DK2874 CH4

4
Fenton and Modified Fenton

Methods for Pollutant Degradation
Matthew A. Tarr
University of New Orleans, New Orleans, Louisiana, U.S.A.
I. INTRODUCTION
The biorefractory nature of many persistent organic pollutants has resulted in

efforts to devise chemical and physical methods of degrading pollutants in
waste streams or in contaminated sites such as soils, sediments, and ground-
water. Fenton reagent has been applied to the degradation of a wide range
of contaminants, predominantly persistent organic pollutants. The primary
benefits of the Fenton reagent are its ability to convert a broad range of
pollutants to harmless or biodegradable products, its benign nature (residual
reagents do not pose an environmental threat), and the relatively low cost
of the reagents. The major drawbacks to utilization of Fenton reagent are
interferences from nonpollutant species, difficulty in application to the sub-
surface, generation of excessive or explosive heat under aggressive condi-
tions, and wasted reagent costs due to inefficient application or inefficient
pollutant degradation in the subsurface. This chapter will detail the funda-
mental chemistry of Fenton reagent, discuss the kinetics and mechanisms
of pollutant degradation, illustrate the advantages and disadvantages of its
application to subsurface remediation, and evaluate recent advances that may
improve the utility and efficiency of Fenton reagent for pollutant degradation
and subsurface remediation.
The term Fenton reagent refers to aqueous mixtures of Fe(II) and
hydrogen peroxide. The Fenton reagent was first reported by Fenton [1,2] in
1876. Although Fenton did not elucidate the mechanism of the reaction
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Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved.
166 Tarr
named after him, subsequent research has indicated the following net reaction
as the predominant process:
Fe2þ þ H2 O2 ! Fe3þ þ HO þ OH ð1Þ
2+ 3+ 2+
where Fe and Fe represent the hydrated species, Fe(H2O)6 and
Fe(H2O)63+, respectively.* Reaction (1) is often referred to as the Fenton
reaction, although many other reactions occur in Fenton systems. The
primary utility of the Fenton reagent in the degradation of pollutants is the
formation of hydroxyl radical. Hydroxyl radical is a very strong, nonselective
oxidant capable of degrading a wide array of pollutants. Numerous studies
have addressed the applicability of Fenton reagent to pollutant degradation
and remediation.
Although formation of hydroxyl radical is a key step in the Fenton
reagent, other important reactions also occur. In fact, the overall process is
dramatically affected by the conditions under which the reaction occurs. Ad-
ditional important reactions occurring in aqueous mixtures of iron and hy-
drogen peroxide include the following:
Fe3þ þ H2 O2 ! Fe2þ þ Hþ þ HO2 ð2Þ
Fe 3þ
þ HO2 ! Fe 2þ þ
þ H þ O2 ð3Þ
Fe 2þ
þ HO2 i 6Fe 3þ
þ HO
2 ð4Þ
Fe 2þ
þ HO ! Fe 3þ
þ HO
ð5Þ
H2 O2 þ HO ! H2 O þ HO2 ð6Þ
Reactions (2) and (3) indicate processes that regenerate Fe2+ in the catalytic
cycle. As long as peroxide is available in the system, the iron species
continually cycle between Fe2+ and Fe3+, unless additional reactions result
in formation of insoluble iron oxides and hydroxides. The rate of formation
of hydroxyl radical can be expressed as:
Rate ¼ k1 ½Fe2þ ½H2 O2 ð7Þ
The concentration of Fe2+, however, is governed by all of the processes

involving iron (reactions (1) through (6)) as well as other reactions that may
control the concentration of free radical species in the system. Furthermore,
the second-order rate constant k1 is dependent on the coordination chemistry
* Throughout this chapter, waters of coordination are omitted for clarity. However, the reader
should be aware that any open coordination site on iron will be occupied by water. Iron typ-
ically has six coordination sites.
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Fenton and Modified Fenton Methods for Pollutant Degradation 167
of the iron. For example, Fe2+ in pure aqueous solution may exist as the
hexaaqua species, which has a rate constant different from that of iron bound
by other ligands such as phosphate. Therefore, the presence of both inorganic
and organic iron ligands in natural systems or waste streams can have a
dramatic influence on the Fenton reaction. Not only can the rate of reaction
(1) be influenced by other species present, but the lifetime of free radicals can
also be altered, resulting in changes in the Fe2+ concentration, again
influencing hydroxyl radical formation rate. Additional species can also affect
the efficiency of hydroxyl radical formation by providing competing sinks for
hydrogen peroxide. For example, manganese reacts with hydrogen peroxide
to form products that do not include hydroxyl radical. Such reactions
represent a waste of reagent, ultimately resulting in higher costs or ineffective
pollutant degradation.
Perhaps the biggest limitation of Fenton reagent for subsurface reme-
diation is the difficulty of delivering the reagent to the pollutant. In addition to
physical limitations in reagent injection efficiency, there are also limitations
on a molecular scale. Nonpollutant species act as hydroxyl radical scavengers,
consuming the radical before it can reach the pollutant. Furthermore, hydro-
phobic pollutants typically sorb to nonpolar sites within the soil. These sites
are not easily accessed by polar reagents such as iron and peroxide and,
therefore, pollutant molecules trapped in inaccessible hydrophobic sites are
likely to remain undegraded even under aggressive remediation conditions. A
thorough understanding of how hydroxyl radical is formed, its reactions with
nonpollutant species, and the interactions between pollutants and nonpollu-
tant species is necessary in order to effectively design pollutant degradation
protocols using Fenton reagent.
II. FENTON REAGENT MECHANISMS AND KINETICS

A. Fenton Reaction
The second-order rate constant k1 for reaction (1) has been reported as 76
M1 sec1 [3] (no detailed conditions provided) and as 41.4 M1 sec1 [4] in
the presence of 0.1 M HClO4. The fundamental mechanism for reaction (1)
has been proposed as [4]:
Fe2þ þ HOOH ! FeðOHÞ2þ þ HO ð8Þ
2þ
FeðOHÞ ! Fe 3þ
þ OH ð9Þ
2+
with reaction (8) being rate-limiting. If excess Fe is present in acidic
solution, an additional reaction (reaction (11)) results in stoichiometric
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conversion of hydrogen peroxide to water, representing a two-electron reduc-

tion of the peroxide:
2Fe2þ þ H2 O2 þ 2Hþ ! 2Fe3þ þ 2H2 O ð10Þ
with mechanistic steps of
Fe2þ þ HOOH ! FeðOHÞ2þ þ HO
Fe2þ þ HO ! FeðOHÞ2þ ð11Þ
2þ þ
FeðOHÞ þ H ! Fe 3þ
þ H2 O ð12Þ
If hydrogen peroxide is available in excess in a Fenton system, or if
additional Fe3+ is present, the overall reaction yields greater O2 formation [4]
by favoring reaction (3).
B. Scavengers
The presence of hydroxyl radical scavengers also plays a key role in the overall
fate of the peroxide. Scavenging of hydroxyl radical minimizes the occurrence
of reactions (5), (6), and (11). Organic scavengers generally react with hy-
droxyl radical in one of the two following types of reactions:
HO þ RH ! H2 O þ R ð13Þ
HO þ R ! ROH ð14Þ
Reaction (13) is typical of aliphatics and alcohols, whereas reaction (14) is
common for double bonds, especially in conjugated and aromatic systems. To
form the final products, the radicals R and ROH undergo additional
reactions. Free radical scavengers are a very important component of Fenton
systems, and their importance in pollutant degradation will be discussed
further in Secs. III and IV.
C. Haber–Weiss Reaction
Although Fenton did not observe hydroxyl radical-mediated reactions for
mixtures of Fe3+ and hydrogen peroxide, more recent work has illustrated
that such systems can produce hydroxyl radical. Haber and Weiss [5]
originally proposed a free radical mechanism for the Fe3+-catalyzed decom-
position of hydrogen peroxide. These reactions include [3]:
Fe3þ þ H2 O2 ! Fe2þ þ Hþ þ HO2
Fe2þ þ H2O2 ! Fe3þ þ HO þ OH
H2 O2 þ HO ! H2 O þ HO2
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Fe3þ þ HO2 ! Fe2þ þ Hþ þ O2

Fe2þ þ HO2 ! Fe3þ þ HO 2
The overall sum of these reactions, in the absence of radical scavengers, is the
Fe3+-catalyzed decomposition of 2 mol of hydrogen peroxide to 2 mol of
water and 1 mol of diatomic oxygen. Although the treatment of pollutants
with Fe3+/H2O2 mixtures has been referred to as the Haber–Weiss process, it
is clear that the same set of reactions is involved in both the Haber–Weiss
process and the Fenton process. The hydroperoxyl radical (HO2) formed in
reactions (2) and (6) is a good reducing agent and, under some circumstances,
it may reduce pollutant species. Studies suggesting this process will be
discussed in Sec. V.
Not only are the series of reactions in iron/peroxide systems complex,
but there are additional equilibrium processes that may effect the overall
reaction kinetics and mechanisms. Some pertinent equilibrium steps are given
below:
Fe3þ þ H2 O2 Ð FeOOH2þ þ Hþ ð15Þ
FeOOH 2þ
! Fe 2þ
þ HO2 ð16Þ
HO2 Ð H þ O2 þ
ð17Þ
þ
H2 O2 Ð H þ HOO ð18Þ
m 2mn
Fe 2þ
þ nL Ð ðFeLn Þ ð19Þ
m 3mn
Fe 3þ
þ nL Ð ðFeLn Þ ð20Þ
where L represents a ligand.
D. Iron Ligands and Coordination

Reactions (19) and (20) represent the coordination of Fe2+ and Fe3+ species.
Common ligands may include OH, Cl, HCO3, CO32, PO43, NO2,
NO3, and SO42. Coordination by anionic ligands makes oxidation of Fe2+
easier, yielding an increased rate constant for reaction (1) [6]. Conversely,
Fe3+-coordinated by anions may be more difficult to reduce to the divalent
species. Such changes in oxidation/reduction potentials for Fe2+ and Fe3+
not only alter the rate constant for reaction (1), but also change the relative
concentrations of the two iron species, consequently changing the rates of
several reactions in iron/peroxide systems. Some anions form insoluble salts
with iron. In these cases, the precipitation of iron may severely decrease or
eliminate its participation in Fenton reactions. Iron hydroxides and oxy-
hydroxides are likely to precipitate under higher pH conditions. As a result,
Fenton processes generally must be carried out at pH values well below 7,
unless iron-solubilizing agents (chelators) are added.
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Although the ligands in reactions (19) and (20) are represented as

negative ions, they could also be neutrals such as water. Furthermore,
multidentate ligands are likely in natural systems or in industrial waste
streams in which metal chelators are present. The presence of organic ligands
has several important implications for Fenton chemistry: (a) the chelated iron
species will have a kinetic behavior different from that of pure aqueous iron;
(b) the distribution and cycling between Fe2+ and Fe3+ states will vary with
different ligands; (c) the solubility of iron, especially at high pH values, can be
dramatically increased through chelation; (d) oxidizable ligands bound di-
rectly to iron (the site of hydroxyl radical formation) may be more likely to
react with the radicals than other species, including pollutants; and (e) some
iron complexes form alternate oxidants other than hydroxyl radical.
A number of reports have evaluated the Fenton reaction as a function
of iron ligands. Among ligands that substantially or completely inhibited
Fenton reactions are phosphate [7,8], desferal, diethylenetriamine penta-
acetic acid (DTPA), ethylenediamine di(o-hydroxyphenylacetic acid)
(EHPG), and phytate [9]. These are all strongly coordinating ligands or
chelators. Graf et al. [9] have proposed that both reactions (1) and (3) require
either a free iron coordination site or an easily displaced ligand (e.g., H2O) at
one iron coordination site. Further evidence to support this hypothesis has
been presented [10].
The activity of iron in the Fenton process varies as a function of its
speciation. As mentioned above, some ligands inhibit the Fenton process,
whereas others may enhance it. Some confusion exists in the literature re-
garding the enhancement of the Fenton process by iron chelators. For exam-
ple, several studies have evaluated the effect of iron chelators on the Fenton
reaction in the presence of phosphate buffers [11–13]. Phosphate is a strong
iron-binding agent and results in the formation of insoluble iron phosphates.
The addition of iron chelators resolubilizes iron, resulting in an increase in
the occurrence of reaction (1) and other reactions necessary in the catalytic
Fenton process. However, such results do not necessarily indicate that the
iron–chelator complex is more efficient than pure aqueous iron, Fe(H2O)62+
[9,14]. Another complicating factor is the hydroxyl radical-scavenging ability
of the chelator. A good scavenger may appear to have a lower production
rate of hydroxyl radical due to rapid trapping of the radical by the chelator.
Croft et al. [15] reported significant increases in k1 when iron was
chelated by DTPA, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic
acid (NTA), and several aminophosphonic acids. Compared to aqueous
Fe2+, increases in k1 from 1000-fold to 50,000-fold were indicated. They also
note that DTPA inhibits reaction (3). Graf et al. [10] suggest that reaction
(3) is completely inhibited by DTPA, EHPG, phytate, and desferal. These
two studies are not entirely consistent in their findings, possibly due to the
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use of aliphatic radical scavengers by Croft et al. These scavengers can

form R upon reaction with hydroxyl radical, possibly resulting in regener-
ation of Fe2+ by:
Fe3þ þ R ! Fe2þ þ Rþ ð21Þ
This point indicates the important role that additional reducing species,
whether free radicals or otherwise, have on the overall Fenton process.
Tannic acid has been reported to inhibit the formation of hydroxyl
radical by chelation of Fe2+ [16]. Because tannic acid is a plant-derived mate-
rial, it and other natural polyphenols may be important for subsurface appli-
cations of Fenton chemistry. A study of 50 different iron chelators assessed
the affect of each chelator on the Fenton process initiated with Fe3+ and hy-
drogen peroxide [17]. Among the nine classes of chelators tested, results indi-
cated that the chelators ranged from inactive to highly active in terms of
hydroxyl radical formation.
E. Photo–Fenton
In the presence of light, additional reactions that produce hydroxyl radical or
increase the production rate of hydroxyl radical can occur [18]:
H2 O2 þ hm ! 2HO ð22Þ
FeðOHÞ 2þ
þ hv ! Fe 2þ
þ HO ð23Þ
Fe ðL Þ þ hv ! Fe
3þ 2þ
þ L ð24Þ
where L is an organic ligand. Often called the photo–Fenton system, ir-
radiation of iron-peroxide solutions can result in more effective pollutant
degradation than dark Fenton systems. Although reactions (22) and (23) can
be important, the photochemical cycling of Fe3+ back to Fe2+ is perhaps the
most important aspect of the photo–Fenton process. Recalling that the rate of
hydroxyl radical formation is governed by the Fe2+ concentration (Eq. (7)), it
is clear that any additional route for reducing iron to the 2+ state will en-
hance the production rate of hydroxyl radical.
Photochemical reduction of Fe3+ has been observed in many systems,
including raindrops [19], water and wastewater [20–24], and natural surface
waters [25]. Concentrations of Fe3+ lower than 108 M are reportedly capable
of catalyzing the photo–Fenton reaction [26].
F. Ferryl Ion or Other High-Valent Iron Species

Although applications of Fenton chemistry to pollutant degradation most
likely involve hydroxyl radical as the primary oxidant, an alternative mech-
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anism that does not involve hydroxyl radical has also been proposed [4].
In this mechanism, instead of reaction (8), the following rate-limiting step
occurs:
HOOH þ Fe2þ ! FeO2þ þ H2 O ð25Þ
The importance of FeO2+ (the ferryl ion) as an alternate oxidant, instead of
hydroxyl radical, has been extensively debated. Much of the debate exists due
to difficulty in definitively detecting the ferryl ion and the hydroxyl radical.
Because of their low concentrations and short lifetimes, these species are
detected through indirect methods.
Fe(IV) has been observed for iron porphyrins reacting with tert-butyl
hydroperoxide in toluene solution [27], and Pignatello et al. [18] have re-
ported the existence of ferryl species in photo–Fenton systems under certain
conditions. Additional evidence using 17O-labeled H2O2 and water indicates
that all of the hydroxyl radical oxygen molecules originate from H2O2,
indicating that any ferryl ion formed must have its oxygen derived from
H2O2 [28]. Shen et al. [29] observed chemiluminescence upon the addition of
H2O2 to aqueous solutions of Fe(II). They postulated that an excited ferryl
species may be the source of the chemiluminescence, but also suggested that
the ferryl species resulted from the reaction of initially formed HO with
Fe3+. Bossmann et al. [30] observed degradation products of 2,4-dimethy-
laniline in Fenton systems, photo–Fenton systems, and with hydroxyl radical
generated by the photolysis of H2O2 in the absence of iron. Because different
products were observed in the absence and presence of iron, the authors
concluded that a different mechanism must occur in the iron-containing
system. An Fe4+ species was suggested to be the electron transfer agent that
oxidized 2,4-dimethylaniline to 2,4-dimethylphenol, whereas hydroxyl rad-
ical is not expected to form this product. Although this report provides
evidence for a nonhydroxyl radical mechanism for the oxidation of 2,4-
dimethylaniline, the nature of the oxidant was still not directly elucidated.
One important factor not considered in this study is the possible importance
of direct coordination of the amine to the iron. Such coordination would
likely alter the kinetics and mechanisms of oxidation.
In contrast to the results of Bossmann et al., Lindsey and Tarr [31,32]
observed equivalent rate constants for polycyclic aromatic hydrocarbon
(PAH) degradation with Fenton systems as had been previously observed
for PAH reaction with hydroxyl radicals as generated by pulse radiolysis
techniques [33]. Such kinetic agreement suggests, but does not confirm,
equivalent mechanisms. PAHs, unlike 2,4-dimethylaniline, are not expected
to directly coordinate iron in aqueous solutions.
Whereas only a few examples have been discussed here, it is obvious that
the exact kinetics and mechanisms for Fenton oxidations are highly depen-
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dent on conditions ([Fe2+], [Fe3+], [H2O2], iron chelators, nature, and con-
centration of the species being oxidized, etc.) Consequently, generalized ki-
netic and mechanistic predictions cannot be made to Fenton systems; rather,
a strong knowledge of the system under study is needed before kinetic models
can be applied. Nevertheless, in most practical applications, hydroxyl radical
appears to be the major oxidative species [18].
G. Other Metals
A number of other transition metal ions can also participate in Fenton-type
cycles to produce hydroxyl radical. Examples include Cu+, VO2+, Ti3+, Cr2+,
and Co2+ [4], although other reducing metals are also active in the formation
of hydroxyl radical from peroxide.
III. HYDROXYL RADICAL REACTIONS WITH ORGANIC

COMPOUNDS
Although there is still debate as to whether hydroxyl radicals or ferryl species

are the key oxidants in Fenton systems, most literature reports on the mech-
anisms of degradation of organic compounds invoke the hydroxyl radical.
Based on the reports discussed above, it seems likely that hydroxyl radical is
a major oxidant during Fenton degradations. Although ferryl ions or other
highly oxidized forms of iron may occur, either to a limited extent or more
abundantly under specific conditions, this section will deal with documented
reaction pathways and kinetics for hydroxyl radical or species assumed to be
hydroxyl radical. The reader should keep in mind that ferryl pathways may
need to be considered under certain conditions.
A. General Mechanisms
For the reaction of hydroxyl radical with organic species, there are three
common reaction pathways: (a) hydroxyl radical addition to unsaturated
systems (e.g., double bonds), (b) hydrogen abstraction (typically from alkyl or
hydroxyl groups), and (c) direct electron transfer. These generic mechanisms
are illustrated in Figure 1. For nonradical reactants, all three mechanisms
result in initial products that are radicals. Subsequent reactions follow to yield
nonradical products. Additional reactants are necessary to complete these
subsequent reactions. Common reactants include Fe2+, Fe3+, O2, H2O, H+,
HO, other metals, other organics, and other radicals present in the system.
Dimerization can also occur if the initially formed radical species reacts with
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Figure 1 Generic mechanisms for hydroxyl radical reaction with organic

compounds.
another identical radical. Typical reaction products include oxygenated

products (alcohols, aldehydes, oxyacids, ketones, etc.), ring opening prod-
ucts, and dimers. In some cases, complete mineralization yields carbon
dioxide as a final product.
B. Mechanistic Examples
The reaction of hydroxyl radical with unsaturated compounds often results
in the addition of the radical to the double bond to produce an unsaturated
alcohol. This reaction is quite common for aromatic systems. A number of
proposed reaction pathways are depicted in Figure 2. These reactions can
yield several products including hydroxylated species, dimers, and polyoxy-
genated products. Stable products, such as phenols and dihydroxybenzenes,
can react further to yield additional degradation products. Ring opening
products are the typical result of subsequent oxidation. The further oxidation
of dihydroxybenzenes by multiple hydroxyl radical attack is illustrated in
Figure 3. Whereas Figures 2 and 3 illustrate some of the possible reactions
occurring in Fenton systems, other pathways are also possible.
The reactivity of initial products will have a dramatic effect on their
buildup during oxidation. Those that react rapidly (e.g., benzoquinones) will
be seen only in minor amounts, whereas less reactive initial or subsequent
products will tend to accumulate. One weakness of in situ remediation
applications, using Fenton or other biochemical or chemical degradation
methods, is a failure to monitor potentially harmful degradation products.
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Figure 2 Proposed reaction pathways for hydroxyl radical reaction with benzene.
(From Refs. 3, 4, 105, and 106.)
Substituted aromatics can react either by addition of hydroxyl radical to

the aromatic ring structure or by reaction with the ring substituents. For
example, phenol can react through the addition of hydroxyl radical as
depicted for aromatics in Figure 2, or it can undergo hydrogen abstraction
from the alcohol, followed by subsequent steps. The relative importance of
these pathways will depend on the rate constants for each. Because the
aromatic structure generally has a higher rate constant than alcohols, attack
by HO addition to the ring is more prevalent. Similar comparisons can be
made for other substituents.
The final products of Fenton oxidation are dependent on several fac-
tors. The amount of hydroxyl radical is clearly important. In addition, the
amount of hydroxyl radical scavengers and the amount of pollutant present
will affect the array of final products. The concentrations of Fe2+ and Fe3+,
as well as those of other metals, also affect product distributions because
these species are involved in some degradation pathways. The presence of
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Figure 3 Proposed reaction pathways for hydroxyl radical reaction with hydroxyl-
ated aromatics. (From Refs. 3, 4, and 107.)
other radicals, including those produced from the Fenton cycle (e.g., HO2),
can provide alternate reaction pathways and thereby affect the distribution of
products. Under certain conditions (e.g., high peroxide concentration), sub-
stantial amounts of reducing species (HO2, O2) are present in high-enough
quantity that reductive pathways become important [34,35].
If hydroxyl radical availability is high enough, the pollutants present
will be degraded to CO2 and other mineralized products. However, if a species
of low reactivity is produced, this species may become a major degradation
product, and complete mineralization will not be observed. For example, ox-
alic acid has a relatively low rate constant for reaction with hydroxyl radical
(1.4 106 M1 sec1, about three to four orders of magnitude lower than
aromatics). Such highly oxygenated compounds, however, are likely to be
biodegradable. Consequently, such species can be acceptable end points for
remediation or waste stream treatment.
C. Kinetics
Hydroxyl radical reacts rapidly with a wide array of species. Typically, re-
actions follow second-order kinetics. In many cases, aqueous reactions with
hydroxyl radical are diffusion-limited. Two comprehensive sources of sec-
ond-order rate constants for reactions with hydroxyl radical are available
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[33,36]. Most compounds that have been studied have rate constants between
107 and 1010 M1 sec1, but a few compounds with lower rate constants
have been observed. These few examples include compounds with strong
electron-withdrawing groups or without C-H bonds [4]. Electron-donating
groups are believed to increase reactivity with hydroxyl radical [4]. In general,
alkenes and aromatics react rapidly with hydroxyl radical (k=109–1010 M1
sec1), whereas alkanes react somewhat more slowly (k=107–109 M1 sec1).
A few examples of rate constants are given in Table 1.
D. Other Important Factors

As has already been made clear, there are many factors that affect the ki-
netics and mechanisms of Fenton-based degradation. Rate constants, hy-
droxyl radical concentration, pollutant concentration, and the presence of
other species are all among the factors previously discussed. Additional im-
portant factors include those related to solubility and homogeneity.
Iron solubility is an obvious factor in Fenton oxidation because the rate
of hydroxyl radical formation is directly proportional to [Fe2+]. At elevated
pH values, iron hydroxides and oxides form and precipitate, causing a
dramatic decrease in hydroxyl radical formation rate. Iron chelators can be
used to offset this factor. A related issue is the rate of Fe3+ reduction to Fe2+,
which, if insufficient, can result in Fe2+ concentrations that are too low to
Table 1 Rate Constants for Reaction with Hydroxyl Radical

for Selected Compounds
Compound k (M1 sec1) Reference
Urea 7.910 5
36
Oxalic acid 1.4106 36
Benzene 7.8109 33
Phenanthrene 1.91010 32
Pyrene 1.51010 32
2-Methyl-2-(methylthio)propanal, 8.1109 36
O-[(methylamino)carbonyl]oxime
(Aldicarb)
Aniline 1.41010 33
Hexachlorocyclohexane (Lindane) 9.1108 36
Tetrachloroethylene (PCE) 2.6109 33
Dichloromethane 6107 33
Carbon tetrachloride Unreactive 104
Ethanol 2.2109 36
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produce hydroxyl radical at sufficient rates. The presence of reducing species

(e.g., HO2 and citrate) and the state of the Fe3+ are both important. Iron(III)
bound in very stable complexes may be resistant to reduction.
Homogeneity is a very important factor that has not been sufficiently
discussed in the literature. Even in aqueous-based systems, hydrophobic
pollutants may be isolated from iron that is coordinated by hydrophilic
ligands. Because hydroxyl radical is formed at the site of the iron, any factor
that causes the separation of iron and the pollutant will decrease the ef-
ficiency of pollutant degradation. Hydroxyl radical concentration will be
highest near iron species, and its concentration will decrease with increasing
distance from the iron site as the radical is scavenged. Consequently, any
species that has a reduced concentration near the iron ions will experience a
lower hydroxyl radical concentration than species that are randomly dis-
tributed throughout the solution. Furthermore, species that associate with
iron will be more likely to scavenge hydroxyl radical, preventing its reaction
with pollutants.
This effect has been illustrated for dissolved natural organic matter
(NOM) [31,32]. Because iron is chelated in hydrophilic regions and nonpolar
pollutants are often bound to hydrophobic regions of the NOM, the like-
lihood of pollutant oxidation is substantially reduced.
Soil systems present even greater challenges. In these systems, hydro-
phobic pollutants can be sorbed to soil in sites that have low accessibility for
the hydroxyl radical. Dissolved iron is not likely to enter into hydrophobic
soil pores and, therefore, pollutants in these sites can be extremely difficult to
degrade.
Studies on the degradation of polychlorinated biphenyls (PCBs) have
indicated that dissolved PCBs are much more readily degraded by hydroxyl
radical than are PCBs sorbed to sand [37]. PCBs sorbed to glass were also
difficult to degrade [38]. These studies suggest that hydroxyl radical is unlikely
to cross a phase boundary in order to react with the solid or sorbed pollutant.
The inability of hydroxyl radical to reach sorbed or otherwise seques-
tered pollutants is one of the major drawbacks to the in situ application of
Fenton degradation methods. Several reports have suggested that aggressive
conditions (i.e., high H2O2 concentration) can allow for direct degradation of
sorbed species [39–41].
IV. APPLICATIONS
A. Typical In Situ Applications
Fenton oxidation has been applied at many sites for in situ remediation of
contaminated soils. Typical applications have involved the degradation of
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light nonaqueous phase liquids (LNAPLs) and dense nonaqueous phase

liquids (DNAPLs), although some work has been done on larger molecules
(e.g., PAHs, PCBs, and energetic compounds). Application in soil systems
requires care and should only be carried out by experienced individuals.
Fenton treatment can liberate both heat and gas, and therefore can present
hazards when carried out in the subsurface, especially when high concen-
trations of peroxide are used.
Research conducted at Washington State University, as well as in situ
applications by commercial entities, has indicated that stabilization of hydro-
gen peroxide is necessary for effective subsurface injection [39]. Without
stabilization, added peroxide decomposes rapidly through interaction with
iron oxyhydroxides, manganese oxyhydroxides, dissolved metals, and en-
zymes (e.g., peroxidase and catalase). Some of these peroxide decay pathways
involve nonhydroxyl radical-forming mechanisms, and therefore are espe-
cially detrimental to Fenton oxidation systems.
Monobasic potassium phosphate was found to be an effective stabi-
lizer to prevent premature decomposition of hydrogen peroxide in soil
systems [39]. In this laboratory study, a disturbed silt loam was collected
from a diesel-contaminated maintenance and equipment storage yard.
Unstabilized 15 M hydrogen peroxide decomposed completely within the
first 2–4 cm of a column packed with this soil. With 150 mM KH2PO4 added
to the peroxide solution, the penetration depth of the peroxide was increased
threefold. The protective effect of the stabilizer was diminished through the
removal of phosphate from the solution as it passed through the soil
column. Removal was believed to be via ion exchange or another fixation
process. Hexadecane oxidation in this soil was improved by the addition of
>30 mM KH2PO4. Furthermore, degradation of hexadecane was spread
over a longer column depth when the stabilizer was added, whereas only the
hexadecane in the top 2 cm was degraded in the absence of the stabilizer.
These results further demonstrate that observation of peroxide decomposi-
tion rates is not necessarily a good indicator of pollutant degradation rate
because nonhydroxyl radical-forming pathways may contribute substantial-
ly to peroxide decomposition.
In addition to in situ soil applications, Fenton reagent has also been
studied for treatment of industrial waste streams. For example, the treatment
of residual Kraft black liquor from the pulp-and-paper industry has been
shown to be effective [42]. Near-complete degradation of lignin (95–100%)
and decolorization were achieved under optimized conditions. Basic oxygen
furnace slag was evaluated as a source of iron for degradation of 2-chloro-
phenol in industrial wastewater [43], and favorable results were achieved.
Treatment of olive mill wastewater has also been carried out with
Fenton reagent [44]. This study also used Fenton treatment in conjunction
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with subsequent aerobic biotreatment. The Fenton treatment moderately

reduced chemical oxygen demand (COD) and had a significant impact on the
polyphenolic content of the wastewater.
Reports of industrial applications to waste stream treatment are less
abundant than in situ soil applications because many of these applications
are developed in commercial applications and are not disclosed in the liter-
ature.
B. Iron Minerals as Fenton Catalysts

Aqueous Fe2+ and many of its coordination complexes serve as excellent
catalysts for the formation of hydroxyl radical from hydrogen peroxide. Iron
oxyhydroxides have also been found to catalyze the formation of hydroxyl
radical [45], although at a much slower rate than dissolved iron. Conse-
quently, a number of researchers have investigated the potential for using
soil minerals as catalyst to avoid the need for the addition of soluble iron to
the system.
In laboratory studies, Ravikumar and Gurol [46] monitored the Fenton
degradation of pentachlorophenol (PCP) and trichloroethylene (TCE) from
sand. In both column and batch studies, they observed the degradation of
PCP and TCE with the addition of hydrogen peroxide only. They concluded
that iron naturally present in the sand was an effective catalyst for the
formation of hydroxyl radical from the added peroxide. However, addition
of soluble ferrous salts caused a more rapid degradation of the pollutants,
indicating that either insufficient iron was present in the sand or the nature of
the iron in the sand made it a poor catalyst.
Without added iron, 7 mol of hydrogen peroxide were needed per mole
of PCP oxidized, whereas the peroxide demand for TCE degradation was
3.7 mol of peroxide per mole of TCE oxidized. With Fe2+, these peroxide
demands decreased to 4.3 and 2.1 for PCP and TCE, respectively. Chloride
release was f80–90% of the theoretical value for each compound and was
only slightly higher with added iron. This early study demonstrated the po-
tential to perform in situ Fenton oxidation without added iron. However,
the added complexity of most real systems increases the need for added
soluble iron.
Although the authors in this sand study reported the iron content of the
sand, there remains a possibility that noniron species were acting as catalysts.
In fact, a study of coal (anthracite) oxidation by hydrogen peroxide indicates
that formation of hydroxyl radical occurs even after the removal of iron from
the coal [47]. This study suggested that surface sites on the coal may have
acted as catalytic centers for hydroxyl radical formation. Whereas coal is
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quite distinct from the sand system that Ravikumar and Gurol used, the work
on coal raises the possibility that noniron soil minerals or organic matter
could also serve as catalysts for hydroxyl radical formation.
In other laboratory studies, Watts et al. [48] found that iron oxyhy-
droxides yielded a better stoichiometric efficiency (mole of H2O2 consumed
per mole of pollutant degraded) than soluble iron. This observation may be
related to inefficiencies in hydroxyl radical utilization if it is formed too rap-
idly, as in the system with dissolved Fe2+.
Watts et al. [49] have also studied the hydrogen peroxide-induced deg-
radation of several chlorinated aromatics sorbed to hematite (a-Fe2O3) with
no other source of iron. 1,3,5-Trichlorobenzene, 1,2,3,4-tetrachlorobenzene,
pentachlorobenzene, and hexachlorobenzene were all degraded by sufficient
concentrations of added peroxide (0.1–5%). Hydroxyl radical concentration
was found to be independent of hydrogen peroxide concentration, indicating
that the catalytic sites were peroxide-saturated at the concentrations used.
As with other reports by Watts et al., at high peroxide concentration, deg-
radation rates exceeded desorption rates. This result has been interpreted as
evidence of direct oxidation of sorbed species, although alternate explana-
tions are possible.
Goethite (a-FeOOH) has also been studied as a potential Fenton-like
catalyst [50]. Hydrogen peroxide decay over goethite exhibited second-order
kinetics according to:
d½H2 O2 =d t ¼ k½FeOOH½H2 O2 ; k ¼ 0:0031 M1 sec1 ð26Þ
at pH=7. The kinetics were determined to be dependent on the intrinsic

reaction rates at the oxide surface. In comparison, the rate constant for Fe2+
reaction with H2O2 (Eq. (1)) is in the range of 40–80 M1 sec1 [3,4]. In
additional studies, it was suggested that hydroxyl radical reacted with the
pollutant sorbed on the mineral surface [51,52]. Although several reports
make this assertion, such conclusions should be scrutinized carefully because
some evidence may be indirect. In a separate study, goethite was observed to
be a better catalyst than ferrihydrite or semicrystalline iron oxides for the
Fenton-based degradation of quinoline [53].
Lepidocrocite (g-FeOOH) has also been used as a catalyst for Fenton-
like reactions [54]. First-order decomposition of hydrogen peroxide was
observed in the presence of this catalyst. Peroxide decay at 20 g/L catalyst
was found to be pseudo-first-order and pH-dependent, with rate constant
values reported from 0.102 hr1 at pH 3.3 to 0.326 hr1 at pH 8.9. In this
system benzoic acid degradation was fastest at the low pH value. Under these
conditions, acid dissolution of the lepidocrocite was observed to produce
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Fe2+. Because peroxide decomposition was slowest under the same con-
ditions at which benzoic acid decomposition was highest, it is important to
consider the efficiency of hydroxyl radical formation from peroxide decom-
position. With the surface catalyst, either hydroxyl radical is not readily
available to benzoic acid and is scavenged by other species, or the mineral-
catalyzed decomposition of hydrogen peroxide involves additional, non-
hydroxyl radical-forming pathways for peroxide decomposition.
This last point emphasizes a weakness in the Fenton literature pointed
out previously. Often, the rate of peroxide decomposition is assumed to be
proportional to the hydroxyl radical formation rate. However, nonhydroxyl
radical-forming pathways and the formation of radicals that are not ac-
cessible to pollutants may significantly decrease the yield of useable hydroxyl
radical.
Hematite has been studied as a Fenton catalyst [55,56]. Catalytic
decomposition of hydrogen peroxide by hematite was found to be slower
than that for ferrihydrite or goethite, although hematite had the highest
activity for 2-chlorophenol degradation [55]. The degradation efficiency of 2-
chlorophenol was correlated with the inverse sequence of specific area and
point-of-zero charge of the Fe oxides. Furthermore, particle size and porosity
characteristics played important roles in governing the degradation kinetics.
Unlike magnetite, hematite was not observed to catalyze the disproportion-
ation of hydrogen peroxide, which, if it occurs, is a source of inefficiency [56].
The release of free iron was observed in these systems, but the use of ferrozine
and desferrioxamine, strong iron chelators, prevented the activity of dissolved
iron with respect to peroxide.
Ferrihydrite catalysis of hydroxyl radical formation from peroxide has
also shown experimental results consistent with a surface reaction [57]. The
yield of hydroxyl radical formation was lower for ferrihydrite than for dis-
solved iron, resulting in a higher peroxide demand to degrade a given amount
of pollutant. As mentioned above, although ferrihydrite exhibited a faster
rate of peroxide decomposition than goethite or hematite, the rate of 2-
chlorophenol degradation with these catalysts was fastest for hematite [55].
In other studies, quinoline oxidation by peroxide was not observed when
ferrihydrite was used as catalyst [53].
Mixed element oxides such as Fe–Si–O, Fe–Mg–O, and Fe–Mg–Si–O
complex oxides have also been used as catalysts for Fenton-like oxidations
[58]. Some of these catalysts exhibited selectivity for phenol hydroxylation.
Whereas these catalysts are unlikely to be useful for in situ applications, they
may be valuable for waste stream treatment, especially when a well-defined
waste stream with specific pollutants exists.
Other iron species have also been evaluated as potential Fenton
catalysts. These include magnetite [59], pyrite [60], and basic oxygen furnace
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slag [43]. As with other studies, these solids were able to catalyze pollutant
degradation in the presence of hydrogen peroxide, but at a slower rate than
for dissolved iron. Furthermore, the presence of Fe2+ (aq) dissolved from the
solids may be the key catalyst in some systems.
Because of the slower kinetics for hydroxyl radical formation with
mineral catalysts, most applications of Fenton oxidation for in situ re-
mediation or waste stream treatment involve the addition of dissolved
iron(II).
C. Iron Chelators
Iron speciation is a major factor in Fenton chemistry. As previously dis-
cussed, iron solubility, redox potentials, and concentrations of Fe2+ and
Fe3+ are all dependent on the ligands that coordinate iron. In order to pro-
duce hydroxyl radical, there must be a readily accessible coordination site for
H2O2 to bind to [9,10]. Very strong iron chelators, therefore, inhibit the
formation of hydroxyl radical. Iron ligands can also act as hydroxyl radical
scavengers. Because the radical is always formed in close proximity to these
ligands, they are more likely to react with hydroxyl radical than pollutants
that are not in close proximity to the iron.
In many in situ applications, phosphate or other peroxide stabilizers are
added. These species are likely the dominant iron ligands; however, natural
ligands and chelating agents may coordinate some of the iron. Such coordi-
nation will alter the kinetics of hydroxyl radical formation as well as the
dynamics of hydroxyl radical interaction with pollutants.
Several studies have investigated the effect of chelators on the Fenton
reaction. Addition of chelators to Fe(III)–H2O2 systems allows for effective
degradation at near-neutral pH values [17,23,61]. Much of the influence of the
iron chelators stems from increased solubility of iron species at higher pH
values. These chelators were also effective for combined Fenton bioremedia-
tion treatment because they eliminate the need for low pH, which can harm
useful bacteria.
Many phosphates have been observed to inactivate iron as a catalyst for
the formation of hydroxyl radical [17]. Included in those studied are pyro-
phosphate, phytate, adenosine 5V-triphosphate, and others. Of the 50 com-
pounds tested in one study, those having the highest activity in terms of 2,
4-dichlorophenoxyacetic acid degradation were: nitrilotriacetic acid, hydroxy-
etheliminodiacetic acid, picolinic acid, gallic acid, rhodizonic acid, tetrahy-
droxy-1,4-quinone, and hexaketocyclohexane [17]. Additional studies
indicated that several of these iron chelators were effective in Fenton degra-
dation of other pollutants at near-neutral pH, including 2,4,5-trichlorophe-
noxyacetic acid, atrazine, picloram, baygon, and carbaryl [23].
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These iron chelators improved the Fenton oxidation of pollutants by

increasing iron solubility, and perhaps also by increasing the rate constant
for hydroxyl radical formation from peroxide. However, despite their posi-
tive effects, these chelators also acts as hydroxyl radical scavengers. Not only
does this scavenging remove hydroxyl radical from potential interaction
with pollutants, but it also degrades the chelator. Over time, loss of chelator
results in poor iron solubility and slow rates of hydroxyl radical formation.
Earlier studies indicated that at pH 7.3, each EDTA–Fe complex was able to
produce more than 50 hydroxyl radicals before being degraded [13].
Flavenoids, common plant-derived compounds that are widespread in
the environment, have been tested for their effect on the Fenton reaction [62].
These compounds are known hydroxyl radical scavengers. Myricetin, quer-
cetin, catechin, morin, and kaempferol were all found to enhance the for-
mation of hydroxyl radical in Fe(III)–EDTA systems. No change in radical
formation was observed with added flavone. In the presence of ascorbate, a
good reducing agent that converts Fe3+ to Fe2+, the flavenoids had little
effect on hydroxyl radical formation. This observation suggests that the
flavenoids enhanced hydroxyl radical formation by reducing Fe3+ to Fe2+.
However, this study utilized a phosphate buffer and a strong iron chelator
(EDTA). Therefore, the flavenoids may not have been able to effectively
coordinate the iron under these conditions. In the absence of EDTA and
phosphate, compounds such as flavenoids could act both as iron chelators
and as iron-reducing agents. Unfortunately, insufficient data are available to
determine the effects of these and other natural chelators in systems without
other additives.
In the presence of adenosine triphosphate, flavenoids were observed to
inhibit hydroxyl radical formation [63]. These contrasting results further
emphasize that the effect of iron chelators is highly dependent on the other
species present. The relative efficiencies of the chelators for hydroxyl radical
formation will determine whether the added chelator will have a positive or
negative effect on radical formation. Furthermore, increased radical forma-
tion is not always correlated with improved pollutant degradation. Catechol
groups and 4-keto,5-hydroxyl benzene groups are believed to be important
iron coordination sites for flavenoids [63].
Other catechol-containing natural compounds have been implicated as
Fenton-enhancing compounds in white rot fungi, brown rot fungi, and mold-
mediated degradation of lignin and wood [64,65]. In addition to their poten-
tial effect on in situ remediation, these compounds may be of potential benefit
for the pulp-and-paper industry.
Tannic acid, a plant polyphenol, has also been studied with respect to its
effect on Fenton reaction [16]. Formation of a Fenton-inactive Fe(II)–tannic
acid was believed to be the mechanism by which tannic acid inhibits Fenton
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reaction. Although tannic acid is a good hydroxyl radical scavenger, its scav-
enging effects appeared to be secondary in this study. Tannic acid is also
capable of reducing Fe3+ to Fe2+, but because the Fe(II)–tannic acid is
Fenton-inactive, the reduction of tannic-bound iron does not contribute to
the catalytic cycle. Tannic acid is able to compete with EDTA for complex-
ation of iron. Therefore, in soil systems with significant levels of tannic acid,
addition of beneficial iron chelators may not be completely effective.
Numerous studies have evaluated the effects of chelators [8,12,15,66–
71]. However, the effects of natural chelators have not been thoroughly
studied, especially as related to in situ remediation. Consequently, in situ
applications may suffer from decreased efficiency caused by interferences
from natural chelators present in the site.
D. Photo–Fenton
As previously discussed, the concentration of Fe2+ is an important factor in
the rate of hydroxyl radical formation from hydrogen peroxide. Consequent-
ly, any process that can speed the reduction of Fe3+ to Fe2+ will increase
the formation rate of hydroxyl radical. UV or visible radiation can play
this role by photoreducing iron. However, the photo–Fenton process in-
volves three additional mechanisms that can contribute to pollutant degra-
dation: (a) direct photolysis of H2O2 to yield two hydroxyl radicals (Eq. (22));
(b) photolysis of Fe(OH)2+ to form hydroxyl radical (Eq. (23)); and (c)
degradation of pollutants by direct photolysis (i.e., absorption of a photon
by the pollutant molecule followed by decomposition of the photoexcited
pollutant molecule).
Photo–Fenton systems have been studied for the degradation of a wide
range of pollutants. Chlorophenoxy herbicide degradation by Fenton pro-
cesses was found to be significantly enhanced by UV radiation [23,72].
Additional compounds that were effectively degraded using photo–Fenton
systems include metolachlor and methyl parathion [73], organophosphorous
compounds [74], PCBs [75], polychlorinated dibenzo-p-dioxins, and dibenzo-
furans [76]. Dyes found in textile wastewater have also been degraded using
photo–Fenton techniques; Orange II (an azo dye) [77] and the reactive
dyestuff, R94H [78], were degraded. Whereas Orange II was effectively
mineralized, R94H was decolorized, but not mineralized. Interference from
polyvinyl alcohol, a common component of textile wastewaters, was cited as
interfering with R94H degradation. As discussed before, the presence of
hydroxyl radical scavengers can be a major impediment to the degradation of
targeted pollutants. In contrast, the photo–Fenton degradation of penta-
chlorophenol was found to be enhanced by the presence of humic acid [79].
Although humic acid is a good scavenger of hydroxyl radical, the phenolic
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acid groups of humic acid were believed to play a major role in Fe3+ photo-
reduction, thereby significantly enhancing the PCP degradation.
Lignin, a major structural component of wood, was also degraded by a
photo–Fenton technique [80]. Although this report demonstrated the ability
of the method to degrade lignin, the study did not elaborate on potential
applications in the pulp-and-paper industry. The treatment of kraft mill
bleaching effluent by Fenton and photo–Fenton methods has been studied,
and was reportedly more effective and more economical than several other
techniques [81].
Attempts have been made to immobilize iron in photo–Fenton systems.
Iron immobilized in NafionR was successfully used to degrade 4-chlorophe-
nol [82] and Orange II [83]. In both studies, the authors indicated that the
NafionR-bound iron was resistant to aging or fouling.
Efforts to develop large-scale or prototype photo–Fenton reactors have
also been reported [84–86]. As with any photocatalytic method, the ability of
the photons to reach the catalyst is a key design issue.
E. Combined Fenton Biodegradation

Biodegradation is often a desirable approach to in situ remediation because
it is of relatively low cost and low intervention. However, many microbial
systems are limited by the toxicity of pollutants, especially when high con-
centrations or mixtures of compounds are present. Furthermore, microbial
systems may be limited to a single compound or to a group of structurally
related compounds. Consequently, diverse mixtures of contaminants can
be problematical for biodegradation systems. Finally, biodegradation tech-
niques are relatively slow and, therefore, cannot be used in sites where im-
mediate action is required. Chemical systems do not generally suffer from the
above listed limitations, although they may be more costly, require more ex-
tensive activity at the site, or may have other limitations. In order to capitalize
on the benefits of both biological and chemical systems, it is often beneficial to
utilize a chemical pretreatment step, followed by a longer-term biodegrada-
tion phase of treatment.
Tetramethyl ammonium hydroxide (TMAH) toxicity, as measured by a
MicrotoxR assay, was dramatically reduced after pretreatment with Fenton
reagent. Subsequent biodegradation was successful. Without the Fenton
pretreatment, biodegradation was slow and required a substantial accla-
mation period [35]. The biodegradation of anthracene [87] and benz(a)an-
thracene [88] were improved with Fenton pretreatment. For anthracene
biodegradation over 30 days, 30% of the compound was degraded without
pretreatment, whereas 90% was degraded with Fenton pretreatment. Benz-
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(a)anthracene was only 12% biodegraded in 63 days without pretreatment,

but was 98% degraded with Fenton pretreatment. Both compounds were
converted to intermediate products by Fenton oxidation: anthracene was
mainly converted to 9,10-anthraquinone and benz(a)anthracene was sub-
stantially converted to benz(a)-7,12-dione. These intermediate products were
readily biodegraded. Tetrachlordibenzo-p-dioxin (TCDD) pretreated with
Fenton reagent yielded chlorophenols and chlorobenzenes that were readily
biodegraded [89].
Although there are reports of improved biodegradation with Fenton
pretreatment, there are also reports indicating limitations of Fenton pretreat-
ment. Acid conditions often used for Fenton treatment are usually incompat-
ible with microbial activity, and measures to overcome this incompatibility
must be taken. For example, the use of iron chelators and higher pH values is
one approach that has been taken [61].
In the case of a biorecalcitrant textile effluent from a site in southern
France, photo–Fenton pretreatment was not successful in improving biode-
gradability even when 70% of the effluent was mineralized by photo–Fenton
treatment [90]. Aromatic intermediates were believed to be responsible for the
recalcitrance of the pretreated effluent.
F. Examples of In Situ Applications

In situ treatment of contaminated soil or groundwater requires specific de-
sign parameters that are site-dependent. Treatment of a site requires several
steps, including site assessment (contaminant identification and distribution
as well as site geology and hydrology), bench-scale and/or pilot field-scale
testing, design of remediation strategy, implementation of remediation, and
site monitoring (before, during, and after remediation). Reports detailing
treatment on government properties are publicly available. Consequently, a
large amount of information is available on the details of these remediation
projects, either through government agencies or directly from the remedia-
tion firm that performed the work. An overview of two examples is given
below, representing only a small sampling of the many contaminated sites
that have been remediated with Fenton technologies.
Volatile organic compounds (VOCs) were degraded in groundwater at
the Naval Air Station, Pensacola, FL (NAS Pensacola) using Fenton-based in
situ chemical oxidation [91]. Trichloroethene (TCE) at 2440 Ag/L and its
degradation products cis-1,2-dichloroethene (403 Ag/L) and vinyl chloride
(976 Ag/L) were the major contaminants at this site. These contaminants were
focused predominantly in a region from 35 to 45 ft below the surface. The soil
at this site consisted of marine terrace sands of fine to medium quartz. An
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impermeable clay layer existed at a depth of 35–45 ft. Dense nonaqueous

phase liquids tend to settle to the lowest depth, and often reside just above
such impermeable clay layers.
For this site, pressurized injection of concentrated hydrogen peroxide
and ferrous ion was used to carry out in situ Fenton oxidation. Fourteen in-
jectors were installed at various depths in order to maximize the effectiveness
of the degradation approach. These injectors were placed either in the
contaminant source zone or downgradient from the source in the ground-
water flow. Injectors and wells were designed and constructed to withstand
elevated temperatures and pressures expected during Fenton treatment.
Reagents (hydrogen peroxide and ferrous ion catalyst solution) were mixed
at the head of the injector just prior to injection into the subsurface. The
design of the injectors used at this site is presented in Figure 4.
In the first phase of treatment, approximately 4089 gal of 50% H2O2
and an equal volume of ferrous ion catalyst solution were injected over a
Figure 4 Design of hydrogen peroxide and iron injector used for remediation of
contaminated sites. (From GeoCleanse International, Inc., U.S. Patents 5,525,008
and 5,611,642.)
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5-day period with injection rates of each reagent of between 0.2 and 1.4 gal/
min per injector. Air was also injected at rates of up to 3 ft3/min to facilitate
reagent distribution. Groundwater pH, alkalinity, total iron, hydrogen perox-
ide concentration, chloride concentration, headspace VOCs, oxidation–re-
duction potential, and conductivity were monitored. pH values of less than 6
were needed, and total iron levels of z5 mg/L in groundwater were optimal.
Offgas production was monitored in order to follow the progress of the
degradation. Carbon dioxide was indicative of pollutant (or at least organic
compound) degradation. Oxygen was taken as an indicator of Fenton re-
action occurring in the absence of organic compounds (see reaction (3)).
After the first phase of treatment, the site was recharacterized to deter-
mine the extent of degradation and the new distribution of pollutants. A
second phase of reagent injection was carried out (6038 gal of each reagent)
over a 5-day period approximately 5 months after the first phase of in-
jections. This phase of treatment was also accompanied by site monitoring.
After the first phase of treatment, VOC concentration decreased in one
monitoring well, but remained relatively unchanged in the remaining wells.
After the second phase of treatment, which utilized phosphoric acid as a
peroxide stabilizer to increase its radius of influence, VOC concentrations
were substantially decreased, on the order of 96–100%. In a 30-day posttreat-
ment sampling, levels of VOCs were found to be the same as immediately after
treatment, indicating successful treatment of the site. Chromium(III) present
in the site was not oxidized to Cr(VI) to any detectable level during the
treatment. The formation of Cr(VI) in oxidizing treatment technologies is
always a concern in any site that has substantial levels of Cr(III).
In another study, bench-scale and field pilot tests were conducted to
assess the applicability of in situ Fenton treatment of explosives (nitro-
aromatic compounds) dissolved in groundwater at the Pueblo Chemical
Depot (PCD), CO [92]. The soil in the site consisted of eolian, alluvial, and
colluvial deposits over a layer of shale bedrock. Groundwater concentrations
of 1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT) were 18,000
and 3000 Ag/L, respectively. Additional nitroaromatic compounds were pre-
sent at lower concentrations. The pilot program was designed to test the abil-
ity of Fenton reagent to degrade these contaminants under the site geological
and hydrological conditions, as well as to determine the optimum design
parameters for delivery of the reagents (e.g., injector spacing, reagent com-
position, and injection rate). The effect of treatment on nitrate production,
soil pH, and heavy metal mobility was also assessed.
Bench-scale tests revealed several important conclusions. First, the
groundwater buffering capacity was found to be relatively high. This is a key
issue because Fenton treatment is often ineffective at high pH due to iron
precipitation. Bench tests also indicated that from some field-collected soil
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samples, explosives were leached from soil by application of iron and lowered
pH. Other sites did not exhibit increased mobility of the pollutants. Increased
mobility of pollutants may be beneficial because they are more easily de-
graded in the desorbed state. However, the mobility of undegraded pollutant
must be carefully monitored. Lack of pollutant desorption from soils in-
dicates the potential that some of the pollutants may be difficult to degrade if
sorbed in inaccessible pores. Bench-scale oxidation trials did indicate some
degradation of the pollutants upon Fenton treatment. However, interfer-
ences were observed when using the EPA Method 8330, and an alternate
analysis method was required (Method 8321A). No significant increase in
nitrate concentration was observed in these trials. Hexavalent chromium,
total chromium, cadmium, lead, silver, and mercury showed no changes after
treatment, whereas arsenic and barium levels increased slightly. The concen-
tration of these latter two species remained below regulatory levels. The
concentration of manganese showed a dramatic increase from 160 Ag/L be-
fore treatment to 6400 Ag/L after treatment.
The pilot-scale study involved the injection of 1975 gal of 50% H2O2
and 7964 gal of acidic ferrous solution into the site over a 7-day period.
Injection wells were found to have a radius of influence of 20–24 ft. The
groundwater concentrations of the minor contaminants were substantially
reduced after treatment, although the major contaminant (TNB and TNT)
groundwater concentrations increased. These increases were believed to be
due to desorption. The observed increase of nitrate, over 100 times beyond
that expected from dissolved pollutants, suggested that sorbed explosives
were degraded in this treatment. Microbial activity was reduced but not
eliminated after treatment. Metal desorption was noted during treatment, but
subsided as ambient conditions returned. No oxidation of chromium to
Cr(VI) was observed. Based on the results of this pilot study, Fenton treat-
ment was considered to be a viable method for treating ‘‘hot spots’’ (i.e., high
concentration areas) of explosives-contaminated soils.
V. NEW DEVELOPMENTS
A. Complexing Agents to Improve Fenton Selectivity
and Efficiency
Recent work at the University of New Orleans has focused on methods of
bringing pollutants and hydroxyl radical together to improve selectivity and
to enhance the rate and efficiency of pollutant degradation. As previously
discussed, sorption of pollutants into hydrophobic sites substantially inhibits
their degradation because hydroxyl radicals are less likely to penetrate into
these sites. Because the catalyst for hydroxyl radical formation (Fe2+) is
hydrophilic, it is unlikely that the pollutant will be near the formation site of
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the radical in most systems. In order to alleviate these problems, we have

utilized natural compounds that are capable of simultaneously complexing
with both a hydrophobic pollutant and a hydrophilic iron ion. In this manner,
several improvements can be achieved: (a) the pollutant is more likely to en-
counter a hydroxyl radical because they are formed nearby; (b) the pollutant
is removed from its isolated, hydrophobic site that is not accessible to dis-
solved hydroxyl radicals; and (c) the importance of scavengers is reduced
because the pollutant is, on average, closer to the formation site of the radical
than is a dissolved scavenger.
The natural molecules that have been found to be successful in
improving Fenton degradation of hydrophobic pollutants are cyclodextrins
(CDs). Cyclodextrins are cyclical oligosaccharides with six, seven, or eight
glucose rings fused to form a-cyclodextrins, h-cyclodextrins, or g-cyclodex-
trins, respectively. The interior portion of these torus-shaped molecules is
relatively hydrophobic. The upper and lower rims contain primary and sec-
ondary hydroxyl groups that extend outward and give the molecules rela-
tively high water solubility [93–95]. Cyclodextrins have been used for a
number of applications, including chromatography [93,94]; introduction of
catalysts that stabilize the transition state of the substrate [96–98]; and
pharmaceutical, agricultural, and food applications. Because of their hydro-
phobic interior and ability to include nonpolar molecules, CDs enhance the
aqueous solubility of hydrophobic compounds [99,100].
Wang and Brusseau [95] and Brusseau et al. [101] studied a derivitized
CD, carboxymethyl-h-cyclodextrin (CMCD), for simultaneous soil washing
of metals and organic contaminants. Metals such as Cd2+ are chelated di-
rectly by the oxygen atoms on the rim of the CMCD, and hydrophobic or-
ganic pollutants can also be included within the nonpolar cavity [95–101].
Consequently, both classes of pollutants can be mobilized with CDs.
In order to further profit from the dual complexing ability of CDs, we
have studied Fenton-type processes in the presence of CDs. Several classes of
compounds showed enhanced degradation rates in the presence of CDs in
aqueous solution: PCBs, PAHs, TNT, and chlorinated phenoxyacetic acids
[38,102]. Dissolved natural organic matter typically inhibits Fenton degra-
dation by sequestering the iron away from the pollutant [31,32]. However,
addition of cyclodextrins overcame the inhibitory effect of the NOM and
resulted in enhanced degradation rates [38].
Fluorescence spectroscopy and mass spectrometry have suggested that
a ternary complex of iron–cyclodextrin–pollutant exists in solution. Such a
complex is believed to play a key role in increasing pollutant degradation
rates. Studies using added scavengers also support this theory [38]. A sche-
matic illustration of such a theorized ternary complex is depicted in Figure 5.
Table 2 presents representative enhancements in observed degradation
rates for several aqueous pollutants upon the addition of CMCD. As can be
TM
192 Tarr
Figure 5 Preliminary schematic representation of a ternary iron–cyclodextrin–

pollutant complex believed to be involved in improving the efficiency and selectivity
of Fenton degradation of hydrophobic organic pollutants.
seen, up to 10-fold rate enhancements have been observed. In general, these

studies used millimolar concentrations of iron and cyclodextrin to degrade
pollutants present in low-micromolar to near-millimolar concentrations. The
optimum concentrations of iron, peroxide, and cyclodextrin are dependent on
the specific pollutant, its concentration, and the nature and concentration of
other species present. Another advantage of the CMCD system is the ability
to work at near-neutral pH values in many cases. Just as for other iron
chelators discussed above, the cyclodextrin improves the water solubility of
iron and helps prevent the precipitation of iron hydroxides. Although these
results are promising, the demonstration of this approach in soil-containing
systems has not yet been achieved.
B. Reductive Degradation
As can be seen from reactions (2), (6), (16), and (17), the reducing species
HO2 (hydroperoxyl radical) and O2 (superoxide) are formed in Fenton
TM
Table 2 Observed Enhancements in Degradation Rate Constants with

CMCD Added
CMCD added No CMCD
Pollutant k/koa (no NOM) k/ko (with NOM) k/ko (with NOM)
Naphthalene 2.3
Phenanthrene 1.9 0.44
Pyrene 1.3 1.3 0.8
TNT 7.3 (pH=3) 2.5 (pH=3)
9.3 (pHf7)
2,4,5-T 1.2 0.5
PCB-54 13b
(sorbed to glass)
a
k/ko=ratio of observed rate constant with additives (k) to observed rate constant without
additives (ko). Additives were either CMCD or NOM.
b
Ratio of total amount of PCB degraded with CMCD to total amount of PCB degraded
without CMCD.
systems. Whereas the concentrations of these species are generally low, under
high peroxide concentrations, substantial amounts of these reducing species
can be produced. Under such conditions, reductive degradation can become
an important pathway for the removal of pollutants. Furthermore, reductive
pathways have been suggested as potential mechanisms for the desorption of
pollutants from soil sites.
Enhanced desorption of chlorinated aliphatic compounds from a sandy
loam soil was observed in Fenton systems with peroxide concentrations
greater than 0.3 M [34]. Observed degradation of hexachloroethane, which
does not react with hydroxyl radical, was provided as evidence of alternate
degradation pathways other than hydroxyl radical or other strongly oxidizing
species. Addition of a reductant scavenger (chloroform) resulted in a com-
plete inhibition of hexachloroethane degradation, again providing evidence
for a reductive pathway. Furthermore, the appearance of a reduced product,
pentachloroethane, also suggested a reductive pathway. A report written in
Korean also detailed the degradation of CCl4, presumably through reaction
with superoxide and hydroperoxide [103].
Studies of CCl4-containing systems treated with Fenton reagents with
high peroxide concentrations have led to the conclusion that a reductive
pathway is involved [104]. Carbon tetrachloride was unreactive with hydroxyl
radical, but was degraded in high-peroxide-concentration Fenton systems to
yield free chloride. Hexachloroethane, bromotrichloromethane, and tetrani-
tromethane, additional compounds that are difficult to degrade with hydroxyl
TM
194 Tarr
radical, were also degraded using high-peroxide Fenton systems. Superoxide

was suggested as the key reductant responsible for the degradation of these
compounds. The observation of a reductive pathway in Fenton systems may
expand the applicability of Fenton treatment to pollutants that can only be
degraded by reductive pathways. Initial reduction products may be further
degraded by reaction with hydroxyl radical. Of even greater importance may
be the ability of the reducing species to desorb hydrophobic pollutants [104],
which can then be further degraded by reductive or oxidative pathways.
Although the high concentration of hydrogen peroxide needed to produce
significant levels of reducing species might seem cost-prohibitive, such con-
ditions are typically used in current site remediation protocols. Consequently,
it is likely that current remediation strategies are capable of desorbing bound
pollutants. Additional research is necessary to further understand and op-
timize the reductive and desorbing properties of these systems.
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4

Fenton and Modified Fenton

The biorefractory nature of many persistent organic pollutants has resulted in

Rate ¼ k1 ½Fe2þ ½H2 O2  ð7Þ

The concentration of Fe2+, however, is governed by all of the processes

II. FENTON REAGENT MECHANISMS AND KINETICS

conversion of hydrogen peroxide to water, representing a two-electron reduc-

Fe3þ þ HO2  ! Fe2þ þ Hþ þ O2

D. Iron Ligands and Coordination

Although the ligands in reactions (19) and (20) are represented as

use of aliphatic radical scavengers by Croft et al. These scavengers can

F. Ferryl Ion or Other High-Valent Iron Species

III. HYDROXYL RADICAL REACTIONS WITH ORGANIC

Although there is still debate as to whether hydroxyl radicals or ferryl species

Figure 1 Generic mechanisms for hydroxyl radical reaction with organic

another identical radical. Typical reaction products include oxygenated

Substituted aromatics can react either by addition of hydroxyl radical to

D. Other Important Factors

Table 1 Rate Constants for Reaction with Hydroxyl Radical

Compound k (M1 sec1) Reference

produce hydroxyl radical at suﬃcient rates. The presence of reducing species

light nonaqueous phase liquids (LNAPLs) and dense nonaqueous phase

with subsequent aerobic biotreatment. The Fenton treatment moderately

B. Iron Minerals as Fenton Catalysts

d½H2 O2 =d t ¼ k½FeOOH½H2 O2 ; k ¼ 0:0031 M1 sec1 ð26Þ

at pH=7. The kinetics were determined to be dependent on the intrinsic

These iron chelators improved the Fenton oxidation of pollutants by

E. Combined Fenton Biodegradation

(a)anthracene was only 12% biodegraded in 63 days without pretreatment,

F. Examples of In Situ Applications

impermeable clay layer existed at a depth of 35–45 ft. Dense nonaqueous

the radical in most systems. In order to alleviate these problems, we have

Figure 5 Preliminary schematic representation of a ternary iron–cyclodextrin–

seen, up to 10-fold rate enhancements have been observed. In general, these

Table 2 Observed Enhancements in Degradation Rate Constants with

CMCD added No CMCD

radical, were also degraded using high-peroxide Fenton systems. Superoxide

ferric-complexes and hydrogen peroxide: an evaluation of fourteen iron che-

44. Beltran-Heredia J, Torregrossa J, Garcia J, Dominguez JR, Tierno JC. Degra-

62. Puppo A. Eﬀect of ﬂavenoids on hydroxyl radical formation by Fenton-type

sunlight induced reactions via Fenton type reagents. J Photochem Photobiol, A

94. Lamparczyk H, Zarzycki P, Ochocka RJ, Sybilska D. Structure-retention

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Rate ¼ k1 ½Fe2þ ½H2 O2 ð7Þ

Fe3þ þ HO2 ! Fe2þ þ Hþ þ O2

d½H2 O2 =d t ¼ k½FeOOH½H2 O2 ; k ¼ 0:0031 M1 sec1 ð26Þ