w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 0 3 e4 1 2

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/watres

Effects of Fenton treatment on the properties of effluent

organic matter and their relationships with the degradation
of pharmaceuticals and personal care products
Wei Li a, Venkateswarlu Nanaboina b, Qixing Zhou a,*, Gregory V. Korshin b
a

Key Laboratory of Pollution Processes and Environmental Criteria at Ministry of Education, College of Environmental Science and
Engineering, Nankai University, Weijin Road 94, Tianjin 300071, China
b
Department of Civil and Environmental Engineering, Box 352700, University of Washington, Seattle, Washington 98195-2700, USA

article info

abstract

Article history:

This study examined effects of Fenton oxidation on trace level pharmaceuticals and

Received 13 April 2011

personal care products (PPCPs) commonly occurring in wastewater. The tested PPCPs

Received in revised form

included acetaminophen, atenolol, atrazine, carbamazepine, metoprolol, dilantin, DEET,

25 October 2011

diclofenac, pentoxifylline, oxybenzone, caffeine, fluoxetine, gemfibrozil, ibuprofen, iopro-

Accepted 1 November 2011

mide, naproxen, propranolol, sulfamethoxazole, bisphenol-A and trimethoprim. Trans-

Available online 15 November 2011

formations of effluent organic matter (EfOM) caused by Fenton oxidation were also
quantified. All tested PPCPs, except atrazine and iopromide, were completely removed by

Keywords:

Fenton treatment carried out using a 20 mg/L Fe (II) concentration and a 2.5 H2O2/Fe (II) molar

Fenton oxidation

ratio. Up to 30% on the total carbon concentration was removed during Fenton treatment

Pharmaceutical and personal care

which was accompanied by the oxidation of EfOM molecules and formation of oxidation

products

products such as oxalic, formic and acetic acids and, less prominently, formaldehyde,

Effluent organic matter

acetaldehyde, propionaldehyde and glycolaldehyde. The absorbance of EfOM treated with

Absorbance spectroscopy

Fenton reagent at varying Fe (II) concentration and contact time underwent a consistent

Size exclusion chromatography

decrease. The relative decrease of EfOM absorbance was strongly and unambiguously
correlated with the removal of all tested PPCPs.
2011 Elsevier Ltd. All rights reserved.

1.

Introduction

The occurrence of pharmaceuticals and personal care products (PPCPs) in aquatic systems and their complex, yet to be
ascertained environmental effects are a matter of increasing
concern. Several comprehensive studies have determined
that a great variety of PPCPs are present in surface water and
wastewater (Kasprzyk-Hordern et al., 2008; Yoon et al., 2010;
Kosma et al., 2010). Although environmental concentrations
of PPCPs are typically in the nanogram to microgram per liter

range, its continuous input and persistence may constitute

potential long-term risks for aquatic organisms (Klavarioti
et al., 2009).
Previous studies have shown that PPCPs cannot be removed
completely by conventional wastewater treatment plants
(Lishman et al., 2006; Kasprzyk-Hordern et al., 2009). In
contrast, advanced oxidation processes (AOP) effectively
degrade most PPCPs occurring in wastewater (Ikehata et al.,
2006; Klavarioti et al., 2009; Rosario-Ortiz et al., 2010). Among
various AOP variants, Fenton oxidation is an attractive option

* Corresponding author. Tel.: 86 22 23507800.

E-mail address: zhouqx@nankai.edu.cn (Q. Zhou).
0043-1354/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2011.11.002

404

w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 0 3 e4 1 2

because of its low cost, lack of toxicity of its reagents (Fe (II) and
H2O2) and relative, simplicity of this technology (Wang, 2008).
In Fenton processes, hydroxyl radicals ( OH) are rapidly
generated through the decomposition of H2O2 catalyzed by Fe
(II) (Eq. (1)). The Fe (II) catalyst can be regenerated at a slow
rate (K 0.01e0.02 M1 s1) through reaction (2) (Burbano,
et al., 2008; Bautista et al., 2008). The oxidation of organic
pollutants (denoted as RH) proceeds via reaction between OH
radicals and RH (Eq. (3)). Generally, Fenton treatment of
wastewater proceeds via four stages: oxidation, neutralization, coagulation/flocculation and solid-liquid separation
(Deng, 2007). While both coagulation and oxidation can
remove target contaminants, the role of the latter process in
Fenton treatment is deemed to be by far prevalent.


FeII H2 O2 /FeIII $ OH OH ;

K 76 M1 s1

(1)

FeIII H2 O2 /FeII HO2 $ H ; K 0:01e0:02 M1 s1

(2)

RH $ OH /$ R H2 O

(3)

The efficiency of Fenton process is affected by H2O2 and Fe

(II) dosage, concentration and properties of effluent organic
matter (EfOM) and the solution pH, with optimal pH values
between 2 and 4 (Trapido et al., 2009). Furthermore, the efficiency of Fenton treatment of wastewater can be enhanced by
UV or solar irradiation. This process known as photo-Fenton
oxidation is characterized by photo-reduction of ferric to
ferrous ions that is promoted concomitantly with the generation of additional OH radicals. The photo-Fenton process can
be effective even at neutral pH whereas the Fenton oxidation
per se is typically limited only to acidic pH (Bandala et al.,
2004; Rozas et al., 2010).
Considerable efforts have been made to examine the
degradation of representative PPCPs by Fenton processes (Ay
and Kargi, 2010; Elmolla and Chaudhuri, 2009; Perez-Moya
et al., 2010; Mendez-Arriaga et al., 2010; Trovo et al., 2009).
For instance, Ay and Kargi (2010) investigated effect of Fe (II)
and H2O2 concentrations on the degradation of amoxicillin at
pH 3 and determined that amoxicillin could be completely
degraded, with 37% of its initial amount mineralized at the
optimum H2O2/Fe/amoxicillin weight concentrations of 255/
25/105 mg/L. A complete degradation of another antibiotic,
sulfamethazine at its initial concentration of 50 mg/L was
observed in Fenton oxidation with 600 mg/L H2O2 and 50 mg/L
Fe (II) concentrations and a 2 min exposure time and pH 3
(Perez-Moya et al., 2010).
The outcome of Fenton treatment of wastewater is influenced by EfOM that interacts readily with hydroxyl radicals,
with apparent EfOM/ OH reaction rates exceeding 109 M1 s1
(Rosario-Ortiz et al., 2008; Wert et al., 2009a, Dong et al., 2010).
As a result, EfOM can be expected to be the primary reaction
substrate in all practically relevant conditions of Fenton
treatment. Still, most of the experiments reported in prior
literature were carried out using PPCPs dissolved in deionized
water, with only a few studies reporting the degradation of
PPCPs in real wastewater (Klamerth et al., 2010a, b).
While the involvement of EfOM in these processes has not
been examined in adequate detail, relevant changes of EfOM
properties can be ascertained using a number of methods. For
instance, high-performance size exclusion chromatography

(HPSEC) has been used to quantify contributions of different

apparent molecular weight (AMW) EfOM fractions (Her et al.,
2003; Nam and Amy, 2008; Korshin et al., 2009). Fluorescence
spectroscopy has also been used to determine contributions of
dissimilar class of compounds constituting EfOM (Her et al.,
2003; Nam and Amy, 2008). Differential absorbance spectroscopy (DAS) has been shown to be capable of detecting changes
of EfOM properties caused by water treatment processes and
correlating them with the degradation of PPCPs caused by
ozonation (Nanaboina and Korshin, 2010).
In this study, we pursued a hypothesis that the oxidation of
EfOM during Fenton treatment (quantified, for instance, by
HPSEC and/or absorbance spectroscopy) proceeds concurrently with and is indicative of the degradation of multiple
PPCPs present in the wastewater being treated. Conceptually,
this hypothesis is similar to that successfully employed by
Wert et al., (2009b), Nanaboina and Korshin (2010) in the
studies of the removal of PPCPs in ozonated wastewater. This
approach has not been applied to Fenton oxidations, nor have
the relevant changes of EfOM properties and attendant
generation of characteristic EfOM oxidation products such as
carboxylic acids and aldehydes been ascertained. These issues
are addressed in detail in this paper.

2.

Methods and materials

2.1.

Reagents

Acetaminophen, atenolol, atrazine, carbamazepine, metoprolol, dilantin, DEET, diclofenac, pentoxifylline, oxybenzone,
caffeine, fluoxetine, gemfibrozil, ibuprofen, iopromide, naproxen, propranolol, sulfamethoxazole, bisphenol-A and
trimethoprim were acquired from SigmaeAldrich. These
compounds were selected based on their frequent occurrence
in surface water and wastewater (Ellis, 2006; KasprzykHordern et al., 2008; Yoon et al., 2010; Kosma et al., 2010).
Stock solutions were prepared by weighing and dissolving
requisite amounts of each compound in Milli Q water to yield
a 2 mg/L concentration. Other chemicals and solvents were
purchased from various commercial suppliers and detailed
information is provided in Text S1 of Supplementary Material
(SM section).

2.2.

Wastewater characterization

A sample of secondary effluent (before disinfection) from

West Point Wastewater Treatment plant in Seattle was
collected in a pre-cleaned 10-L polypropylene container. Upon
arrival at the laboratory, the wastewater was filtered through
a 0.45 mm filter and stored at 4  C for no more than a week until
used in experiments. The wastewater had the following
chemical parameters: DOC 9.6 mg/L, pH 7.2, ammonia
13.6 mg/L NH3eN, nitrate 13.7 mg/L.

2.3.

Fenton oxidation experiments

The wastewater was spiked using the stock solution to reach

a 1 mg/L concentration of each individual PPCP compound.
Fenton treatments were conducted at room temperature, in

w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 0 3 e4 1 2

the presence of low-intensity interior lighting and utilized

varying Fe (II) and H2O2 concentration and reaction times. The
pH of the wastewater was first adjusted to 3 with H2SO4 to
prevent the formation of iron oxyhydroxides. Then, requisite
amounts of Fe (II) and H2O2 were added to the solution to
initiate the oxidation. The reagents were mixed by a magnetic
stirrer to ensure complete homogeneity. After certain contact
time, Fenton oxidation was stopped by increasing the pH to ca.
8. At this pH, the generation of hydroxyl radical is effectively
prevented (Muruganandham and Swaminathan, 2004; Zhang
et al., 2006). The treated wastewater was filtered through
a 0.45 mm filter for analyses that followed. The detailed
experiment methods are provided in Text S2 (SM section).

2.4.

Analytical methods

Dissolved organic carbon (DOC) concentrations in the samples

were determined with a Shimadzu TOC-Vcsh analyzer.
Absorbance spectra were recorded using a Perkin Elmer
Lambda 18 spectrophotometer using 1 cm quartz cells. Nitrate
concentrations were determined with a Dionex ICS-3000 ion
chromatograph. PPCPs analyses were performed according to
the method established by Nanaboina and Korshin (2010)
using a Prominence Shimadzu HPLC coupled with an Applied
Biosystems 4000 Q Trap tandem mass spectrometer (LC-MS/
MS) equipped with electrospray ionization (ESI) operated in
both positive and negative ion modes. All relevant details of
chromatographic separations and MS/MS quantitation of the
analytes are reported in Nanaboina and Korshin (2010).
Aldehydes concentrations were determined by a GC-2010
Shimadzu gas chromatograph (GC) equipped with an electron capture detector (ECD) according to Method 6252 (Disinfection by-products: aldehydes) (APHA, 1998). Concentrations
of carboxylic acids were determined using an ICS-3000 ion
chromatograph. High performance size exclusion chromatography (HPSEC) was carried out using a Dionex HPLC system
with Ultimate 3000 diode array detector. Details of the analysis methods are provided in the Text S3 (SM section).

3.

Results and discussion

3.1.

Effect of Fenton treatment on PPCPs concentrations

Initial experiments were performed with varying H2O2/Fe (II)

molar ratios at a constant Fe (II) concentration of 10 mg/L,
a 30 min fixed treatment time and pH 3. The H2O2/Fe (II) molar
ratios used in these experiments were 0.5, 1, 1.5, 2, 2.5 and 3.
Their effects on the degradation of selected PPCPs and the
radical probe pCBA (Yao and Haag, 1991) is shown in Fig. 1(a).
In all cases, the removal of pCBA and PPCPs increased with the
increase of H2O2/Fe (II) molar ratio but little change was
observed when this ratio was above 1.0. For instance, the
degradation of acetaminophen and diclofenac was 90.9% and
91.1%, respectively, at a 1.0 H2O2/Fe (II) molar ratio, while
oxybenzone and fluoxetine were completely degraded at a 0.5
H2O2/Fe (II) molar ratio. When H2O2/Fe (II) molar ratio were
increased from 1 to 3, degradation levels of almost all
compounds were practically stable, except those for atrazine
and iopromide for which the removal increased with the

405

Fig. 1 e (a) Degradation of pCBA and PPCPs by Fenton

oxidation carried out using varying H2O2/Fe (II) molar
ratios. Fe (II) concentration 10 mg/L, pH 3, reaction time
30 min. (b) Degradation of PPCPs by Fenton oxidation at
varying Fe (II) concentrations. H2O2/Fe (II) molar ratio 2.5,
pH 3, reaction time 30 min.

H2O2/Fe (II) molar ratio but did not exceed 56.1% and 61.9%,
respectively. Although not much difference existed among the
degradation of PPCPs when H2O2/Fe (II) molar ratios increased
from 1 to 3, a 2.5 H2O2/Fe (II) molar ratio was employed in the
experiments that followed to ensure that the removal of most
PPCPs be at least 80%.
In the experiments that employed a constant H2O2/Fe (II)
molar ratio of 2.5, Fe (II) concentrations were set at 0.625, 1.25,
2.5, 3.75, 5, 7.5, 10, 15 and 20 mg/L. The pH was 3 and the
treatment time was 30 min. Fig. 1(b) and Fig. S1 (SM section)
show results of these experiments. The degradation of pCBA
gradually increased with the Fe (II) concentration to reach
a 97.3% level at a 20 mg/L Fe (II) dose. The removal of organic
species other than pCBA also increased with the Fe (II)
concentration but the patterns were somewhat different for
different groups of compounds. For instance, acetaminophen,
diclofenac, oxybenzone,
sulfamethoxazole, naproxen,
bisphenol-A, fluoxetine were largely removed at Fe concentrations <7.5 mg/L as shown in Fig. 1(b). Another group of
species that included dilantin, DEET, trimethoprim, propranolol, ibuprofen, carbamazepine, caffeine, gemfibrozil, metoprolol, pentoxifylline and atenolol was removed less readily
but their oxidation was nearly complete at Fe concentrations
<15 mg/L (Fig. S1(a), SM section). Finally, atrazine, iopromide
and pCBA were most resistant toward Fenton oxidation,
especially iopromide and atrazine, whose degradation was

406

w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 0 3 e4 1 2

86.6% and 88.9%, respectively, at a 20 mg/L Fe (II) concentration (Fig. S1(b), SM section).
Possible effects of coagulation on PPCPs removal by Fenton
process were explored using different concentration of ferric
chloride (0.625, 1.25, 2.5, 3.75, 5, 7.5, 10, 15 and 20 mg Fe3/L) in
the absence of H2O2; all the other experiment conditions were
the same as those used in the Fenton oxidations. Results of
these experiments demonstrated that coagulation did not
cause any significant removal (<5%) of nearly all PPCPs, except
propranolol (40%) and metoprolol (20%). This result is in
accordance with the data of prior research (Ternes et al., 2002;
Westerhoff et al., 2005) demonstrating that coagulation did
not significantly affect the levels of diclofenac, carbamazepine, atrazine, DEET and several other PPCPs. The low removal
efficiency can be explained by their hydrophilicity, although
propranolol and metoprolol are more hydrophobic (Carballa
et al., 2005).
Additional measurements examined effects of treatment
time variations at a constant Fe (II) concentration of 10 mg/L
and H2O2/Fe (II) molar ratio of 2.5. In all cases, PPCPs oxidation
was very rapid during the initial 2 min reaction. Most PPCPs
can be degraded up to 80% of the initial concentration (Fig. S2,
SM section). Only atrazine and iopromide were degraded
slowly (36% and 35%, respectively after 2 min of reaction) and
their oxidation continued in some extent beyond the initial
rapid phase.

3.2.

Effect of Fenton oxidation on EfOM

3.2.1.

DOC removal during Fenton process

DOC concentrations in the Fenton-treated wastewater were

measured at varying Fe (II) concentration at a constant H2O2/
Fe (II) molar ratio of 2.5. Similar experiments were also performed for Fenton treatment that utilized a constant Fe (II)
concentration (10 mg/L) and H2O2/Fe (II) molar ratio (2.5) and
varying contact times.
In experiments with varying Fe (II) doses, the DOC
concentrations decreased gradually from 9.6 mg/L in the
untreated wastewater to 6.8 mg/L at a 15 mg/L Fe (II) dose due
both to EfOM removal by coagulation and possibly its mineralization to CO2. Little additional DOC removal took place
when the Fe (II) concentration increased from 15 to 20 mg/L
(Table S3, SM section).
Similarly to the observations concerning the degradation
of PPCPs, the removal of DOC was very rapid during initial
4 min of Fenton oxidation (Table S3, SM section). Approximately 17% of DOC was removed during the first 4 min of
contact time following which the DOC removal slowly
increased to ca. 25%. Because little change occurred after
reaction time exceeding 30 min that contact time was judged
to be optimal for Fenton oxidations.

3.2.2. EfOM oxidation and formation of aldehydes and

carboxylic acids
The role of oxidative process in EfOM transformations caused
by Fenton treatment was explored based on the measurements of the formation of aldehydes and carboxylic acids,

typical products of EfOM oxidation by AOP (Swietlik
et al.,
2004). Four aldehydes (formaldehyde, acetaldehyde, propionaldehyde and glycolaldehyde) were determined to be present

Fig. 2 e Formation of (a) aldehydes and (b) carboxylic acids

in wastewater treated by Fenton process using varying Fe
(II) concentrations. H2O2/Fe (II) molar ratio 2.5, pH 3,
reaction time 30 min.

in the treated wastewater. Fig. 2(a) demonstrates that their

concentrations increased with the Fe (II) concentration and
that formaldehyde was the most prevalent among these
species. Similarly to the degradation of PPCPs and removal of
DOC, the formation of aldehydes was fast, with their
concentrations reaching a plateau within 15 min (Fig. S3(a),
SM section). The behavior of glycolaldehyde was somewhat
different, with its concentration reaching a maximum value
(18.0 mg/L) at 8 min and then decreasing.
The concentrations of formate, acetate and oxalate found
in the Fenton-treated wastewater were much higher than
those of aldehydes, reaching as much as 1.7 mg/L in the case
of oxalate (Fig. 2(b) and Fig. S3(b) in the SM section). This result
is similar to the formation of oxidation byproducts in ozonated wastewater, in which carboxylic acids concentration
was ca. 4.3 times higher than aldehydes concentration (Wert
et al., 2007). The acetate and oxalate levels increased monotonically with Fe (II) concentrations and/or reaction time,
while the behavior of formate was somewhat different, with
its concentration reaching a maximum value of 1.2 mg/L at
mid-range Fe (II) doses and then decreasing.
Examination of contributions of formate, acetate and
oxalate in the total of these three carboxylic acids generated at
varying Fe (II) concentrations and reaction times showed that
at low Fe (II) concentrations and/or short reaction times,
formate accounted for up to 61% of the total carboxylic acids
(Table S4, SM section). As Fe (II) concentration and/or contact

w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 0 3 e4 1 2

time increased, the percentage of formate decreased while

that of oxalate increased to reach ca. 41%.
The yields of aldehydes and carboxylic acids generated via
the oxidation of the EfOM substrate were calculated by Eqs. (4)
and (5), respectively;
P
Yield

Caldehydes
 100%
DOCinitial

(4)

Cacids
 100%
(5)
DOCinitial
P
where
Caldehydes represents the sum of the equivalent
concentration of formaldehyde, acetaldehyde, propionaldeP
hyde and glycolaldehyde, Cacids represents the sum of the
equivalent concentration of formate, acetate and oxalate
(expressed in mg/L as carbon) and DOCinitial represents the
initial DOC concentration of the wastewater.
Yield

407

Fig S4(a) (SM section) demonstrates that the yields of

aldehydes and carboxylic acids increased with Fe(II) concentration and achieved 1.01% and 11.62% (compared with the
initial concentration of organic carbon in the wastewater),
respectively, at Fe(II) concentration of 20 mg/L. Strong linear
correlations were found to exist between DOC removal and
the yields of the aldehydes (R2 0.99) and carboxylic acids
(R2 0.96) during Fenton treatment (Fig. S4(b), SM section).
These correlations demonstrate that for every 1 mg of EfOM
removed during the Fenton treatment, on the average 0.03 and
0.3 mg (as dissolved organic carbon) of aldehydes and
carboxylic acids, respectively, were formed. While the yields
of the aldehydes did not change significantly with variations
of Fe concentrations, those of the carboxylic acids were
<0.25 mg per mg of EfOM removed for Fe concentrations
<5 mg/L while for Fe concentrations >7.5 mg/L, they were as
high as 0.35e0.4 mg per mg of removed EfOM. This trend is
indicative of an increasingly deep oxidation of EfOM and high

Fig. 3 e SEC elution profiles for the wastewater before and after Fenton oxidation with varying Fe (II) concentration at
wavelengths of 254 nm (a) and 220 nm (b).

408

w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 0 3 e4 1 2

yields of formation of its identified degradation products.

Fig. S5 (SM section) presents an additional summary of the
contributions of the removed DOC, identified aldehydes and
carboxylic acids and unidentified DOC fractions remaining in
wastewater treated with the Fenton reagent at varying Fe (II)
concentrations. It demonstrated that the percentage of the
sum of aldehydes and carboxylic acids in the remaining
organic carbon was about 18% at Fe (II) concentration of
20 mg/L.

3.2.3.

Changes of EfOM properties in Fenton process

The prominent formation of carboxylic acids and aldehydes in

the Fenton-treated wastewater is indicative of the oxidation of
EfOM by the Fenton reagent. HPSEC analysis provided additional data related to this observation. Fig. 3 shows the SEC
profiles for the wastewater before and after Fenton oxidation
with varying Fe (II) concentration at H2O2/Fe (II) molar ratio of
2.5. The wavelengths of 220 and 254 nm were selected because
prior research established that the absorbance of NOM at
220 nm is associated with both carboxylic and aromatic
chromophores, while EfOM absorbance at 254 nm is primarily
determined by aromatic groups in EfOM (Korshin et al., 2009).
The SEC profiles generated using the absorbance data at
254 nm have three major peaks with maxima corresponding
to elution times 14.1, 15.1 and 16.0 min (Fig. 3(a)). The feature
with a 16.0 min maximum had an additional shoulder located
at ca. 16.5 min elution time. As high molecular weight molecules are eluted first in HPSEC separations, we divided the
observed HPSEC profiles into four segments corresponding to
varying elution times. These HPSEC segments corresponded
to EfOM species with operationally defined very high apparent
molecular weight, AMW (VHMW, 12.0e14.0 min), high AMW

Fig. 4 e (a) Changes of relative contributions of EfOM

fraction caused by Fenton treatment with vayring Fe (II)
concentrations and (b) correlation between the
contributions of EfOM fractions and SUVA254.

Fig. 5 e Correlations between relative changes of absorbance of treated wastewater and degradation of representative PPCPs
by Fenton oxidation that utilized varying Fe (II) concentrations (B) and contact times (C).

409

w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 0 3 e4 1 2

(HMW,
14.0e14.7 min),
intermediate
AMW
(IMW,
14.7e15.5 min) and low AMW (LMW, 15.5e18.0 min). The
contributions of different EfOM fractions were quantified by
the integration of absorbances within each a priori defined
range of the elution times (Fig. 4(a)).
Examination of the HPSEC profiles of Fenton treated EfOM
showed that the contribution of the VHMW fraction decreased
while that of IMW fraction increased with the increase of Fe (II)
concentration. This demonstrated that Fenton oxidation causes VHMW fraction to break down to form small fragments.
SUVA254 (Table S3, SM section) was also correlated with the
contributions of VHMW and IMW (Fig. 4(b)) demonstrating that
the breakdown of the large AWM fractions of EfOM involved
the preferential oxidation of its aromatic chromophores.
Fig. 3(b) shows the SEC profile for wavelength of 220 nm. Its
shape is different from that recorded for the wavelength of
254 nm due to the presence of intense features corresponding
to the absorbance by carboxyl- and carbonyl-rich molecules
present in the IMW and LMW fractions of EfOM. In these
profiles, the intensity of the absorbance associated with the
EfOM fraction eluted at 15.5e16.3 min decreased rapidly,
while that having lower molecular weights and eluted at
16.1e8.0 min increased.

These observations indicate that the low AMW fraction of

EfOM associated with a prominent HPSEC peak at 16.5 min is
likely to include both the identified (e.g., aldehydes and
carboxylic acids quantified in this study) and unidentified
EfOM oxidation products (e.g., EfOM molecules enriched with
carbonyl and carboxylic functionalities). This point is
confirmed by the existence of strong correlations between the
intensity change of SEC feature at 16.5 min (measured at
220 nm) and total concentrations of aldehydes (R2 0.99) and
carboxylic acids (R2 0.99) formed upon Fenton oxidation
(Fig. S6, SM section).

3.2.4. Changes of wastewater absorbance induced by Fenton

treatment and their relationships with PPCPs degradation
Examination of the absorbance spectra of EfOM affected by
Fenton treatment that utilized varying Fe (II) concentrations
and reaction times showed that the absorbance of EfOM
decreased at all wavelengths exceeding 240 nm (Fig. S7 and
Fig. S8, SM section). Evolution of the absorbance spectra
showed patterns similar to those observed in the degradation
of PPCPs. For example, the difference between the absorbance
of untreated wastewater and that after 1 min of Fenton
oxidation was relatively large but its increments at increasing

Table 1 e DA254/A0254 values and Fe(II) doses corresponding to the removal of 50% and 90% of selected PPCPs and relevant
degradation rate constants KOH.
Compounds
Oxybenzone
Acetaminophen
Fluoxetine
Naproxen
Diclofenac
Propranolol
Sulfamethoxazole
Bisphenol-A
Trimethoprim
Dilantin
Carbamazepine
DEET
Caffeine
Ibuprofen
Atenolol
Metoprolol
Pentoxifylline
Gemfibrozil
Atrazine
Iopromide
pCBA

(DA254/A0254)50%

(DA254/A0254)90%

[Fe(II) dose]50%
(mg/L)

[Fe(II) dose ]90%

(mg/L)

pKaa

KOH (M1 s1)

0.18
0.23
0.24
0.25
0.26
0.28
0.25
0.26
0.30
0.31
0.31
0.32
0.32
0.33
0.33
0.33
0.35
0.35
0.44
0.45
0.36

0.27
0.32
0.42
0.35
0.42
0.43
0.46
0.46
0.46
0.46
0.46
0.46
0.48
0.49
0.51
0.51
0.51
0.5
0.58
0.58
0.55

0.5
1
1.2
1.5
2.4
2.5
2
2
3.2
3.5
3.7
4
4.1
4
4.4
3.1
5
5.3
8.5
9.2
5.6

2.2
3.8
7.5
5
7.5
8.2
10.7
10.2
10.9
9.8
10
10
11.1
12
12.6
12.4
13
12.4
>20
>20
15.3

NA
NA
NA
4.2b
4.2c
9.5
5.7c
9.6e10.2
3.2, 7.1g
8.3
<2
<2
6.1
4.9
9.6
NA
NA
4.7
<2(1.6)
<2 and >13
NA

NA
NA
NA
9.6  109b
7.5  109c
1.0  1010d
8.5  109e
1.0  1010f
6.9  109g
NA
8.8  109c
5.0  109h
NA
6.5  109b
7.1  109i
NA
NA
1.0  1010j
3.0  109k
3.3  109c
5.0  109c

a Yoon et al. (2010).

b Packer et al. (2003).
c Huber et al. (2003).
d Benner et al. (2008).
e Mezyk et al. (2007).
f Rosenfeldt and Linden (2004).
g Dodd et al. (2006).
h Song et al. (2009).
i Song et al. (2008).
j Razavi et al. (2009).
k Acero et al. (2000).

410

w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 0 3 e4 1 2

1.20E+10

Degradation rate constant (KOH , M-1 S-1 )

Bisphenol-A
Propranolol

1.00E+10

Gemfibrozil

Naproxen
Carbamazepine
Sulfamethoxazole

8.00E+09

Diclofenac
Trimethoprim
Caffeine

6.00E+09

Metoprolol
Atenolol
Ibuprofen
DEET

pCBA

4.00E+09

R = 0.61

Atrazine
Iopromide

2.00E+09

0.00E+00
0.2

0.25

0.3

0.35

0.4

0.45

0.5

( A 254 /A254 0 )50%

Fig. 6 e Correlation between (DA254/A0254)50% values and intrinsic rates of oxidation of the tested PPCPs by hydroxyl radicals.

contact times were much less prominent (Fig. S8, SM section).

This was consistent with the fast degradation of PPCPs during
the initial fast phase of Fenton oxidation (Fig. S2, SM section).
The differential spectra generated using the data shown in
Fig. S7(a) and Fig. S8(a) are presented in Fig. S7(b) and Fig. S8(b)
(SM section), respectively. They demonstrate that the intensity
of differential absorbance increased monotonically as a function of Fe (II) concentration and reaction time. The differential
absorbance spectra of EfOM oxidized by Fentons reagent had
a relatively prominent maximum in the wavelength range of
265e275 nm. The broad absorbance band observed in Fenton
oxidation of EfOM was similar to that observed for EfOM
affected by ozone (Nanaboina and Korshin, 2010).
Correlations between the removal of PPCPs and changes of
EfOM absorbance were examined based on absorbance
measurements at the wavelength of 254 nm that is frequently
used in practical applications (Abellan et al., 2007; Korshin
et al., 1997). Typical features of relationships between relative changes of EfOM absorbance (denoted as DA254/A0254) of
the wastewater and the degradation of several important
PPCPs such as sulfamethoxazole, naproxen, atrazine and
iopromide are shown in Fig. 5. Similar patterns were observed
for all the other PPCPs (Figs. S9 and S10, SM section). The
relationships between the degradation of individual PPCPs
and relative changes of absorbance at 254 nm were essentially
the same for Fenton oxidations carried out at varying reaction
times and Fe (II) concentrations.
In all cases, little or no oxidation of the PPCPs took place at
DA254/A0254 values <0.1. This indicates that the initial stage of
Fenton oxidation of the wastewater corresponds to the
engagement of highly reactive EfOM chromophores that
consume all oxidants released in reactions (1)e(3) while less
reactive EfOM fractions and individual PPCPs remain intact in
these conditions.
DA254/A0254 values exceeding the threshold of 0.1 were
indicative of the commencement of PPCPs breakdown. For

instance, 50% and 90% of the initial sulfamethoxazole

concentration were removed at DA254/A0254 values of 0.25 and
0.46, respectively. Further increases of DA254/A0254 values were
accompanied by a complete removal of all the PPCPs except
atrazine and iopromide.
The DA254/A0254 values corresponding to the removal of 50%
and 90% of PPCPs initial concentrations are compiled in Table
1. Compounds listed in it can be operationally separated into
three groups. For the readily degradable PPCPs group (e.g.
oxybenzone, acetaminophen, fluoxetine), (DA254/A0254)50%
values were in the range 0.18e0.28, while the (DA254/A0254)90%
values varied from 0.27 to 0.46. For the moderately degradable
PPCPs group, the (DA254/A0254)50% values were quite similar
ranging from 0.30 to 0.35. The DA254/A0254 value of the refractory PPCPs such as atrazine and iopromide were relative high,
up to 0.58.
For all examined PPCPs, major features of DC/C0 vs. DA254/
A0254 relationships obtained in the experiment with varying Fe
(II) concentrations or contact time were close (Fig. 5). This
observation is similar to that made in the studies of the
oxidation of PPCPs by ozone (Nanaboina and Korshin, 2010).
This result can be considered as a further confirmation that
the DA254/A0254 parameter is useful for estimating the removal
of PPCPs in wastewater treated using widely varying reaction
conditions.
Table 1 also shows the Fe (II) concentrations required to
remove 50% and 90% of the PPCPs used in this study, as well as
the reported rate constants kOH determined in prior
researches for PPCPs oxidations by OH. A strong correlation
(R2 0.95 and 0.93, respectively) was observed to exist between
DA254/A0254 and Fe (II) concentrations required to attain 50%
and 90% PPCPs removal thresholds. A noticeable correlation
(R2 0.61) also existed between (DA254/A0254)50% and kOH values
(Fig. 6). This correlation supports the point that the extent of
the degradation of PPCPs is intrinsically correlated with the
attendant changes of EfOM absorbance


w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 4 0 3 e4 1 2

4.

Conclusions

This study quantified effects of Fenton treatment on the

degradation of trace level PPCPs and concurrent transformations of EfOM. Results of the study can be outlined as
follows:
 All examined PPCPs except atrazine and iopromide could be
completely removed by Fenton oxidation carried out at
a 20 mg/L Fe (II) dose and a 2.5 H2O2/Fe (II) molar ratio.
 Fenton treatment caused a considerable degree of DOC
removal (up to 30%), while SEC data demonstrated that
preferential removal of high molecular weight EfOM molecules and their breakdown into smaller fragments took
place.
 Fenton treatment caused 13% of DOC to be oxidized to yield
formate, acetate, oxalate and, less prominently, formaldehyde, acetaldehyde, propionaldehyde and glycolaldehyde.
The formation of these oxidation products was strongly
associated with changes of DOC and intensities of prominent features in the SEC profiles measured at 220 nm.
 Fenton oxidation caused the absorbance of EfOM to decrease
consistently at all wavelengths >240 nm. The relative
changes of absorbance at 254 nm (denoted as DA254/A0254)
were strongly correlated with Fe (II) concentrations introduced into the system and also with the relative changes of
concentrations of all tested PPCPs. Similar DC/C0 vs. DA254/
A0254 correlations were observed to exist in experiments with
varying Fenton reagent doses and reaction times.
 DA254/A0254 values corresponding to 50% or 90% of removal of
the tested PPCPs by Fenton reagent were well correlated
with the intrinsic rates of interactions of these compounds
with hydroxyl radical.

Acknowledgments
Wei Li would like to thank the China Scholarship Council for
supporting her studies at the Department of Civil and Environmental Engineering of the University of Washington. All
authors wish to acknowledge the University of Washington
and its VISIT program for their support of student exchange
with Nankai University. The authors are deeply grateful to the
Murdock Foundation whose support was critical for this
study. The authors also want to thank the National Natural
Science Foundation of China (grant No. 21037002) for their
kind support and express their appreciation to the personnel
of West Point Treatment Plant, Seattle and especially to Robert
Bucher of King County Wastewater Technology Assessment
Program for helpful discussions and their interest in and
support of this study.

Appendix. Supplementary material

Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.watres.2011.11.002

411

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