was most effectively removed by T3 and least effectively by T2. obtained were compared with those obtained from the

Please cite this article in press as: Marothu, V.K. et al., Photocatalysis of b-blockers – An overview. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/
j.arabjc.2014.10.044
Photocatalysis of b-blockers 5

experiments of single adsorption (i.e., absence of radiation and constitute bioluminescence of V. fischeri. Toxicity study
ozone), single ozonation (i.e., absence of radiation and cata- revealed that, degradation of propranolol in ultrapure water
lyst), catalytic ozonation (i.e., absence of radiation), photolytic showed toxicity in the early stage of irradiation treatment
ozonation (i.e., absence of catalyst), TiO2 photocatalysis (i.e., due to accumulation of transformation products but in case
absence of ozone) and photocatalytic ozonation with Degussa of propranolol spiked wastewater toxicity was not observed
P25. Among the tested experimental conditions photocatalytic due to lower rate of oxidation.
ozonation with Degussa P25 or TiO2 magnetic activated car- Chen et al. (2011) investigated the photodegradation of
bon catalyst shown higher metoprolol removal rate and total propranolol by Fe(III)–citrate complexes and effect of metal
organic carbon (TOC) degradation (mineralization) due to ions (Ca2+, Mg2+, Mn2+ and Cu2+) and humic substances
the production of large number of hydroxyl radicals. It was on the photoreactivity of Fe(III)–citrate complexes. Fe(III)–
observed that efficiency of TiO2 magnetic activated carbon cat- citrate complexes are excellent photocatalysts by generation
alyst was somewhat lower than that of the Degussa P25, even of hydroxyl radicals, which are main reactive oxygen species
though, the prepared catalyst is an interesting alternative responsible for the photodegradation of propranolol. Metal
material for photocatalysis due to its stability and reusability. ions inhibited the photodegradation of propranolol by com-
Photolytic ozonation was also equally effective that of photo- petitive complexation with Fe(III) for citrate and the inhibition
catalytic ozonation when using a metoprolol initial concentra- effect was in the order of Mn2+ > Cu2+ > Ca2+ > Mg2+.
tion of 10 mg/L, this result provides a new way, solar The presence of humic substances also suppressed the photo-
photolytic ozonation for the degradation of emerging contam- degradation of propranolol by competitive complexation of
inants from water. humic substances with citrate for Fe(III). The photolysis
Abramovic et al. (2011) investigated the photocatalytic deg- experiments were performed in Pyrex vessel under 150-W
radation of metoprolol tartrate in suspensions of two TiO2- Xenon Short Arc Lamp and the degradation products formed
based photocatalysts (Degussa P25 or Wackherr) with differ- were identified by GC–MS. 4-hydroxypropranolol, naphtha-
ent surface area. TiO2 Wackherr has 6 times less surface area len-1-ol, 1,5-dihydroxy-naphthalene, 1,6-dihydroxy-naphtha-
than Degussa P25. Faster degradation was observed with lene, some benzene series compounds, and low-molecular-
TiO2 Wackherr compared to Degussa P25 due to lesser radia- weight carboxylic acids were formed upon photodegradation
tion scattering and slower back reactions, which compensate of propranolol in Fe(III)–citrate system. The proposed
the lower surface area of TiO2 Wackherr. In case of Degussa pathways for the Fe(III)–citrate-induced photodegradation
P25 slower initial degradation rate was observed due to higher of propranolol are shown in Fig. 5 (Chen et al., 2011).
radiation scattering and back reactions. After 240 min of irra-
diation metoprolol was mineralized completely in both the
cases. Degradation intermediates were detected and identified
by LC–DAD and LC–MS/MS techniques. Major degradation
pathways involved in the photocatalysis of metoprolol are
hydroxylation of the aromatic ring, shortening of the meth-
oxyl-containing lateral chain and cleavage of, or addition of
hydroxyl radical to, the amine-containing chain.
Santiago-Morales et al. (2013) studied visible light photo-
catalytic degradation of propranolol using cerium doped tita-
nium dioxide as catalyst in ultrapure water and biologically
treated wastewater. Cerium doping of TiO2 increases the pho-
tocatalytic efficiency of TiO2 by shifting its absorption from
near UV region of the solar spectrum to the visible region.
Photocatalysis of propranolol was carried out in a Duran
tubular photoreactor with the concentration of 25 mg/L and
radiation source is Xe-OP lamp with a photon flux of
(6.19 ± 0.20) · 10 6 Einstein/s (290–400 nm). Propranolol
was completely disappeared in less than 2 h of irradiation.
Photocatalytic rate was less in biologically treated wastewater
compared with ultrapure water due to the presence of radical
scavengers and competing substances. More than thirty reac-
tion intermediates were formed during the process and those
were detected by liquid chromatography coupled to quadru-
pole-time-of-flight mass spectrometry (LC-ESI-QTOF-MS/
MS). The major degradation pathways of the propranolol
are cleavage of the ether bond and addition of hydroxyl groups
to the aromatic nuclei or to the ring opening attack of hydro-
xyl radicals on the naphthol moiety. The toxicity of the degra-
dation products was determined using the green algae
Pseudokirchneriella subcapitata and the marine bacterium
Vibrio fischeri. Multigenerational toxicity was assessed by
measuring the growth inhibition of P. subcapitata and acute Figure 5 The proposed pathways for the Fe(III)-citrate-induced
toxicity was evaluated by measuring the decrease in the photodegradation of propranolol (Chen et al., 2011).

Please cite this article in press as: Marothu, V.K. et al., Photocatalysis of b-blockers – An overview. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/
j.arabjc.2014.10.044
 6
j.arabjc.2014.10.044
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Table 1 Summary of the works published on the photocatalysis of b-blockers.

b-Blocker Matrix Initial Catalyst Irradiation source Analytical Methods % removal References
concentration
Metoprolol Distilled water 0.05 mM Degussa P25 (1.0 mg/mL), UV HPLC, TOC, HPLC/MS–MS Complete in 30 min for TiO2 Abramovic et al.
TiO2 Wackherr Wackherr and 60 min for (2011)
(1.0 mg/mL) Degussa P25
Propranolol Deionized water 0.00002 M Fe(III)–citrate complex 150 W xenon short arc lamp HPLC, GC–MS 50 in 37 min Chen et al. (2011)
Metoprolol Water 50 mg/dm3 T1, T2, T3 and T4 UV lamp (254 nm, 0.7 Kw) UV–Vis spectroscopy COD 50 in 120, 145, 210 and Czech and
113 min for T1,T2, T3 Rubinowska (2013)
and T4, respectively
Propranolol Milli-Q water 50 mg/L Degussa P25 (0.4 g/L) 1 Kw Xe-OP lamp, Sun light HPLC, TOC, BOD5, COD, 81 for sun light and 94 De la cruz et al.
Toxicity bioassay by for Xe-lamp in 240 min (2013)
Chlorella vulgaris
Metoprolol Water 0.05 mM Mesoporous TiO2 UV HPLC Complete in 60 min Golubovic et al.
nanopowder (1 mg/cm3) (2013)
Atenolol Pure water and treated 5–30 mg/L Degussa P25 1 Kw Xe-OP lamp Spectrophotometer, TOC, 80 in 120 min Ioannou et al.
propranolol municipal water (50–3000 mg/L) Toxicity bioassay by D. magna (2011)
Atenolol pH 6.8 Milli-Q water 37.6 lM Degussa P25 (2.0 g/L) High pressure mercury lamp HPLC, TOC, HPLC/MS–MS Complete in 60 and Ji et al. (2013)
and river water (Emax = 365 nm) 180 min in pH 6.8 Milli-Q
water and river
water, respectively
Atenolol Milli-Q water 40 lM Sodium nitrate (5 mM) 1000 W Xe arc lamp HPLC, TOC, HPLC/MS–MS, 72 in 240 min Ji et al. (2012)
Toxicity
bioassay by D. magna
Metoprolol Aqueous solution 50 mg/L Titania – coated magnetic 1500 W xenon arc lamp HPLC, TOC Complete in 3 h Rey et al. (2012)
activated carbon (k > 300 nm, 550 W/m2)
Metoprolol Aqueous solution 0.0001 M Degussa P25 Low pressure mercury lamp HPLC, TOC 30 for UV-C/1 g/L TiO2 Rivas et al. (2010)
(Emax = 254 nm) system and 45 for UV-C/
0.001 M H2O2/ TiO2
(0.25–2.0 g/L) system
in 180 min
Metoprolol Milli-Q water 50 mg/L Degussa P25 (0.4 g/L) 1 Kw Xe-OP lamp HPLC, TOC, BOD5, COD, Complete in 300 min Romero et al.
propranolol Toxicity bioassay by Vibrio fischeri for metoprolol and (2011)
360 min for propranolol
Propranolol Ultrapure water, 25 mg/L Ce-doped TiO2 (cerium 1 Kw Xe-OP lamp HPLC, TOC, COD, Toxicity Complete in 90 min in Santiago-Morales
biologically treated loading of 0.5 wt.% bioassay by P. subcapitata pure water and 360 min et al. (2013)
wastewater and bulk catalyst and Vibrio fischeri in wastewater
concentration
of 0.14 g/L)
Atenolol Milli-Q water 100 lM Degussa P25 (2.0 g/L) High pressure mercury lamp HPLC, TOC, HPLC/MS–MS Complete in 40 min Yang et al. (2010)
Metoprolol (Emax = 365 nm)

V.K. Marothu et al.

Propranolol
Abbreviations:
HPLC-MS/MS: High performance liquid chromatography-tandem mass spectrometry.
TOC: Total organic carbon.
BOD5: Biochemical oxygen demand.
COD: Chemical oxygen demand.
Photocatalysis of b-blockers 7

Golubović et al. (2013) investigated the efficiency of sol–gel TiO2 photocatalysis. Finally photocatalysis is an efficient and
synthesized mesoporous TiO2 nanopowders for photocatalytic inexpensive treatment technique for the removal of b-blockers
degradation of metoprolol. Mesoporous TiO2 nanopowders from the aquatic environment.
have been synthesized by using titanium tetrachloride (TiCl4)
as the precursor. The photocatalytic efficiency of the mesopor- References
ous TiO2 was compared with Degussa P25 and effect of calci-
nation time (1–7 h) on photocatalytic activity of mesoporous Abramovic, B., Kler, S., Šojic, D., Lausevic, M., Radovic, T., Vione,
TiO2 was investigated. The mesoporous TiO2 samples calcined D., 2011. Photocatalytic degradation of metoprolol tartrate in
for 4 h have displayed higher photocatalytic performance com- suspensions of twoTiO2-based photocatalysts with different surface
pared with other calcination time samples due to greater mean area. Identification of intermediates and proposal of degradation
pore diameter and the pore structure complexity. Samples pathways. J. Hazard. Mater. 198, 123–132.
calcined for 4 and 5 h have displayed higher photocatalytic Alder, A.C., Schaffner, C., Majewsky, M., Klasmeier, J., Fenner, K.,
2010. Fate of b-blocker human pharmaceuticals in surface water:
performance compared with Degussa P25, whereas the sample
comparison of measured and simulated concentrations in the Glatt
calcined for 3 h has shown similar activity. This study Valley Watershed, Switzerland. Water Res. 44, 936–948.
indicated that, photocatalytic degradation of metoprolol was Andreozzi, R., Campanella, L., Fraysse, B., Garric, J., Gonnella, A.,
strongly effected by pore size and morphology of TiO2 Lo Giudice, R., Marotta, R., Pinto, G., Pollio, A., 2004. Effects of
nanopowders. advanced oxidation processes (AOPs) on the toxicity of a mixture
An overview of the works published on the photocatalysis of pharmaceuticals. Water Sci. Technol. 50, 23–28.
of b-blockers is presented in Table 1. Bendz, D., Paxeus, N.A., Ginn, T.R., Loge, F.J., 2005. Occurrence and
fate of pharmaceutically active compounds in the environment, a
case study: Hoje River in Sweden. J. Hazard. Mater. 122, 195–204.
3. Summary Benner, J., Ternes, T.A., Scholz, J., 2009. Ozonation of beta-blockers:
kinetic studies, identification of oxidation products and pathways.
In recent years, the presence of b-blockers in environmental Environ. Sci. Technol. 42, 10–18.
matrices has received a special attention by the scientific com- Brun, G.L., Bernier, M., Losier, R., Doe, K., Jackman, P., Lee, H.B.,
munity due to increasing use and limited human metabolism 2006. Pharmaceutically active compounds in Atlantic Canadian
sewage treatment plant effluents and receiving waters, and potential
(Alder et al., 2010; Huggett et al., 2003; Rivas et al., 2010).
for environmental effects as measured by acute and chronic aquatic
After being used, they are released into sewage waste water toxicity. Environ. Toxicol. Chem. 25, 2163–2176.
treatment system and surface waters as metabolites as well as Calza, P., Sakkas, V.A., Medana, C., Baiocchi, C., Dimou, A.,
unchanged parent molecules. These compounds are persistent Pelizzetti, E., Albanis, T., 2006. Photocatalytic degradation study
and resistant to biodegradation, accumulating in the environ- of diclofenac over aqueous TiO2 suspensions. Appl. Catal., B:
ment. They are producing harmful effects (changes in cardiac Environ. 67, 197–205.
rhythm, generation of abnormalities, inhibition of the growth Carlsson, G., Orn, S., Larsson, D.G., 2009. Effluent from bulk drug
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Please cite this article in press as: Marothu, V.K. et al., Photocatalysis of b-blockers – An overview. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/
j.arabjc.2014.10.044