w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 3 7 8 7 e3 7 9 6

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Effects of water parameters on the degradation of microcystin-

LR under visible light-activated TiO2 photocatalyst

Miguel Pelaez a, Armah A. de la Cruz b, Kevin O’Shea c, Polycarpos Falaras d,

Dionysios D. Dionysiou a,*
a
Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0071, USA
b
Office of Research and Development, U.S. Environmental Protection Agency, Cincinnati, OH 45268, USA
c
Department of Chemistry and Biochemistry, Florida International University, University Park, Miami, FL 3319, USA
d
Institute of Physical Chemistry, NCSR Demokritos, 15310 Aghia Paraskevi, Attiki, Greece

article info abstract

Article history: A study was performed to determine the effect of pH, alkalinity, natural organic matter (NOM)
Received 29 January 2011 and dissolved oxygen in the performance of nitrogen and fluorine doped TiO2 (NF-TiO2) for
Received in revised form the degradation of hepatotoxin microcystin-LR (MC-LR) in synthetic and natural water under
16 April 2011 visible light irradiation. The initial degradation rate of MC-LR was fastest under acidic
Accepted 18 April 2011 conditions (3.50
0.02  103 mM min1 at pH 3.0) and decreased to 2.29
0.07  103 and
Available online 23 April 2011 0.54
0.02  103 mM min1 at pH 5.7 and 7.1, respectively. Attractive forces between the
opposite charged MC-LR and NF-TiO2 are likely responsible for the enhancement in the
Keywords: photocatalytic decomposition of MC-LR resulting from increased interfacial adsorption. For
NF-TiO2 carbonate buffered solutions, the photocatalytic activity of NF-TiO2 was reduced when
NOM increasing the carbonate concentration up to 150 mg CaCO3 L1. The scavenging of radical
pH species by the bicarbonate ion at pH 7.1 is discussed. In the presence of NOM, the degradation
Alkalinity rates decreased as pH and initial concentration of the NOM increased. The inhibition was
Dissolved oxygen higher with fulvic acid than humic acid under alkaline conditions. Oxygenated solution
Water treatment yields higher NF-TiO2 photocatalytic degradation of MC-LR compared to nitrogen sparged
MC-LR solution at pH 5.7. The involvement of specific reactive oxygen species implicated in the
photodegradation is proposed. Finally, no significant degradation is observed with various
natural waters spiked with MC-LR under visible light (l > 420 nm) but high removal was
achieved with simulated solar light. This study provides a better understanding of the
interactions and photocatalytic processes initiated by NF-TiO2 under visible and solar light.
The results indicate solar photocatalytic oxidation is a promising technology for the treat-
ment of water contaminated with cyanotoxins.
ª 2011 Elsevier Ltd. All rights reserved.

1. Introduction source of energy, for a wide variety of applications including

environmental remediation and energy conversion. The use
Recently, modifications towards visible light response of of non-metals (i.e., nitrogen, fluorine, sulfur and/or carbon)
titanium dioxide (TiO2) has extended the capacity of TiO2 to has proven to be an effective strategy for doping TiO2 for the
utilize a larger portion of the solar spectrum, a renewable degradation of organic contaminants and bacteria in water

* Corresponding author. Tel.: þ1 513 556 0724; fax: þ1 513 556 2599.
E-mail address: [email protected] (D.D. Dionysiou).
0043-1354/$ e see front matter ª 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2011.04.036
3788 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 3 7 8 7 e3 7 9 6

under visible light irradiation (Asahi et al., 2001; Choi et al., the ionization of compounds present in solution is critical to
2007; Czoska et al., 2008; Fu et al., 2006; Goldstein et al., 2008; the adsorption and interaction between catalyst and toxin.
Kontos et al., 2008; Li et al., 2005; Park et al., 2009; Pelaez MC-LR initial degradation rate increased in acidic pH when
et al., 2009, Pelaez et al., 2010a,b; Periyat et al., 2008; Rengifo- employing thin TiO2 films compared to thick films (Antoniou
Herrera et al., 2009). et al., 2009). On the other hand, at neutral pH the interac-
An emerging issue in drinking water industry is the presence tions between the catalysts and the toxin were weaker and
of cyanotoxins in fresh and brackish water sources. Cyanotox- both types of films exhibited similar reaction rate constants.
ins are naturally produced metabolites of cyanobacteria (also The presence of natural organic matter (NOM) can have
known as blue-green algae) and they have been positively a pronounced influence on the photocatalytic degradation of
identified throughout the world and an increase in their organic molecules via TiO2. NOM, which consists mainly of
occurrence and persistence is evident (Pelaez et al., 2010b). The fulvic and humic substances, can act as photosensitizers
most frequently detected are microcystins, including (lw290 nm to visible light) and mediate photodegradation.
microcystin-LR (MC-LR), which exhibit the highest environ- Under natural sunlight, several microcystins showed indirect
mental concentrations of any of the cyanotoxins analyzed. photolytic degradation when natural dissolved organic matter
Unfortunately, the concentration of these toxins often exceeds and fulvic acids were present in natural waters (Welker and
the provisional guidelines set by international agencies (i.e., Steinberg, 2000). Feitz et al. (1999) suggested that high
1 mg L1 by the World Health Organization) (Antoniou et al., 2005, concentrations of natural dyes secreted by cyanobacteria in
2008). Established drinking water treatment processes for natural water scavenged the surface-generated hydroxyl
recalcitrant contaminants have been a challenge for drinking radicals or the organic radicals generated can react among the
water suppliers (Antoniou et al., 2005; Graham et al., 2010). With exudate and lose their oxidizing ability. Kull et al. (2006)
this in mind, alternative technologies to ensure the availability studied the influence of NOM during the oxidation of MC-LR
of clean potable water are of great interest and non-metal doped by chlorine dioxide and confirmed that the degradstion rate
TiO2 is a good candidate. MC-LR has been found susceptible to decreases in the presence of NOM. This tendancy was stronger
photocatalytic degradation with undoped TiO2 under UV in the case of humic acid than that observed with fulvic acid,
(Antoniou et al., 2009; Feitz et al., 1999; Lawton et al., 2003) and probably due to the higher degree of aromaticity of the later
non-metal doped TiO2 under visible light (Choi et al., 2007; (Kull et al., 2006). These NOM constituents also retarded the
Pelaez et al., 2009, Pelaez et al., 2010a,b). However, most of the photocatalytic degradation of carbamazepine, clofibric acid
studies evaluated these materials with ‘clean’ synthetic water. and iomeprol with two commercially available TiO2 materials
Several matrices and conditions present in natural water can by competition for active sites and surface deactivation of the
influence the photocatalytic reaction of heterogeneous systems catalyst by adsorption (Doll and Frimmel, 2005). The concen-
such as TiO2-photomediated processes. The characteristics of tration of dissolved oxygen is crucial in the photocatalytic
the solution matrix (i.e., alkalinity, pH, natural organic matter oxidation process. The addition of oxygen in solution will
and dissolved oxygen) are critical to determine the photo- reduce the electron-hole recombination process and increase
catalytic degradation of organic contaminants in water with the degradation rates through the oxidative pathways.
this so-called ‘green’ technology (Antoniou et al., 2005). Their However, the effect of oxygen is not always positive for the
role on the photocatalytic process needs to be evaluated and photocatalytic system. For dye-sensitized metal doped TiO2,
understood to develop effective solar-driven technologies for the presence of dissolved oxygen can completely inhibit the
water purification. photoreductive activity or reduced the visible light reactivity,
Specific anions can influence the degradation process by depending on the metal deposited (Bae and Choi, 2003). In this
affecting the concentration of reactive oxygen species formed case, oxygen competes for the electrons on the conductive
during the photocatalytic process (Dionysiou et al., 2000). For band with the target molecule in the reductive pathway.
instance, anions can react with the hydroxyl radical to form the In this study, the effects of alkalinity, pH, NOM and dis-
corresponding anion radical. Carbonate ions are strong scav- solved oxygen were evaluated using nitrogen and fluorine
engers of hydroxyl radicals resulting in carbonate radical doped TiO2 (NF-TiO2) nanoparticles for the photocatalytic
(CO3) (Zhu et al., 2007). Another route to inhibit the photo- degradation of MC-LR under visible light. To the best of our
catalytic degradation of organic compounds with TiO2 is the knowledge, this is the first study that utilizes visible light-
adsorption of the anions at the active sites of the TiO2 surface. activated TiO2 photocatalyst to examine the effect of these
This generates a competition between the anion and the water parameters during the photocatalytic transformation of
organic compound to interact with the surface where the contaminants, and in particular of MC-LR, in water. These
reactive oxygen species are generated. The inhibition of results provide insight in the area of visible light-activated
substrate adsorption depends on the concentration of anions photocatalysis and the influence of key water parameters.
adsorbed which is influenced by solution pH. Zhu et al. (2007)
found that the oxidation rates of aqueous ammonia with TiO2
under UV light were inhibited by CO32 but not by other inor- 2. Materials and methods
ganic anions (i.e., SO42, H2PO4/HPO42) at pH w9 and w10.
Nevertheless, at lower pH values (w7.5), all anions tested were 2.1. Reagents and sample preparation
found to hinder the photocatalytic oxidation of ammonia.
A major factor influencing the rate of degradation of MC-LR standard was obtained from Calbiochem. Suwannee
organic compounds in TiO2-based photocatalytic processes is River humic and fulvic acids (SRHA and SRFA, respectively)
pH. Changes in pH could affect the surface charge of TiO2 and were purchased from the International Humic Substances
 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 3 7 8 7 e3 7 9 6 3789

Society (IHSS, University of Minnesota, St. Paul, Minnesota visible light irradiation. To obtain visible light irradiation only,
USA) and used as representatives of NOM in water. Stock a UV block filter (UV420, Opticology) was mounted below two
solutions were prepared in MilliQ-grade water, sonicated for 15 W fluorescent lamps (ColeeParmer) to eliminate spectral
1 h and filtered with a 0.45 mm glass fiber filter (Acrodisc GHP, range below 420 nm. To certify that no UV light passed
Pall Corporation, East Hills, NY USA). From this, specific through the filter, a spectroradiometer (Ocean Optics) was
amounts of solution were transferred to each reactor to ach- employed to obtain the light spectrum after the filter. Fig. 1
ieve initial concentrations of 5 and 10 mg L1 of SRHA and shows the lamp spectrum with and without UV block filter.
SRFA. Solutions with specific concentrations (50, 100 and UV wavelengths with peaks at around 310, 356 and 410 nm can
150 mg/L) were prepared by adding different amounts of be observed when the filter was not mounted. The light
sodium carbonate (Na2CO3, Fisher) into MilliQ-grade water to intensity of the visible light was 7.81  105 W cm2 and it was
evaluate the effect of alkalinity. In solutions in which determined with a radiant power meter (Newport Corpora-
50 mg L1 of sodium carbonate were added, the pH was 10.3. tion). For the solar experiments with the natural water
Sodium hydroxide (Fisher) and monopotassium phosphate samples, the filter was removed and the light intensity was
(Fisher) were used to prepare buffer solutions at slightly 9.52  105 W cm2. To prevent evaporation, a fan was posi-
alkaline pH (i.e., 7.1 and 8.0). Nitric acid was used to adjust the tioned behind the reactor. Sampling was done at specific
pH at 3.0 in experiments dealing with acidic pH. periods of time and the samples were quenched with meth-
To evaluate the effect of dissolved oxygen, MilliQ-grade anol to stop any further reaction, filtered (L815, Whatman) to
water was sparged with N2 or saturated with O2 for 30 min remove the suspended nanoparticles, transferred to 0.2 ml
prior to use without subsequent addition during the experi- glass inserts and placed in sample vials. MC-LR samples were
ment. NF-TiO2 nanoparticles were prepared using a modified analyzed by liquid chromatography (LC, Agilent Series 1100).
sol-gel method previously developed and denominated as The analytical conditions were similar to those reported by
Particle 1 (Pelaez et al., 2009). In brief, a fluorosurfacant was Antoniou et al. (2008) but the column employed was a C18
used as a pore template and fluorine dopant and ethylenedi- Discovery (Supelco) column (4.6 mm  150 mm, 2.1 mm
amine as nitrogen precursor. The sol-gel was stirred for 24 h, particle size). The flow rate was 0.2 ml/min and the injection
dried at room temperature and calcined at 400  C in air. volume was 20 ml. A Spectramax M2 spectrophotometer
Aqueous suspensions of NF-TiO2 nanoparticles were freshly (Molecular Devices Corp., Sunnyvale, CA) was employed to
prepared for every experiment and used after 30 min of obtain the absorbance for experiments involving NOM anal-
sonication (2510R-DH, Bransonic). ysis without MC-LR. Samples were filtered prior to analysis.
All the experiments were conducted in an Advanced Ster-
2.2. Photocatalytic experiments ilchemgard III Class II biological safety cabinet (Baker
Company, Sanford, ME) with full exhaust since MC-LR is
A specific solution previously adjusted for the desired exper- highly toxic and an irritant, so appropriate handling of the
iment (i.e., alkalinity, pH, dissolved oxygen or NOM analysis) toxin is needed.
with an aqueous NF-TiO2 suspension was spiked with an Water samples obtained from Lake Erie and St. John’s River
aliquot of MC-LR standard to reach an initial concentration of (Florida) were employed to evaluate the photocatalytic effi-
500
10 mg L1. The reactor was sealed with parafilm and ciency of NF-TiO2 in natural waters. Water quality parame-
mixed continuously during the photocatalytic reaction with ters, including pH, total alkalinity, total hardness and

5000

Lamp Spectrum with

UV block filter
Lamp Spectrum without
4000 UV block filter
Intensity (a.u)

3000

2000

1000

0
200 300 400 500 600 700 800

Wavelength (nm)

Fig. 1 e Spectral distribution of fluorescent lamp after UV cut off filter.

3790 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 3 7 8 7 e3 7 9 6

conductivity, were measured in the Greater Cincinnati Water

a

Normalized MC-LR Concentration (C/Co)

Works water quality certified laboratory prior to the experi- 1.0

ments. The amount of natural organic matter was estimated

as total organic carbon (TOC) and was obtained using a TOC 0.8

analyzer (Shimadzu). All the experiments were performed in

triplicates and the standard error from the mean is repre- 0.6
sented by vertical error bars on the graphs.
0.4
2.2.1. Micro solid-phase extraction (Micro-SPE) for NOM
pH 3.0
The method was developed based on Rivasseau et al. (1998) 0.2 pH 5.7
pH 7.1
work but in smaller scale due to the total volume from each pH 8.0
sample. All SPE cartridges (1cc/50 mg, Waters Corporation)
0.0
were conditioned with 1 ml of acetonitrile, followed by 1 ml of 0 1 2 3 4 5 6
methanol and 1 ml of water. Each sample was diluted to Reaction time (hr)
obtain a final concentration of 5% of methanol and then
4

M min-1)
percolated through the cartridge. Afterwards, the cartridge Point of Zero Charge
of NF-TiO2
b
was washed with 1 ml of 20% methanol solution. MC-LR was -
(TiOH2+) (TiO )
eluted with 250 ml of 75% methanol solution and then with
3 -
100 ml of 85% methanol solution. Finally, each sample was pH 2.2< (MC-LRH ) <pH 12.5

MC-LR Reaction Rate x 10-3

transferred to a 250 ml insert and analyzed with liquid chro-
matography, as described above.
2

2.2.2. Recovery test

A recovery test was performed to determine the recovery
1
percentage of MC-LR after the solid phase extraction and liquid
chromatography analysis. Standard solutions with MC-LR only
and with SRFA and SRHA were prepared. An average recovery
0
of 85.3
5.2% was obtained. This recovery was verified during
3 4 5 6 7 8
the analysis of the samples of each experiment.
pH

Fig. 2 e a) Photocatalytic degradation of MC-LR in the

3. Results and discussion presence of NF-TiO2 at pH 3.0, 5.7, 7.1 and 8.0 under visible
light b) MC-LR initial degradation rates after 120 min of
3.1. Effect of pH reaction time with NF-TiO2 at different pH conditions.

To explore the effect of pH, the photocatalytic degradation of

an initial concentration of 500 mg L1 of MC-LR with NF-TiO2
was explored at four pH conditions (3.0, 5.7, 7.1 and 8.0). Fig. 2a becomes protonated (TiO2Hþ). Lawton et al. (2003) found that
shows the toxin degradation profile under visible light for the a net charge for each microcystin can be calculated by iden-
four pH values. To assure that the observed MC-LR removal tifying the likely species to be protonated or dissociated at
occurred mostly when both the catalyst and visible light were different pH values. According to their calculations, MC-LR is
present, dark adsorption was studied for MC-LR at all pHs. positively charged at pH 2.1 and below and negatively charged
Under dark conditions, the adsorption of MC-LR was approx- at higher pH values. As a result, attractive forces between the
imately 39.6% at pH 3.0 after 5 h compared to 30.1% at pH 5.7. catalyst and the toxin are expected at the surface where the
When increasing the pH solution to 7.1 and 8.0, the adsorbed oxidizing species are formed at pH below the PZC and repul-
MC-LR percentage dropped to 9.2% and 7.9%, respectively. The sive forces above the PZC. Nevertheless, a small degradation
initial degradation rates have been found to be significantly percentage was observed after 300 min of reaction time (27%
influenced by pH as shown in Fig. 2b. The highest initial at pH 7.1 and 16% at pH 8.0; see Fig. 1). A possible lag phase
reaction rate after 120 min of visible light irradiation was followed by oxidation of MC-LR through diffusion of the
found at pH 3.0 (3.50
0.02  103 mM min1) and decreased at oxidizing species to the bulk of the solution, along with weak
pH 5.7 (2.29
0.07  103 mM min1). When the solution pH van der Waals forces between the catalyst and the toxin, is
was neutral or alkaline (pH 7.1 and 8.0), the degradation rate most likely responsible of this observation.
significantly decreased (0.54
0.02  103 mM min1 and The reaction rates after 120 min with an initial MC-LR
0.36
0.05  103 mM min1, respectively). This is in agree- concentration of 1000 mg L1 (Pelaez et al., 2009) were rela-
ment with our previous study when employing 1000 mg L1 of tively higher compared to an initial concentration of 500 mg L1
initial toxin concentration. We determined the point of zero at pH 3.0 and 5.7, respectively, with NF-TiO2 under visible
charge (PZC) for NF-TiO2 to be 6.4 (Pelaez et al., 2009). At a pH light. The dependency of the reaction rate on concentration
higher than the PZC, the TiO2 surface becomes hydroxylated indicates that the photocatalytic degradation of MC-LR
(TiOH) and the overall surface becomes negatively charged. follows pseudo-first order reaction during the initial stages
At lower pH, the surface is positively charged and the surface of the photocatalytic process.
 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 3 7 8 7 e3 7 9 6 3791

Normalized MC-LR Concentration (C/Co)

1.0

0.9

0.8
pH 7.1
50 mg L-1 Na2CO3 , no phosphate buffer
50 mg L-1 Na2CO3 @ pH 7.1
0.7
100 mg L-1 Na2CO3 @ pH 7.1
150 mg L-1 Na2CO3 @ pH 7.1

0.6
0 1 2 3 4 5 6
Reaction time (hr)

Fig. 3 e The effect of alkalinity at three different Na2CO3

concentrations for the photodecomposition of MC-LR in the
Fig. 4 e Photolysis of SRFA and SRHA only under visible
presence and absence of phosphate buffered solution.
light. Insert shows the UVevis absorbance spectra of each
representative natural organic matter.

3.2. Effect of alkalinity

added, carbonate ion was mainly present in solution and the
As shown in Fig. 3, the addition of 50 mg L1 of Na2CO3 without reactivity with the radical species generated is faster than with
any phosphate buffer solution (pH 10.3) inhibited completely the bicarbonate ion (Nemes et al., 2000) making it a stronger
degradation of MC-LR with NF-TiO2 under visible light irradia- scavenger. Additionally, the increase in the pH value contrib-
tion. In order to differentiate the contribution between the pH uted to the repulsive forces between MC-LR and NF-TiO2 (see
and the presence of carbonate/bicarbonate ions to the inhibition Section 3.1). Therefore, with 100 mg L1 of Na2CO3 at pH 7.1,
of MC-LR degradation, a phosphate buffer solution was there is a reduction on the degradation of MC-LR but with
employed. In this case, at 50 mg L1 of Na2CO3 with a pH of 7.1, 50 mg L1 of Na2CO3 and no phosphate buffer (pH 10.3) the
the initial degradation rate of the cyanotoxin (after 120 min of inhibition was higher. Thus, by adjusting the pH, the inhibiting
reaction time) was almost identical to that obtained in the effect of alkalinity can be altered in the system using NF-TiO2.
buffered solution only (0.54
0.02  103 and
0.54
0.04  103 mM min1, respectively). When the concen- 3.3. Effect of NOM
tration increased to 100 mg L1 of Na2CO3, a decrease in the
initial reaction rate was observed with a value of Fig. 4 shows that no photolytic degradation of either SRFA or
0.34
0.02  103 mM min1. This represents a reduction of SRHA was observed under visible light irradiation in the
approximately 35% in the same reaction time when doubling the absence of the catalyst. Humic and fulvic substances are
concentration of sodium carbonate. The addition of 150 mg L1 known to be photosensitizers in natural waters under solar
of Na2CO3 was more evident in the decrease of the initial reac- light; however, it is clearly observed that no significant
tion rate (0.09
0.01  103 mM min1) for 120 min of reaction absorption occurs in the visible region according to the
time. Thus, by increasing the Na2CO3 concentration three times, UVevis spectra (see insert in Fig. 4). As expected, no change in
a reduction of 80% in the initial reaction rate was obtained. the concentration of SRFA and SRHA is observed over time
The main species responsible for alkalinity in water are under the conditions tested. To check the possibility of NOM
bicarbonate ion (HCO3), carbonate ion (CO32) and hydroxide degradation in the presence of NF-TiO2, dark conditions
ion. Both carbonate and bicarbonate can act as a scavenger of experiments and irradiation under visible light at three
the radical species produced (i.e., hydroxyl radical, superoxide different pH values (3.0, 5.7 and 7.1) with SRFA and SRHA were
radical anion) and reduce the initial degradation rates of carried out. The residual absorbance at 254 nm (UV254) was
MC-LR. They can also partially inhibit the surface photo- monitored as a function of reaction time. This wavelength
catalytic reactions with MC-LR by increasing the negative indicates the absorbance of aromatic structures or conjugated
charge at the surface of NF-TiO2 at pH above the PZC. The double bonds in the humic and fulvic acid molecules. It was
equilibrium between all of them is pH dependent. At pH 7.0, the found that under dark conditions, the adsorption of SRFA onto
predominant ion is bicarbonate and at pH greater than 10, NF-TiO2 was higher than that of SRHA but both were pH
carbonate ion will mainly be present in solution according to dependent. At pH 3.0, the highest adsorption was observed for
their pKa values (Kumar and Mathur, 2006). Lower initial rates both SRFA and SRHA at 5 and 10 mg L1; the adsorption
were obtained by increasing the alkalinity concentration at capacity decreased when increasing pH. For instance, the
a constant pH value which indicates that the bicarbonate ion average relative UV254 (%) of an initial concentration of
concentration increased and therefore the scavenging effect 5 mg L1 of SRHA was 30.1%, 22.5% and 16.7% at pH 3.0, 5.7 and
was more pronounced. In the case where no phosphate buffer 7.0, respectively, after 5 h. In the case of an initial concen-
was employed and 50 mg L1 of Na2CO3 with a pH of 10.3 were tration of 5 mg L1 of SRFA, the UV254 (%) in solution was
3792 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 3 7 8 7 e3 7 9 6

55.1%, 32.3% and 24.1% at pH 3.0, 5.7 and 7.0, respectively. TiO2 to an appropriate electron acceptor. A similar mecha-
Organic matter is comprised of a wide variety of protonated nism can occur with SRHA and SRFA when they are highly
and unprotonated moieties (i.e., carboxylic and hydroxyl adsorbed at low pH on the NF-TiO2 surface. At higher pH
acids, carbonyls, ketones) (Westerhoff et al., 2007). Under values, the adsorption of both types of NOM is less and the
acidic conditions, the organic matter becomes negatively scavenging effect becomes dominant.
charged overall and the NOM interactions are governed by
electrostatic attraction towards the positively charged 3.4. Effect of dissolved oxygen
NF-TiO2. In alkaline solutions, the many acidic functional
groups are deprotonated and negatively charged and repul- To assess the photoreactivity of NF-TiO2 towards MC-LR in the
sive forces are dominant. A higher adsorption capacity of presence of excess oxygen and limited oxygen under visible
SRFA onto NF-TiO2 was obtained and may be due to the more light irradiation, the solution was sparged with oxygen or
functional groups of acidic nature in the molecule and lower nitrogen for 30 min prior to irradiation and the results are
hydrophobicity (Esparza-Soto and Westerhoff, 2003). shown in Fig. 6. The photocatalytic conversion of MC-LR was
Few studies have used humic or fulvic acid to evaluate the higher when the solution was sparged with oxygen with an
photocatalytic activity of synthesized doped photocatalysts initial reaction rate of 3.00
0.08  103 mM min1 compared to
under visible light. Li et al. (2007) observed a small degradation the control at pH 5.7 (2.29
0.07  103 mM min1) after 120 min
of humic acid when employing palladium-modified nitrogen- of reaction time. The opposite effect was observed when the
doped TiO2. With the optimum palladium loading, they ob- oxygen was limited by sparging nitrogen gas before irradiation.
tained less than 20% reduction of an initial concentration of This is depicted as a reduction on the degradation efficiency (as
100 mg L1 of humic acid after 10 h of irradiation time (Li et al., seen in Fig. 6) during the same reaction time with a degradation
2007). However, no adsorption studies were performed to rate of 1.87
0.18  103 mM min1. This implies that the
differentiate between both phenomena. In our study, no photocatalytic degradation of MC-LR was relatively more effi-
significant difference was obtained between adsorption under cient under O2 sparged conditions than under N2 sparged
dark conditions and photocatalytic degradation with visible conditions. Higher reaction rates at high dissolved oxygen
light of SRFA and SRHA (data not shown). This can be attrib- concentrations had been attributed to the scavenger effect of
uted to the complexity of each molecule, the slower produc- conduction band electrons by the dissolved O2 molecules and
tion of the radical species formed (see also effect of dissolved the generation of superoxide anion radical that can subse-
oxygen) and the competition between possible byproducts quently lead to the formation of hydroxyl radical and singlet
produced and these radicals formed. The byproducts can have oxygen (Cho et al., 2004). When oxygen concentration is
similar absorbance at 254 nm. This suggests that the reactions reduced, the photogenerated electron-hole pair’s recombina-
rates are not controlled by adsorption but are rather limited by tion rate is faster and the rate of generation of reactive oxygen
the generation rate of the radical species responsible for the species decreased. In order to identify the dominant radical
oxidation reactions. species formed under the conditions tested, an alcohol
The results obtained for the degradation of MC-LR with NF- quenching agent was employed. In the presence of methanol,
TiO2 under visible light in the presence of SRFA or SRHA in a well-known OH free and surface radical scavenger, MC-LR
water are depicted in Fig. 5. The presence of SRFA or SRHA degradation was significantly inhibited and a reaction rate of
reduced the overall MC-LR degradation even though some 0.91
0.11  103 mM min1 was obtained after 120 min of
significant reduction of the toxin can be observed, in partic- irradiation even though the solution was sparged with oxygen.
ular at pH 3.0. Table 1 lists the initial reaction rates of MC-LR in Nevertheless, even in the presence of methanol, some degra-
the presence of two different concentrations of SRFA and dation is observed indicating that other reactive oxygen
SRHA under various pH values. It can be observed that, for species that can be formed in such process (Cho et al., 2004)
most cases, the degradation rates decreased as pH and initial may be present in the system and can play a role in the pho-
concentration of the NOM increased. Moreover, the inhibition tocatalytic degradation of MC-LR with NF-TiO2.
was higher with fulvic acid that humic acid at all pH values. Fu et al. (2006) reported the presence of hydroxyl and
For instance, a reaction rate of 3.48
0.05  103 mM min1 was superoxide radicals during the photoactivation of N-doped
determined for 10 mg L1 of SRHA compared to a reaction rate TiO2 under visible light. The peak intensity of the electron spin
of 3.08
0.06  103 mM min1 for 10 mg L1 of SRFA at pH 3.0. resonance signals for each radical was more intense under UV
This is related to the higher adsorption of SRFA and the direct irradiation than with visible light, suggesting a lower
competition for active sites and surface-generated oxidizing production of hydroxyl and superoxide radicals. The authors
species on NF-TiO2 (Feitz et al., 1999). When comparing to attributed this to a Lewis acid-base-type of reaction that is
Fig. 2, the degradation of MC-LR is inhibited by the presence of responsible for initiating the generation of the reactive oxygen
SRFA and SRHA according also to the initial reaction rates species, which differs from the well established water pho-
values reported in Table 1. Nevertheless, MC-LR is still being toxidation via electron-transfer-type reaction. Moreover, the
degraded under acidic conditions and a considerable reduc- conjugated double bond at the ADDA moiety of the MC-LR
tion of the reaction rates is observed at alkaline pH. The role of molecule, which plays a critical role in the biological activity
natural organic matter may not be simply as a radical scav- (Antoniou et al., 2008), is the most sensitive part of the cya-
enger. Paul et al. (2007) suggested the formation of a surface notoxin molecule with respect to singlet oxygen oxygenation
coordination complex between adsorbed fluoroquinolone, (1O2) (Welker and Steinberg, 2000). The formation mechanism
a synthetic broad-spectrum antibiotic, and TiO2 that can of singlet oxygen is closely related to the presence of super-
mediate the electron transfer from the conduction band of oxide radicals since the latter can undergo further oxidation to
 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 3 7 8 7 e3 7 9 6 3793

Normalized MC-LR Concentration (C/Co)

1.0

0.8 pH 3.0
5ppm SRHA @ pH 3.0
10ppm SRHA @ pH 3.0
5ppm SRFA @ pH 3.0
0.6 10ppm SRFA @ pH 3.0

0.4

0.2

0.0
Normalized MC-LR Concentration (C/Co)

1.0
b
pH 5.7
5ppm SRHA @ pH 5.7
0.8 10ppm SRHA @ pH 5.7
5ppm SRFA @ pH 5.7
10ppm SRFA @ pH 5.7

0.6

0.4

0.2

0.0
c
Normalized MC-LR Concentration (C/Co)

1.0

0.8

0.6

0.4
pH 7.1
5ppm SRHA @ pH 7.1
0.2 10ppm SRHA @ pH 7.1
5ppm SRFA @ pH 7.1
10ppm SRFA @ pH 7.1

0.0
0 1 2 3 4 5 6

Reaction time (hr)

Fig. 5 e Photocatalytic degradation of MC-LR in the presence of 5 and 10 mg LL1 of SRFA and SRHA at a) pH 3.0, b) 5.7 and
c) 7.1 under visible light.
3794 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 3 7 8 7 e3 7 9 6

Table 1 e MC-LR initial degradation rates with 5 and

Normalized MC-LR Concentration (C/Co)

1.0
10 mg LL1 of SRFA and SRHA after 120 min of visible light
irradiation with NF-TiO2. The confidence interval is based
on the standard error of the mean values. 0.8
3
NOM Concentration MC-LR Initial Reaction Rate  10
(mg L1) (mM min1) 0.6

SRHA pH 3.0 pH 5.7 pH 7.1

5 3.49
0.02 2.31
0.07 0.29
0.03 0.4
WE6 + visible light
10 3.48
0.05 2.27
0.07 0.26
0.06 WE7 + visible light
SRFA WE9 + visible light
0.2 GWL + visible light
5 3.20
0.06 2.12
0.11 0.46
0.03
WE7 + simulated solar light
10 3.08
0.06 2.01
0.07 0.31
0.06 GWL + simulated solar light
Control 3.50
0.02 2.29
0.07 0.54
0.02 0.0
0 1 2 3 4 5 6
Reaction time (hr)
form singlet oxygen. The redox potential of 0.34 V vs NHE
Fig. 7 e Evaluation of the photocatalytic activity of NF-TiO2
indicates that the relation (O2/1O2) is favored thermody-
with different natural waters spiked with MC-LR under
namically (Rengifo-Herrera et al., 2009). This can explain the
visible and solar light.
enhanced reduction on the normalized concentration of
MC-LR when the solution was sparged with oxygen and the
photocatalytic activity of NF-TiO2 in the presence of meth-
anol. It should be noted that ongoing studies are being carried interaction and competitive phenomena involving the water
out in this group to elucidate the mechanism of visible light- parameters present in solution and discussed in the above
activated photocatalysis including the formation of reactive sections. As seen in Table 2, all of the waters tested contained
oxygen species for this particular photocatalyst. high concentrations of alkalinity, had pH values in the alkaline
region, and had relatively high natural organic matter content
3.5. Natural water samples (expressed as TOC), among others. The inhibition of the pho-
tocatalytic activity of NF-TiO2 in these natural waters, under
Fig. 7 shows the results when the photocatalyst was added to visible light irradiation, was likely due to an accumulation of
four natural waters from three utilities (over intake) from the scavenging effects between the water parameters that were
western end of Lake Erie (named WE6, WE7 and WE9) and the evaluated in this study and perhaps other ions that might be
St. John’s River in Florida (named GWL) spiked with MC-LR. present. The contribution of visible light photocatalysis with
Besides providing a natural-containing aqueous matrix to NF-TiO2 was significantly reduced under these conditions but it
assess the performance of NF-TiO2 photocatalyst, these is relevant to understand the interactions and photoreactivity
samples were collected from regions that have reported of non-metal doped TiO2 materials with inorganic and organic
increasing episodes of cyanobacterial blooms over the last compounds present in water when aiming to solar-driven
decade. Several potentially toxin (including MC-LR)-producing technologies for drinking water applications.
cyanobacteria have been monitored and identified in both To evaluate the performance of NF-TiO2 under solar light,
locations (Pelaez et al., 2010b). two natural waters were selected (WE7 and GWL) and the UV
Essentially, no degradation of MC-LR occurs when employ- block filter was removed from the radiation source set up
ing visible light only. This observation is related to the surface system (see Fig. 1 for spectrum). As mentioned before, UV
radiation with peaks at around 310, 356 and 410 nm can be
observed in the absence of filtering. The results obtained using
1.0
Normalized MC-LR Concentration (C/Co)

the simulated solar light are shown in Fig. 7. For both cases,
a high photocatalytic removal of MC-LR was obtained after 5 h
0.8 of solar irradiation. This result differs from the data obtained
when irradiating WE7 and GWL with visible light only. This
0.6

0.4
Table 2 e Physicochemical properties of western Lake
Erie and St. John’s water samples.
pH 5.7
0.2 N2 purged @ pH 5.7 WE6 WE7 WE9 GWL
O2 purged @ pH 5.7
O2 purged + 50mM MeOH
pH 8.5 8.25 8.60 7.40
0.0 Total Alkalinity (mg CaCO3/L) 94.2 89.6 92.3 117.8
0 1 2 3 4 5 6
Total Hardness (mg/L) 104 94 92 110
Reaction time (hr) Turbidity (NTU) 0.51 0.12 0.52 0.23
Conductiviy (mS) 691 572 657 873
Fig. 6 e Performance of NF-TiO2 in oxygen and nitrogen
Absorbance @ 254 nm (UV254) 0.10 0.04 0.08 0.17
sparged conditions and a scavenger compound (methanol) TOC (mg/L) 4.23 2.55 3.91 9.49
in the degradation of MC-LR under visible light.
 w a t e r r e s e a r c h 4 5 ( 2 0 1 1 ) 3 7 8 7 e3 7 9 6 3795

can be attributed to the fact that when using solar light, the Commission (Clean Water - Grant Agreement number 227017).
photoactivation of NF-TiO2 is enhanced and NOM may act as Clean Water is a Collaborative Project co-funded by the
photosensitizer with the UV portion of the solar spectrum Research DG of the European Commission within the joint RTD
promoting MC-LR degradation. In general, NOM displays activities of the Environment and NMP Thematic Priorities/FP7.
increasing absorptivity towards shorter wavelengths and We are thankful to Cincinnati Water Works for the assistance
decreases at longer wavelength up to about 400 nm (see insert provided during the analysis of the water quality analysis. Judy
in Fig. 4 as representative example). When NOM is present in Westrick and GreenWaterLabs are acknowledged for collecting
solution, a series of interfacial electron transfers may occur to and sending the natural water samples.
initiate a photosensitized reaction with MC-LR with the UV
portion of the solar light (Welker and Steinberg, 2000). This
can lead to a UV light induced degradation mediated by the references
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