Академический Документы
Профессиональный Документы
Культура Документы
2
O
2
Photolysis, and TiO
2
Photocatalysis for
Dipyrone Oxidation: Drug Removal, Mineralization, Biodegradability,
and Degradation Mechanism
Ardhendu Sekhar Giri and Animes Kumar Golder*
Department of Chemical Engineering, Indian Institute of Technology, Guwahati, Assam 781 039, India
*S Supporting Information
ABSTRACT: Dipyrone (DIPY), an analgesic drug, is very quickly hydrolyzed to 4-methylaminoantipyrine (4-MAA) in an acidic
solution. Batch study was conducted to compare the performance of dierent oxidation processes such as Fenton (FP), photo-
Fenton (PFP), UV/H
2
O
2
photolysis (UVP), and UV/TiO
2
photocatalysis (UVPC) for removal of 4-MAA from aqueous
solution. The degradation eciency was evaluated in terms of total organic carbon (TOC) reduction and enhancement of
biodegradability. Maximum 4-MAA removals of 94.1, 96.4, 74.4, and 71.2% were achieved in FP, PFP, UCP, and UVPC,
respectively, against mineralization of 49.3, 58.2, 47, and 24.6%. The proposed mechanisms suggest that the cleavage of three
methyl moieties followed by pyrazolinone ring breakage led to formation of various intermediates with low errors (0.88 to 0.11
g/mol). The intermediates primarily were hydroxylated and carboxylic derivatives. BOD
5
to COD (BOD, biochemical oxygen
demand; COD, chemical oxygen demand) ratio of 0.4 resulted from DIPY decomposition in all processes with highest
improvement in PFP (BOD
5
/COD 1.5). The collapse of iron(III)-chelates under UV irradiation gave higher biodegradability.
1. INTRODUCTION
Advanced oxidation processes (AOPs) are widely used for
removal of pharmaceutical and personal care products from
industrial and municipal wastewater.
1
AOPs undergo conditions
through dierent reacting systems such as homogeneous or
heterogeneous phases, in light or dark, etc. However, they have
common characteristics of formation of hydroxyl free radicals
(OH
).
2
It causes consecutive unselective degradation of organic
materials. Complete mineralization and/or oxidization of
contaminants occur even at very low concentration, and the
byproducts formed may also be environmentally nonhazardous.
3
The Fenton process (FP) is based on redox reaction between
Fe
2+
and H
2
O
2
generating OH
radicals,
4
whereas the photo-
Fenton process (PFP) occurs additionally under UVvis
irradiation. Heterogeneous semiconductor photocatalysis using
TiO
2
causes oxidation of organic pollutants via hydroxyl radicals,
OH
ad
, and valence holes (h
+
) generated when the semi-
conductor is exposed to UV irradiation. TiO
2
photocatalysis
works at ambient conditions and may be induced by solar
irradiation.
5
UV photolysis of H
2
O
2
(UVP) and TiO
2
photo-
catalysis (UVPC) generally showa lesser extent of oxidation than
FP and PFP. Both homogeneous and heterogeneous catalytic
processes have shown promising results even at pilot-plant scale
in treatment of nonbiodegradable and toxic compounds.
Dipyrone (DIPY) is one of the most popular analgesics and
antipyretic drug. It is also known as Metamizole and Novalgin.
About one-third of it remains unchanged and can be found in
urinary excretion. DIPY is rapidly hydrolyzed into its main
metabolite, 4-methylaminoantipyrine (4-MAA). 4-MAA is
absorbed and biotransformed by enzymatic reactions.
6
The
metabolites of DIPY can be subdivided into two groups: (i)
decarboxylated metabolites and (ii) metabolites with a degraded
pyrazolinone moiety. The metabolic route is shown in Figure 1.
4-MAA is metabolized to 4-aminoantipyrine (4-AA) in human
liver via demethylation and further acetylated to acetylaminoan-
tipyrine (4-AAA) (Figure 1). 4-Formylaminoantipyrine (4-FAA)
is generated by an uncharacterized oxidation of an n-methyl
group of 4-MAA (Figure 1).
Received: July 16, 2013
Revised: January 1, 2014
Accepted: January 1, 2014
Published: January 1, 2014
Figure 1. Chemical structure of dipyrone drug (sodium [(2,3-dihydro-
1, 5-di methyl -3-oxo-2-phenyl -1-pyrazol -4-yl ) methyl ami no]-
methanesulfonate) and its metabolic pathways.
Article
pubs.acs.org/IECR
2014 American Chemical Society 1351 dx.doi.org/10.1021/ie402279q | Ind. Eng. Chem. Res. 2014, 53, 13511358
The metabolites of DIPY enter into the environment from
several anthropogenic sources such as pharmaceutical industry
and inrmary euent, water disinfection, and waste incineration
facilities. These compounds are not completely eliminated by
biological treatment, and thus their presence has been referenced
in sludge treatment plant euents and surface water at high
concentrations. Proper removal of DIPY and its metabolites
present in water and wastewater has an important role in the
prevention of diseases both in humans and animals. AOPs can be
employed for the detoxication of such compounds until the
biodegradability is improved to a level amicable for subsequent
biological treatment.
7
However, there is a lacuna of investigation
for the selection of suitable oxidation process(es) to achieve
biodegradability to such extent.
Therefore, in this study, four AOPs, i.e., FP, PFP, UVP, and
UVPC, are compared based on their performance for the: (i)
oxidation and mineralization of 4-MAA (primary metabolite of
DIPY), (ii) formation of degradation products, and (iii) variation
of biodegradability (BOD
5
/COD where BOD is the biochemical
oxygen demand and COD is the chemical oxygen demand). A
unied mechanism of 4-MAA oxidation is presented. It would
help to elucidate the eect of unreacted drug and degradation
products on the variation of biodegradability of dierent
oxidation processes.
2. MATERIAL AND METHODS
2.1. Reagents. Dipyrone (purity > 99%) was obtained from
Sigma Aldrich Chemical Ltd. (Hong Kong, China). The
chemical structure of DIPY is illustrated in Figure 1. DIPY is
hydrolyzed rapidly at low concentration. Almost complete
hydrolysis of DIPY to 4-MAA in a solution of 0.01 mM occurs
in 30 min at pH 2.5 and temperature 21 C.
8
Methanol (98% (v/
v) purity) and acetonitrile (99% (v/v) purity) of high
performance liquid chromatographic (HPLC) grade were
procured from Merck Specialties Pvt Ltd. (India). Ferrous
ammoniumsulfate heptahydrate (99%purity), sulfuric acid (98%
purity), titanium dioxide (TiO
2
; purity, 99% (w/w); crystal type,
rutile; specic surface area, 391 m
2
/g), H
2
O
2
(50% (v/v) purity),
silver sulfate (Ag
2
SO
4
), and K
2
Cr
2
O
7
(purity > 98%) were
obtained from Merck. Milli-Q water (model Elix 3, Millipore,
Billerica, MA, USA) was used to prepare all reagent and drug
solutions.
2.2. Analytical Techniques. High performance liquid
chromatography was used for the determination of 4-MAA
concentration. A 20 L sample was injected directly into a C
18
column of 4.6 mm inside diameter and 25 mm length. HPLC
instrument of Shimadzu, Japan (model LC-20AD) equipped
with an UVvisible detector was employed for the chromato-
graphic measurement. Methanol and water at the ow rate of 0.5
mL/min (80:20 (v/v)) was used as the mobile phase. The
scanning was performed at a xed wavelength of 254 nm. Liquid
chromatographytime-of-ight mass spectrometry (LC-TOF-
MS; Waters Q-Tof Premier & Aquity UPLC) system was
employed for the identication of drug fragments. The
chromatographic separation was performed on a YMC
(Wilmington, NC, USA) hydrosphere C
18
reverse phase column
(4.6 mm150 mm, 5 mparticle size) following a guard column
(4 mm 10 mm, 5 m particle size) using a mobile phase ow
rate of 0.8 mL/min at 25 C. The mobile phase was consisting of
H
2
O and acetonitrile with 0.1% (v/v) formic acid. A linear
gradient of 95 to 50% H
2
O was applied over 10 min. A 10 L
aliquot of both sample and calibration solution was injected from
an autoinjector. The samples were analyzed by electrospray
ionization (ESI) method in positive ion mode over the mass
range of 100400 amu. The parent ion was fragmented on the
basis of a suitable range of mass to charge (m/z) ratio. The most
prominent daughter ions were selected for further fragmentation.
Chemical oxygen demand was determined according to the
HACH method. A closed reux digester of HACH, Loveland,
CO, USA (model DRB 200) was used for digestion. Total
organic carbon (TOC) analyzer of O.I. Analytical, College
Station, TX, USA (model 1030C Aurora) was employed for the
measurement of TOCby nondispersive infrared method. A5 day
biochemical oxygen demand (BOD
5
) was found per the standard
method of analysis.
9
Dissolved oxygen (DO) was measured using
a precision dissolved oxygen meter of Hanna Instruments,
Smitheld, RI, USA (model HI 2400). Solution pH was
measured using a precision pH meter of Eutech Instruments,
Malaysia (model pH/ion 510).
2.3. Experimental Procedure. All experiments were
conducted in batch mode with continuous stirring. A 1000 mL
capacity cylindrical borosilicate vessel (i.d., 10.5 cm) was used as
the reactor system. A drug solution of 400 mL was taken for the
experimentation. The Fenton experiment was carried out with 50
mg/L DIPY (4-MAA) at room temperature (2325 C). The
initial concentration of DIPY was chosen based on the maximum
concentration reported in literature.
10
pH of the solution was
adjusted using 0.05 NH
2
SO
4
prior to addition of ferrous catalyst.
It was noted that the concentration of 4-MAA was almost
invariant in 2 h at pH 3.5 and temperature 25 C. Subsequently
the oxidation reaction was performed after 2 h of an initial
premixing period. Until and otherwise outlined, the eciency of
drug degradation and mineralization is reported with respect to
the concentration of 4-MAA.
A predetermined amount of Fe
2+
was added rst and mixed for
about 5 min at 260 rpmon a magnetic stirrer of Tarsons, Kolkata,
India (model Spinot 6020; stirring ba:, i.d., 0.8 mm; length, 40
mm). After that H
2
O
2
was added to 4-MAA/Fe
2+
solution. The
agitation was maintained at the same speed. A sample volume of
10 mL was withdrawn at selected time intervals. A 1 mL aliquot
of 0.1 N NaOH was immediately added into the sample to
terminate the oxidation reaction. Addition of NaOH increased
the solution pH at 12.3. Sludge was separated out by
centrifuging (Remi Instruments Ltd., Mumbai, India; model R-
23 8/06) at 2000 rpm for 30 min. Clear liquid was pipetted out
for pH, COD, TOC content, and drug concentration. Clear
liquid sample was heated at 70 C for the destruction of residual
H
2
O
2
(if any) prior to COD measurement. The supernatant was
ltered using 0.45 mcellulose lter (serial no. 08091ID0683) of
Pall India Pvt. Ltd. (Bangalore, India), before LC-MS analysis. 4-
MAA sorbed in sludge, if any, was determined by washing it in
distilled water followed by digestion (dissolution) in H
2
SO
4
(1
M).
In the case of PFP, the experiment was performed following
the same procedure in the presence of UV light. An UV lamp of 9
W from Hong Kong Jie Meng International Lighting Ltd.
Company, China (wavelength, 362 nm; intensity, 12 W/m
2
) was
employed for this work. The UVP experiment was conducted
with a xed concentration of H
2
O
2
under UV irradiation without
Fe
2+
. The UVPC test was carried out using TiO
2
photocatalyst.
The above experimental procedure was adopted for the UVPC
experiment with a xed amount of TiO
2
(1 g/L) only. All of the
experiments were performed in duplicate, and the average values
are reported.
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie402279q | Ind. Eng. Chem. Res. 2014, 53, 13511358 1352
3. RESULTS AND DISCUSSION
3.1. 4-MAARemoval and Mineralization. Concentrations
of Fe
2+
and H
2
O
2
and pH were varied from 1 to 3 mM, from 5 to
25 mM, and from 2 to 4, respectively. The results are shown in
Figures S1S3 of the Supporting Information. Drug removal
eciency increased with rise of one of these parameters, i.e., pH
and Fe
2+
and H
2
O
2
doses. It reached a maximum and then fell.
So, the catalytic eect of Fe
2+
was reduced at lower as well as at
higher concentration of a reactant. The best performance of
Fenton oxidation in terms of 4-MAA and TOC removal is
illustrated in Figure 2. PFP was carried out with the same
operating conditions. UVP was conducted with the same amount
of H
2
O
2
added in the Fenton reaction. In the case of the
heterogeneous catalytic reaction, catalyst dose and pH were
varied from 0.5 to 2.5 g/L and from 2 to 4.5, respectively. Their
eects on 4-MAA removal are in Figures S4 and S5 of the
Supporting Information. Increase in the TiO
2
dose from 1 g/L
had a negative eect on drug removal. Higher concentration
might cause catalyst agglomeration and hindrance to light
penetration.
11
pH determines the surface charge of the TiO
2
photocatalyst (pH
zpc
6.8). Lower pH favors 4-MAA
adsorption. However, too strong 4-MAA adsorption probably
decreased the absorption eciency of light quanta at lower pH.
The best performance of TiO
2
photocatalysis with these
experimental conditions are in Figure 2.
Temperature, solution volume, reaction time, and extent of
mixing were the same for all of the processes in order to compare
their eciencies for degradation of 4-MAA. The dynamics of 4-
MAA and TOC removal are shown in Figure 2a,b. The order of
percentage removal of 4-MAA at any time of the reactor was
found to be PFP > FP UVP > UVPC. Percentage removal of
drug achieved to 96.4, 94.1, 74.4, and 71.1%, respectively, in 45
min. Production of OH
generation is predominant at
<2.5 min irrespective to the oxidation process. The rate of
formation of OH
falls because of H
+
scavenging (eq 6) and
H
2
O
2
autodecomposition (eq 7) with progress of reaction (>2.5
min). In the case of FP and PFP, drug removal of 73.5 and 83.2%
at 2.5 min of oxidation rose to 94.1 and 96.4%, respectively, in 45
min.
+ +
+
e OH H H O
2
(6)
+
+ +
H O H H O
2 2 3 2
(7)
Application of UV light during Fenton reaction generates excess
hydroxyl radicals, and ferric ions are reduced into ferrous leading
to further generation of OH
radicals are
generated by photolysis of the peroxide bond (eq 3). It formed
on the surface of TiO
2
(eqs 4 and 5), and adsorbed 4-MAAon the
surface is oxidized. Hence, the reaction occurs at the diusion-
controlled regime in UVPC.
13
Figure 2. (a) Removal of 4-MAA in dierent AOPs with reaction time.
(b) Removal of TOC. Initial 4-MAA concentration, 50 mg/L; TOC =
23.4 mg/L; temperature, 25 C. FP: Fe
2+
, 2.25 mM; H
2
O
2
, 22.5 mM;
pH, 3.5. PFP: Fe
2+
, 2.25 mM; H
2
O
2
, 22.5 mM; pH, 3.5; UV light, 9 W.
UVP: H
2
O
2
, 22.5 mM; pH, 3.5; UV light, 9 W. UVPC: TiO
2
, 1.0 g/L;
pH, 2.5; UV light, 9 W.
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie402279q | Ind. Eng. Chem. Res. 2014, 53, 13511358 1353
The trend of mineralization was similar to that of drug
removal. The highest TOC removal took place in PFP. It was
very close in the cases of FP and UVP (Figure 2b). The initial
rapid mineralization was up to 2.5 and 5 min for FP and PFP.
However, it was not so distinct for the other two processes. TOC
removal of 28.4 and 42.78% was obtained in 2.5 and 5 min with
FP in addition to 53.6 and 56.0%being obtained in 2.5 and 5 min
for PFP. The rst stage of TOC removal was very fast due to
mineralization of three-methyl moieties. The slowsecond stage is
related to the opening and mineralization of pyrazolinone ring.
14
Usually, large molecular weight intermediates were either
mineralized or broken to lower molecular weight products like
Figure 3. Degradation pathways of 4-MAA and identication of intermediates were obtained in dierent oxidation processes at 10 min of oxidation
(photoreaction with an UV lamp of 9 W; FP, PFP, and UVP conducted at pH 3.5 and UVPC at pH 2.5): (a) Cleavage of 4-MAA; (b) degradation of D
2
(m/z = 279.11) continued from panel a; (c) D
5
(m/z = 176.07) cleavage continued from panel b. The exact mass to charge ratio is in parentheses.
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie402279q | Ind. Eng. Chem. Res. 2014, 53, 13511358 1354
oxalic and acetic acids.
15
Kavitha and Palanivelu indicated that
carboxylic acids are eliminated in PFP very quickly during the
rst stage of oxidation.
16
Bauer et al. reported continuous
formation as well as degradation of lightweight carboxylic acids
during UVPC.
17
There was a dierence of about 20% in drug
removal between FP and UVP. However TOC reduction was
almost the same. It is necessary to mention that H
2
O
2
(22.5 mM)
alone gave around 12.8% 4-MAA decomposition. However, only
UV irradiation did not show notable eect on drug removal.
There is a signicant role of iron-chelation on drug
mineralization. Iron(III)-chelate complexes are more stable in
PF because of lower possibility of further degradation.
18
PFP
would have higher ability to degrade such complexes under UV
luminesce. Knight et al. suggested that Fe(III)-humate
complexes are easily reduced to Fe(II) by H
2
O
2
in PFP.
19
In
addition, humic acids themselves are photodegraded through
formation Fe(III) complexes.
20
Klamerth et al. pointed out that
PFP could breakdown metal complexes of molecular acids and
iron through separation between heavy metal and its complexing
agent.
21
TOC removed in PFP mostly corresponds to oxidation
of hydrophobic components which predominate in natural
organic compounds present in rawwater.
22
It can be explained by
greater aromaticity of the hydrophobic fraction giving higher
reactivity toward oxidizing agents. The refractory hydrophilic
fraction is consisting of short-chain aliphatic amines, alcohols,
aldehydes, esters, ketones, aliphatic amides (<C
5
), polyfunc-
tional alcohols, carbohydrates, cyclic amides, and polysacchar-
ides.
22
In the present work, acidic digestion of sludge formed in
FP showed 2.74% 4-MAA appearance on sludge phase.
3.2. Mechanisms of Drug Degradation. Fenton, TiO
2
photocatalysis, and their allied processes are characterized by the
formation of a common oxidizing agent, i.e., OH
attack
releasing aniline.
4
It was formed via hydroxylation of the aromatic
ring by addition of OH
at the -carbon of D
4
caused formation of D
11
in the case of PFP.
The carbonyl group is very susceptible to being oxidized at lower
pH (<3.5).
30
The valency of the carbon atom in D
12
is saturated
by two additional hydroxyl groups (-OH) due to the availability
of a partially vacant p-orbital in the N
1
-atom. Path 4 represents
the formation route of D
13
D
19
with m/z = 187.19, 152.19,
152.09, 166.09, 155.06, 183.11, and 212.02, respectively. The
structures of these compounds are proposed with low errors
(2.11 to 0.22 g/mol; Figure 3b). D
13
was formed by
hydroxylation of the -carbon of an intermediate with respect
to the N
2
-atom. Both D
14
and D
15
compounds have almost the
same mass (m/z = 152.19 and 152.09). Structures of these
compounds are dierent and have appeared from the same
intermediate with m/z = 194.08. The rst compound was
originated in PFP by decarboxylation (-CO
2
). The second was
the hydroxylation product with formation of NH
3
and CO
2
.
Identication of D
14
(Figure S7 of the Supporting Information)
is evidence of the opening of pyrazolinone ring by an alternative
route (Figure 3b). The proposed structure suggests oxidative
cleavage of NN bond to a multiple hydroxylated derivative.
OH
attack at the
more electrophilic center of the carbonyl group. D
23
and D
24
were identied in PFP. The N
1
-atom has a vacant p-orbital to
accept the electron of OH
ad
. A total of 29
intermediate products appeared in the mass spectra within the
mass to charge ratio of 100400 in four oxidation processes from
the same parent molecule. Pyrazolinone ring was degraded
preceded by cleavage of methyl moieties. The proposed
mechanism implies that most of the intermediates were formed
by pyrazolinone ring degradation. The order of biodegradability
in dierent oxidation processes was found to be PFPFP > UVP
> UVPC.
ASSOCIATED CONTENT
*S Supporting Information
Table S1 and Figures S1S9 containing additional information
on intermediate products, experimental optimization of CIP
decomposition, and mass spectra as outlined in the text. This
material is available free of charge via the Internet at http://pubs.
acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: animes@iitg.ernet.in. Tel.: +91-361-2582269. Fax: +91-
361-258-2292.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
We gratefully thank the Indian Institute of Guwahati (India), for
providing the research fellowship to Mr. Ardhendu Sekhar Giri
and necessary research facilities to the Department of Chemical
Engineering and Central Instruments Facility (CIF).
REFERENCES
(1) Moldovan, Z. Occurrences of pharmaceutical and personal care
products as micropollutants in rivers from Romania. Chemosphere 2006,
64, 18081817.
(2) Torres, R.; Sarria, V.; Torres, W.; Peringer, P.; Pulgarin, C.
Electrochemical treatment of industrial wastewater containing 5-amino-
6-methyl-2-benzimidazolone: toward and electrochemical-biological
coupling. Water Res. 2003, 37, 713.
(3) Malato, S.; Blanco, J.; Vidal, A.; Richter, C. Photocatalysis with
solar energy at a pilot-plant scale: An overview. Appl. Catal. B: Environ.
2001, 37, 115.
(4) Pignatello, J. J.; Oliveros, E.; MacKay, A. Advanced oxidation
processes for organic contaminant destruction based on the Fenton
reaction and related chemistry. Crit. Rev. Environ. Sci. Technol. 2006, 36,
184.
(5) Malato, S.; Fernandez-Ibanez, P.; Maldonado, M. I.; Blanco, J.;
Gernjak, W. Decontamination and disinfection of water by solar
photocatalysis: recent overview and trends. Catal. Today 2009, 147, 1
59.
(6) Oliveira, R.; Almeida, M.; Santos, L.; Madeira, L. Experimental
design of 2,4-dichlorophenol oxidation by Fentons reaction. Ind. Eng.
Chem. Res. 2006, 45, 12661276.
(7) Morais, J. L.; Zamora, P. P. Use of advanced oxidation processes to
improve the biodegradability of mature landfill leachates. J. Hazard.
Mater. 2005, 123, 181186.
(8) Ergun, H.; Fratarelli, D. A. C.; Aranda, J. V. Characterization of the
role of physicochemical factors on the hydrolysis of dipyrone. J. Pharm.
Biomed. Anal. 2004, 35, 479487.
(9) APHA. Standard Methods for the Examination of Water and
Wastewater, 20th ed.; American Public Health Association: Washington,
DC, USA, 1998.
(10) Huber, M. M.; Gobel, A.; Joss, A.; Hermann, N.; Loffler, D.;
Mcardell, C. S.; Ried, A.; Siegrist, H.; Ternes, T. A.; Von Gunten, U.
Oxidation of pharmaceuticals during ozonation of municipal wastewater
effluents: A pilot study. Environ. Sci. Technol. 2005, 39, 42904299.
(11) Sohrabi, M. R.; Ghavami, M. Taguchi experimental design used
for Nano photo catalytic degradation of the pharmaceutical agent
Aspirin. J. Chem. Pharm. Res. 2008, 153 (3), 12351239.
(12) Jayson, G. G.; Parsons, B. J. Oxidation of ferrous ions by
perhydroxyl radicals. Trans. Faraday Soc. 1972, 68, 236242.
(13) Petrovic, M. M.; Bianca, F. S.; Aleksandra, J. R. Oxidative
transformation of fluoroquinolone antibacterial agents and structurally
related amines by manganese oxide. Chemosphere 2011, 85, 13311339.
(14) Gomez, M. J.; Martnez-Bueno, M. J.; Lacorte, S.; Fernandez-
Alba, A. R.; Aguera, A. Pilot survey monitoring pharmaceuticals and
related compounds in a sewage treatment plant located on the
Mediterranean coast. Chemosphere 2007, 66, 9931002.
(15) Leonidas, A.; Perez-Estrada, S. M.; Ana, A. R. Degradation of
dipyrone and its main intermediates by solar AOPs Identification of
intermediate products and toxicity assessment. Catal. Today 2007, 129,
207214.
(16) Kavitha, V.; Palanivelu, K. The role of ferrous ion in Fenton and
photo-Fenton processes for the degradation of phenol. Chemosphere
2004, 55, 12351243.
(17) Bauer, R.; Waldner, G.; Fallmann, H.; Hager, S.; Klare, M.;
Krutzler, T.; Malato, S.; Maletzky, P. The photo-fenton reaction and the
TiO
2
/UV process for wastewater treatmentNovel developments.
Catal. Today 1999, 53, 131144.
(18) Trovo, A. G.; Raquel, F. P.; Nogueira, A. A.; Carla, S. A.
Photodegradation of sulfamethoxazole in various aqueous media:
Persistence, toxicity and photoproducts assessment. Chemosphere
2009, 77, 12921298.
(19) Knight, R. J.; Sylva, R. N. Spectrophotometric investigation of
iron (III) hydrolysis in light and heavy water at 25C. J. Inorg. Nucl.
Chem. 1975, 37, 779783.
(20) Fukushima, M.; Tatsumi, K.; Nagao, S. Degradation Character-
istics of Humic Acid during Photo-Fenton Processes. Environ. Sci.
Technol. 2001, 35, 36833690.
(21) Klamerth, N.; Malato, S.; Aguera, A.; Fernandez-Alba, A. Photo-
Fenton and modified photo-Fenton at neutral pH for the treatment of
emerging contaminants in wastewater treatment plant effluents: A
comparison. Water Res. 2013, 47, 833840.
(22) Buchanan, W.; Roddick, F.; Porter, N.; Drikas, M. Fractionation
of UV and VUV pretreated natural organic matter from drinking water.
Environ. Sci. Technol. 2005, 39, 46474654.
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie402279q | Ind. Eng. Chem. Res. 2014, 53, 13511358 1357
(23) Ojha, A.; Rathod, R. Quantification of 4-methylaminoantipyrine,
the active metabolite of dipyrone, in human plasma. Bioanalysis 2009, 1,
293298.
(24) Calza, P.; Sakkas, V. A.; Medana, C.; Baiocchi, C.; Dimou, A.;
Pelizzetti, E.; Albanis, T. Photocatalytic degradation study of diclofenac
over aqueous TiO
2
suspensions. Appl. Catal. B: Environ. 2005, 67, 197
205.
(25) Wessel, J. C.; Matyja, M.; Neugebauer, M.; Kiefer, H.; Daldrup,
T.; Tarbah, F. A.; Weber, H. Characterization of oxalic acid derivatives as
new metabolites of metamizol (dipyrone) in incubated hens egg and
human. J. Pharmaceut. Sci. 2006, 28, 1525.
(26) Zepp, R. G.; Faust, B. C.; Hoigne, J. Photoproduction of hydrated
electrons from natural organic solutes in aquatin environments. Environ.
Sci. Technol. 1992, 26, 313319.
(27) Zhou, W.; Moore, D. E. Photochemical decomposition of
sulfamethoxazole. Int. J. Pharm. 2011, 110, 5563.
(28) Hesse, M.; Meier, H.; Zeeh, B. Spectroscopic Methods in Organic
Chemistry, 2nd ed.; Thieme: New York, 2008; pp 1517.
(29) Finar, I. L. Stereochemistry and the Chemistry of Natural Products,
Vol. 2, 5th ed.; Holloway: London, 2001; pp 89.
(30) Fabre, H.; Eddine, N. H.; Bressolle, F.; Mandrou, B. Stability
indicating assay for dipyronePart I. Analyst. 1982, 107, 6166.
(31) Sykes, P. A guidebook to mechanism in organic chemistry, 6th ed.;
Fellow of Christs College: Cambridge, U.K., 2005; pp 320322.
(32) Waki, K.; Zhao, J.; Horikoshi, S.; Watanabe, M.; Hidaka, H.
Photooxidation mechanism of nitrogen-containing compounds at
TiO
2
/H
2
O interfaces: an experimental and theoretical examination of
hydrazine derivatives. Chemosphere 2000, 41, 337342.
(33) Tekin, H.; Bilkay, O.; Selale, S.; Tolga, H. Use of Fenton oxidation
to improve the biodegradability of a pharmaceutical wastewater. J.
Hazard. Mater. 2008, 136, 258265.
(34) Tang, W. Z.; Tassos, S. Oxidation kinetics and mechanisms of
trihalomethanes by Fentons reagent. Water Res. 1997, 31, 11171125.
(35) Hyvonen, H.; Orama, M.; Arvela, R.; Henriksson, K.; Saarinen,
H.; Aksela, R.; Paren, A.; Jakara, I.; Renvall, I. Studies on three new
environmentally friendly chelating ligands. Appita J. 2006, 59, 142149.
(36) Kummerer, K.; Al-Ahmad, A.; Mersch-Sundermann, V.
Biodegradability of some antibiotics, elimination of the genotoxicity
and affection of wastewater bacteria in a simple test. Chemosphere 2000,
40, 701710.
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie402279q | Ind. Eng. Chem. Res. 2014, 53, 13511358 1358