Wat. Res. Vol. 35, No. 4, pp.

10471051, 2001
# 2001 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(00)00342-0 0043-1354/01/$ - see front matter

USE OF FENTON REAGENT TO IMPROVE ORGANIC

CHEMICAL BIODEGRADABILITY
E. CHAMARRO, A. MARCO and S. ESPLUGAS* M
Departament dEnginyeria Qumica i Metal.lurgia, Universitat de Barcelona C/Mart i Franques 1,
08028 Barcelona, Spain

(First received 9 November 1999; accepted in revised form 15 January 2000)

Abstract}Fenton reagent has been used to test the degradation of different organic compounds (formic
acid, phenol, 4-chlorophenol, 2,4-dichlorophenol and nitrobenzene) in aqueous solution. A stoichiometric
coefficient for the Fenton reaction was found to be 0.5 mol of organic compound/mol of hydrogen
peroxide, except for the formic acid where a value of approximately one was obtained (due to the direct
formation of carbon dioxide). The treatment eliminates the toxic substances and increases the
biodegradability of the treated water (measured as the ratio BOD5/COD). Biodegradability is attained
when the initial compound is removed. # 2001 Elsevier Science Ltd. All rights reserved

Key words}Fenton reagent, advanced oxidation technologies (AOT)

INTRODUCTION Hydroxyl radicals may be scavenged by reaction with

Water quality regulations are becoming stricter in the
late decades due to an increasing social concern on
environment. A very interesting field of concern is
what to do with wastewater that contains soluble
organic compounds that are either toxic or non-
biodegradable. Advanced oxidation technologies
(AOT) for water and wastewater treatment show
high efficiency but work at a high cost of both
investment (complex installations) and operation
(higher consume of energy and/or reagents). This
makes these processes only useful when the cheaper
options are not effective. Experiences with different
oxidation technologies and different substrates
have shown that a partial chemical oxidation of a
toxic wastewater may increase its biodegradability up
to high levels (Kiwi et al., 1994; Scott and Ollis,
1995).
One of the most effective technologies to remove
organic pollutants from aqueous solutions is the
Fentons reagent treatment (Bidga, 1995). It is well
known that organic compounds can easily be
oxidized. It consists in a mixture of hydrogen
peroxide and iron salts. There are chemical mechan-
isms that propose hydroxyl radicals as the oxidant
species (Pignatello, 1992; Walling et al., 1974), that
are generated in the following chemical equation:
Fe2 H2 O2 ! Fe3 OH OH 1 are known to be primary metabolites, which act in
*Author to whom all correspondence should be addressed.
Tel.: +34-3-402-12-90; fax: +34-3-402-12-91; e-mail:
esplugas@angel.qui.ub.es
1047
another Fe2+:
OHFe2 ! OH Fe3 2
3+
Fe catalytically decomposes H2O2 following a
radical mechanism that involves hydroxyl and
hydroperoxyl radicals, including (1) and (2):
Fe3 H2 O2 Fe2OOH2 H 3
Fe OOH2 ! HO2 Fe2 4
Fe2 HO2  ! Fe3 HO
2 5
Fe3 HO2  ! Fe2 H O2 6
OHH2 O2 ! H2 O HO2  7
Fenton reagent shows to be a very powerful oxidizing
agent (Sedlak and Andren, 1991; Potter and Roth,
1993). There are, however, species that show
resistance to oxidation by Fenton reaction (Bidga,
1995). These species are small chlorinated alkanes
(tetrachloroethane, trichloroethane), n-paraffins and
short-chain carboxylic acids (maleic, oxalic, acetic,
malonic). These last compounds are indeed a very
interesting kind because they are typical oxidation
products of larger molecules after fragmentation.
Even more interesting is that the cited compounds
energetic cycles of most living organisms. Partial
chemical oxidation yields biodegradable products,
together with destruction of inhibitory species
(Marco et al., 1997). The objective of this paper
1048 E. Chamarro et al.
was the degradation of small organic molecules by
the Fenton reagent.
MATERIALS AND METHODS
Different organic compounds (acetic acid, formic acid,
phenol, 4-chlorophenol, 2,4-dichlorophenol and nitroben-
zene) were choosen to study their degradation in aqueous
solution using Fentons reagent. All chemicals used were
produced by Panreac (Spain) and were of analytical grade.
The experiments were carried out at a ratio Fe2+/compound
equal to 1, 0.1 and 0.01. Initial concentration of organic
pollutants was set to 300 mg/L.
Total organic carbon (TOC) analysis were performed in
order to know the amount of organic compounds that were
depleted to CO2 during the chemical oxidation. The TOC
content of the samples was determined by Dohrman DC-
190 high-temperature TOC analyzer.
Concentration of organic compounds was followed by
HPLC (high-performance liquid chromatography). Chro-
matograms were made with Millennium software using a
Waters 600 Controller with a Waters 996 Photodiode Array
Detector. The column (spherisorb ODS2; 5m; 25  0.46 cm)
was washed with methanol before analysis. A mixture of
50% acetonitrile in 50% water was chosen as the optimal
mobile phase.
Biodegradability was measured by 5-day biochemical
oxygen demand (BOD5) and by 21-day biochemical oxygen
demand (BOD21) analysis of samples at different times of
treatment. As bacterial seed (this synthetic water is sterile) a
small amount of filtered activated sludge from a municipal
wastewater plant was used. This kind of seed was chosen
because it comes from the most common and cheap
biological treatment, and it means that no special or
adapted bacteria are required to reproduce these results.
Chemical oxygen demand (COD) is also an important
parameter that was followed in order to know the degree of
oxidation changes.
EXPERIMENTAL RESULTS AND DISCUSSION
The experimental work was oriented towards
studying how the amount of oxidant applied affects
the biodegradability of initially non-biodegradable
different organic compounds. Figure 1 shows the
BOD/COD ratio (the standard for 5 and 21 days) for
six organic compounds. BOD/COD constitutes a
good measure of the biodegradability of a waste-
water. Contaminants with a ratio of BOD5/
COD>0.4 may be considered thoroughly biodegrad-
Fig. 1. BOD5/COD and BOD21/COD ratios for the tested
organic compounds.
able. It can be observed that acetic acid (ACH) and
phenol (PHE) are quite biodegradable, formic acid
(FOR) is lightly biodegradable, but 4-chlorophenol
(4-CP), 2,4-dichlorophenol (DCP) and nitrobenzene
(NB) are refractory to the biological treatments.
Two kinds of experiments were developed. First
type were conducted to the search of the stoichio-
metric coefficients, that is to know the moles of
organic compound removed by 1 mol of hydrogen
peroxide. Thirty mililiter vials, at room temperature,
were filled with organic/Fe2+ solution at Fe/organic
ratios of 1 : 1, 0.1 : 1 and 0.01 : 1. Different doses of
peroxide were added to these vials (from 0.150 mol
H2O2 mol 1 organic). After 24 h organic remaining
was analyzed by HPLC, TOC, COD and BOD.
Second type were kinetic experiments and were
carried out in a stirred reactor of 1.5 L capacity at
batch operation, isothermal conditions and refriger-
ated by water. For these experiments the measured
variables were: redox potential, pH, temperature,
concentration of organic and TOC.
The stoichiometric coefficients for the five organic
compounds studied are shown in Table 1. They have
been obtained through linear fitting of the experi-
mental results until 90% degradation. The behavior
of the organic compounds is similar with the
exception of the formic acid. The explanation is that
hydroxyl radical generated oxidize the main com-
pound and its intermediates, but in the case of the
formic acid only the main compound is oxidized
because formic acid is already highly oxidized, little
additional oxidation by Fenton reagent is required
before conversion to carbon dioxide.
Organic compound Fe=H2 O2 ! Oxidized products
Oxidized products Fe=H2 O2
! Other oxidized products
Figure 2 shows the organic remaining after 24 h for a
ratio Fe2+/organic of 0.01 : 1 and different hydrogen
peroxide doses. A similar behavior can be seen for
the four compounds (PHE, 4-CP, DCP and NB)
tested. For a ratio H2O2/organic above 3 the organic
reduction is practically complete in all cases. It is not
necessary to add a large quantity of hydrogen
peroxide to the system to remove the organic
compounds. Other ratios Fe2+/organic tested
(0.001 : 1 and 0.1 : 1) have given the same results.
Table 1. Stoichiometric coefficients for FOR, PHE, 4-CP, DCP and
NB (confidence coefficient 95%)
Compound Mol removed/mol H2O2
Formic acid 0.955  0.077
Phenol 0.506  0.023
4-Chlorophenol 0.601  0.044
2,4-Dichlorophenol 0.520  0.031
Nitrobenzene 0.546  0.027
 Use of Fenton reagent to improve organic chemical biodegradability 1049

Fig. 2. Remaining PHE, 4-CP, DCP and NB for initial

concentrations of 300 ppm (Fe2+/organic=0.01 : 1).
Fig. 3. Total organic carbon after 24 h for a ratio
Fe2+/organic=0.01 : 1 (initial concentration of organics:
300 ppm).
The analysis of total organic carbon for these
experiments with a ratio Fe2+/organic 0.01 : 1 shows
a similar behavior for the four compounds. In all the
cases, for a ratio H2O2/organic equal to 3 the
degradation of organic compound was practically
complete. However, the TOC decreased more slowly
and there was no complete mineralization of the
compounds. Figure 3 shows the TOC reduction for
these compounds (Fe2+/organic 0.01 : 1). Similar
results were obtained for the other ratios studied.
The total organic carbon consumed was also
determined for three different ratios Fe2+/organic
(1, 0.1 and 0.01). In these experiments it can be seen
that mineralization increases with iron concentration.
Figure 4 shows the TOC consumed in the case of 4-
chlorophenol for these three Fe2+ concentrations at
a different H2O2/4-CP ratio (050). According to
Fig. 4, it can be seen that there is a limiting TOC
value at high concentrations of hydrogen peroxide. Fig. 4. TOC consumed vs. H2O2 doses at different Fe2+
In order to reduce the TOC, the concentration of ratios.
Fe2+ and H2O2 show to be very important.
In all the experiments, after 24 h of reaction, the
TOC decreased with the concentration of hydrogen biodegradability is attained when the initial com-
peroxide. The COD values decreased too, and the pound is removed.
BOD values were seen to increase. In Figure 5, it can Kinetic experiments were carried out for formic
be seen the variation of BOD5/COD after 24 h for acid and 4-chlorophenol. In experiments with formic
4-chlorophenol experiments with the hydrogen per- acid the H2O2/FOR ratio was 1.2 and the Fe2+/FOR
oxide doses operating at a Fe2+/4-CP ratio of 1 : 1. ratio was 0.4. For these experiments, the TOC
Figure 5 shows 4-chlorophenol solution with a decreased very fast and after 2.5 h it was practically
BOD5/COD ratio initially near zero (as it can be zero. That is because the formic acid reacts with
seen in Fig. 1). It becomes a biodegradable solution radicals to give carbon dioxide directly. The pH
when H2O2 is added (as the hydrogen peroxide increased when hydrogen peroxide was added de-
concentration increases, the BOD5/COD ratio also creasing afterwards to a constant value. Also, the
increases to a value  0.4). redox potential increased when the oxidant was
Figures 5 and 6 show that the Fenton reaction added and afterwards decreased to a constant value,
with these organic compounds yields biodegradable as it can be seen in Figure 7.
substances. Only when the initial organic compounds The experiments with 4-chlorophenol were carried
are depleted, microorganisms are able to degrade the out with a Fe2+/4-CP ratio of 1 : 1 and with different
products. Figure 6 shows the biodegradability of 4- amounts of H2O2. For these experiments the redox
chlorophenol and 2,4-dichlorophenol vs. the percen- potentials increased when hydrogen peroxide was
tage of substance removed. It can be seen that true added to the system and after decreased. For a same
1050
Fig. 5. BOD5/COD vs. H2O2 dose of an initial concentra-
tion of 4-CP of 300 ppm (Fe2+/4-CP=1 : 1).
Fig. 6. Biodegradability of 4-CP and DCP vs. fraction
removed.
Fig. 7. Redox potential vs. time Fe/4CP 1 : 1 different initial
amounts H2O2.
reaction time, when the H2O2 concentration was
increased, the redox potential was also seen to
increase. The pH decreased in all experiments due
to the formation of more acid products than 4-
E. Chamarro et al.
Fig. 8. Reaction rate of 4-chlorophenol at different Fe2+/
H2O2 ratios.
chlorophenol. For the same reaction time, when
concentration of hydrogen peroxide increased, the
pH decreased. In Figure 8 the variation of the
concentration of 4-chlorophenol vs. time can be seen.
For a ratio H2O2/4-CP of 1 : 1, the concentration
decreased to a constant value. In the later case
enough hydrogen peroxide was not available in
solution to degrade all the 4-CP. However, for a
ratio of H2O2/4-CP 10:1 the concentration of 4-CP
decreased until zero. The reaction rate was seen to
increase with Fe concentration. From Fig. 8 it can be
concluded that hydrogen peroxide and iron concen-
tration have an influence on the degradation rate.
The iron concentration was seen to be more
important than the peroxide ratio. For Fe2+/4-CP
ratios larger than 0.1 : 1 the reaction may be
considered instantaneous.
CONCLUSIONS
There are two important factors affecting the rate
of Fentons reaction: peroxide dose and iron
concentration. The peroxide dose is important in
order to obtain a better degradation efficiency, while
the iron concentration is important for the reaction
kinetics.
The extension of the oxidation is determined by the
amount of hydrogen peroxide present in the system.
A total elimination of organic carbon requires large
amount of oxidant and/or large residence times. The
partial oxidation of toxic compounds enhances
biodegradability. Total depletion of organic carbon
requires huge amounts of oxidant and large residence
times. Oxidant may be wasted under these condi-
tions, but subsequent low-cost biological treatment
of pre-treated wastewater is shown in this study as a
effective alternative.
Acknowledgements}The authors wish to express their
gratitude for the financial support given by the Ministry
of Education of Spain (DGICYT, project AMB 96-0906).
 Use of Fenton reagent to improve organic chemical biodegradability
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