IRON OXIDE SURFACE CATALYZED OXIDATION OF QUINOLINE BY

HYDROGEN PEROXIDE

By Richard L. Valentine l and H. C. Ann Wang2

ABSTRACT: The objective of this research was to examine and compare the surface catalyzed loss of quinoline,
a model pollutant, in the presence of three iron oxides: ferrihydrite, goethite, and a semicrystalline iron oxide.
These are ubiquitous in the subsurface environment and have been implicated in the possible abiotic loss of
contaminants when hydrogen peroxide is injected for augmenting bioremediation. This suggests the possible use
of hydrogen peroxide specifically as an oxidant of some compounds in the subsurface. A comparison also reveals
the best candidate for use in a supported oxide fixed bed treatment system utilizing hydrogen peroxide as an
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oxidant. The catalytic activity toward quinoline oxidation was highest for goethite, much less for the semicrys-
talline material, and negligible in the presence of ferrihydrite. Several water constituents affected reaction rates
and stoichiometry by adsorption or through effects on solution chemistry. The stoichiometric efficiency relating
quinoline loss to hydrogen peroxide decomposition was not a function of oxide concentration, nor was it affected
by the presence of carbonate or phosphate that reduced the rate of hydrogen peroxide decomposition. The effect
of humic acid on quinoline loss and hydrogen peroxide decomposition rate depended on its concentration,
suggesting that it may act as a radical scavenger, radical chain promoter, and catalytic site inhibitor.

INTRODUCTION peroxide is sometimes utilized to supply oxygen for biore-

Hydrogen peroxide is a powerful oxidant that has been used
to degrade contaminants either directly or in conjunction with
a catalyst or activator (Plant and Jeff 1994). Fenton's reagent,
a mixture of ferrous iron and hydrogen peroxide, is one of the
most widely used and studied catalytic treatment systems. In
systems utilizing this mixture, decomposition of hydrogen per-
oxide initiated by reaction with the iron leads to the formation
of free radical intermediates, especially the hydroxyl radical.
This radical is capable of reacting with a wide variety of or-
ganic compounds. Fenton's reagent has been applied to treat
a variety of wastes such as those associated with the textile
and chemical industry (Plant and Jeff 1994). More recently,
Fenton's reagent has also been applied to treat contaminated
soils (Miller et al. 1996; Watts et al. 1993). One limitation is
that it is effective only at low pH values, which necessitates
pH adjustments to waste streams before and after. treatment.
The process also produces a large volume of iron oxide pre-
cipitates.
A number of researchers have also investigated the appli-
cation of metal oxides and supported metal oxides, especially
those of iron, as catalytic materials for the oxidation of organic
compounds in batch and fixed bed continuous flow treatment
systems (AI-Hayek and Dore 1990; Mill et al. 1989; Miller
and Valentine 1995). They generally observed a greatly accel-
erated decomposition of hydrogen peroxide but variable
amounts of contaminant loss. Watts et al. (1994) examined the
efficiency of iron minerals toward catalyzed degradation of
hexachlorobenzene by hydrogen peroxide in batch studies, and
noted considerable differences in reactivity with different types
of iron oxides. This observation indicates that the effectiveness
of an iron oxide catalyst will depend on the specific type and
characteristics of the iron oxide.
Recent work also indicates that abiotic surface catalyzed
reactions of hydrogen peroxide may also lead to contaminant
losses in the subsurface environment (Gates and Siegrist 1995;
Gurol and Ravikumar 1994; Yen and Novak 1995). Hydrogen
'Dept. of Civ. and Envir. Engrg.• Univ. of Iowa. Iowa City. IA 52242.
2Dept. of Civ. and Envir. Engrg.• Univ. of Iowa, Iowa City. IA.
Note. Associate Editor: Mark E. Zappi. Discussion open until June I.
1998. To extend the closing date one month. a written request must be
filed with the ASCE Manager of Journals. The manuscript for this paper
was submitted for review and possible publication on July 23.1996. This
paper is part of the Journal of Environmental Engineering, Vol. 124.
No.1. January. 1998. @ASCE, ISSN 0733-9372/98/0001-0031-0038/
$4.00 + $.50 per page. Paper No. 13686.
JOURNAL OF ENVIRONMENTAL ENGINEERING / JANUARY 1998/31
mediation; however, the importance of a parallel abiotic con-
taminant loss pathway is not clear. If such reactions were sig-
nificant, then the addition of hydrogen peroxide to the
subsurface to specifically degrade contaminants might be war-
ranted. Understanding the fate of hydrogen peroxide and con-
taminants in such a complex matrix remains a challenge.
We examined and compared the surface catalyzed transfor-
mation of the model pollutant, quinoline, by hydrogen per-
oxide in the presence of three iron oxides. Quinoline (C9 H7N,
pI<" = 4.94) can be found in the wastes and waters associated
with old coal gasification sites up to several tens of milligrams
per liter, and has a water solubility of 6,000 mglL and an
octanollwater partition coefficient of about 107. Quinoline is
also a known tumor-initiating agent and has toxic and teroto-
genic effects on aquatic organisms (Cushman and McKamey
1981; Dauble et al. 1994; Davis et al. 1981; LaVoie et al.
1984). Additionally, it is a common structural element in many
other N-heterocyclic compounds, and therefore is a model for
these types of contaminants. Quinoline is oxidized by the hy-
droxyl radical and is a good candidate as a probe molecule,
although the exact nature of the products is not well estab-
lished (Andreozzi et al. 1992). Miller and Valentine (1995)
studied its oxidation by hydrogen peroxide in the presence of
aquifer sand, and demonstrated that it reacted through a sur-
face catalyzed reaction.
The three iron oxides utilized in the present study, ferrihy-
drite, a semicrystalline iron oxide, and crystalline goethite, are
all ubiquitous in the subsurface environment. Ferrihydrite rep-
resents freshly precipitated and amorphous iron oxide which,
upon sufficient aging, typically develops through a semicrys-
talline phase to form highly crystalline goethite, which has a
much lower surface area than ferrihydrite. A comparison pro-
vides insight into what might occur in the subsurface environ-
ment, and may also indicate the best choice for a supported
iron oxide fixed bed treatment system. The effect of bicarbon-
ate, phosphate, and natural organic matter on quinoline loss
was examined. The dependence on solid concentration was
also investigated, to provide insight into the possible role of
surface scavenging, as proposed by Miller (1995).
METHODOLOGY
Preparation and Characterization of Iron Oxides
Three different types of iron oxides were prepared from
ferric hydroxide precipitates produced from ferric nitrate so-

J. Environ. Eng., 1998, 124(1): 31-38

 TABLE 1. Physical Characteristics of Synthesized Iron Ox-
ides
Type of
iron oxide Ferrihydrite Semicrystalline
(1) (2) (3)
Structure amorphous poorly crystalline
Particle shape sphere needle
Total iron content 52:!: 1% 59:!: 4%
(by weight)
Specific surface area. 290.1 :!: 43.5 110.3 :!: 16.5
m'/g
Mean particle size,' nm 622.9 852.6
Particle dimension" 30 nm 100 nm X 300 nm 0.1 ....m X 1.9 ....m
Zeta potential of major 19.2 -17, -6.7
particle species,' mV 41.2 0.5.15.4
-
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55.0
'Results of Doppler electrophoretic light scattering analyses; scattering angles
8".
"Estimated from electron micrograph.
lutions at alkaline conditions. A two-line ferrihydrite was pre-
cipitated as ferric hydroxide at neutral pH value (Schwertmann
and Cornell 1991). Goethite was prepared by aging ferric hy-
droxide at pH 12 and 70°C for 60 h (Schwertmann and Cornell
1991). The semicrystalline iron oxide was synthesized by ag-
ing ferric hydroxide at room temperature for 72 h at pH 12
according to the method of Kung and McBride (1989, 1991).
The final oxides were removed from suspension by centrifu-
gation, washed with deionized water, then freeze-dried. Ex-
amination of the X-ray diffraction pattern confirmed the pre-
pared materials to be the desired iron oxides. From Doppler
electrophoretic light scattering analysis, each of the three pre-
pared iron oxides formed distinctively different charged spe-
cies in deionized water. Before using them in any experiments,
the iron oxides were irradiated with 5 X 106 rad of 6OCO
gamma radiation to eliminate any possible biological contam-
ination (Wolf et al. 1989).
Examination by electron microscopy showed that the par-
ticles in each synthetic iron oxide have a single unique mor-
phology. The shape of the ferrihydrite is a small spherical par-
ticle with a diameter of about 0.03 ~m. The synthesized
goethite showed a needle-like shape with dimensions of 0.12
J.Lm X 18.8 J.Lm. The semicrystalline iron oxide was clearly
not a mixture of goethite and ferrihydrite. It was a uniform
long oval shape with dimensions of 0.1 J.Lm X 0.3 ~m.
Physical characteristics of the three synthetic iron oxides are
summarized in Table 1. The iron content of these three oxides
was similar, in the range of 52%-59% by dry weight. Ferri-
hydrite had the largest specific BET surface area of 290.1 :±
43.5 m 2/g, and goethite, the smallest, with a specific area of
58.7 :± 8.8 m 2/g. The semicrystalline iron oxide had an inter-
mediate area of 110.3 :± 16.5 m 2/g. These values compare well
with reported values of 200-300 m 2/g for ferrihydrite
(Schwertmann and Cornell 1991), 91.5 m 2/g for semicrystal-
line iron oxide (Kung and McBride 1991), and 20-90 m 2/g
for goethite (Schwertmann and Cornell 1991).
Experimental Approach
Reactions were studied using dispersed iron oxide suspen-
sions in batch reactors under constant temperature, 20°C. Con-
trol of pH and total carbonate concentration was achieved with
a pH stat combined with normal air or 0.5% COrair mixture
in the head space. This involved periodic additions of 0.1 M
HN03 or 0.1 M KOH to solutions. The volume of the reaction
mixture was monitored and did not increase more than 5%
during the period of experiment. This arrangement provided
three combinations of pH and carbonate alkalinity: (1) pH 7
and carbonate alkalinity 0.6 mEqlL; (2) pH 7 and carbonate
alkalinity 7.8 mEqlL; and (3) pH 7.7 and carbonate alkalinity
5 mEqlL.
32/ JOURNAL OF ENVIRONMENTAL ENGINEERING / JANUARY 1998
J. Environ. Eng., 1998, 124(1): 31-38
A stock quinoline solution was prepared by dissolving 1,000
mg of quinoline (Fisher) into 1.0 L of deionized water, which
was stored at 4°C. Aldrich humic acid was used as a model
Goethite for natural organic matter. Stock Aldrich humic acid solution,
(4)
1,000 mgIL, was prepared by dissolving 1 g of Aldrich humic
crystalline
oval
substances in 1 L of deionized water, followed by filtering
58:!: 1% through a 0.8 J.Lm glass fiber filter and 0.4 J.Lm membrane filter;
it was then stored in the dark at 4°C. Stock hydrogen peroxide
58.7 :!: 8.8 was 30% by weight from Fisher. Experimental solutions were
529.5 prepared in a simulated ground water initially containing 5
mM sodium bicarbonate, 3 mM sodium sulfate, 2 mM calcium
-16.8 chloride, and 1 mM sodium chloride. The foregoing combi-
- nation gave a pH value around 8.0, if the solution was equil-
-
ibrated with normal air.
The reaction solutions, consisting of laboratory prepared
water with the appropriate amount of quinoline, were freshly
prepared for each experiment and then were filtered through a
0.2 J.Lm membrane filter before adding iron oxides. The ionic
strength was kept constant at 0.1 M by the addition of potas-
sium nitrate. After the addition of the oxide, the mixture was
stirred for 24 h to ensure that chemical equilibrium was
achieved before adding hydrogen peroxide. The reaction was
then initiated by the addition of reagent grade hydrogen per-
oxide. All reactors were covered with aluminum foil to prevent
any photocatalyzed decomposition of hydrogen peroxide.
Samples for hydrogen peroxide measurement were prepared
by filtering an aliquot taken from the reactors through a 0.2
J.Lm membrane filter. Immediately after filtration, the hydrogen
peroxide concentration in the filtrate was measured by the io-
dometric titration method, with starch as an indicator (Belcher
and Nutten 1960; Shaw 1967). The whole process was com-
plete within 2 min of taking samples out of the reactors. The
concentration of quinoline was determined by a gas chromat-
ograph (GC) (Hewlett-Packard 5890A) with a capillary col-
umn and flame ionization detector. Samples for GC analysis
were prepared by extracting 1 mL of reaction or standard so-
lution with 1 mL of carbon tetrachloride. A 2 J.LL carbon tet-
rachloride extracting solution was then injected into the gas
chromatograph, which was operated at 185°C with a hydrogen/
nitrogen gas flow rate of 10 mL/min.
RESULTS AND ANALYSIS
Hydrogen Peroxide Decomposition Kinetics
The catalytic decomposition of hydrogen peroxide by iron
oxides is believed to involve a radical chain mechanism and
the reduction-oxidation interconversion of the oxides during
the reaction (Kitajima et al. 1978; Krutikov et al. 1984). Abbot
and Brown (1990) proposed the reduction of ferric hydroxides
as the initial decomposition step. Miller (1995) recently
adapted the model proposed by Ono et al. (1977) to describe
the oxidation of organic contaminants in the presence of oxide
coated aquifer sand (Fig. 1). Specifically included were reac-
tions of the superoxide anion and hydroperoxyl radical (reac-
tions 8 and 9 in Fig. 1) with hydrogen peroxide to form the
hydroxyl radical, and scavenging reactions, which accounted
for the observation that the efficiency of organic oxidation de-
pended on the concentration of sand (Miller et al. 1995). In
the overall scheme (Fig. 1), the importance of -02 and, H02
radicals was not their reactivity with organic contaminants, but
as a source of the more reactive ·OH radical via reactions with
hydrogen peroxide in the water phase (Miller 1995). Although
the overall mechanism is complex, the rate limiting reaction
is the initial reaction between hydrogen peroxide; therefore,
the decomposition of hydrogen peroxide should follow a sim-
ple first-order relationship, as generally observed (Kitajima et
al. 1978; Miller and Valentine 1995; Abbot and Brown 1990).
Consistent with the observations of others (Abbot and
 Brown 1990; Kitajima et al. 1978; Ono et al. 1977), the loss
of hydrogen peroxide followed a first-order rate expression
with respect to hydrogen peroxide concentration in the pres-
ence of all three oxide types (Fig. 2). Additional work also
established a linear relationship between the observed first-
order decay coefficient kobo to the mass of oxide present. al-
lowing a mass normalized kinetic rate coefficient. lem.... to be
defined and a second-order rate expression to be derived
where km ... = koJ(oxide); and (oxide) = concentration of oxide.
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Tables 2-4 summarize a comparison of rate constants for
various reaction conditions. The mass normalized catalytic ac-
tivity. k.n..•• of ferrihydrite is about one order of magnitude
greater than the value for goethite. and two to three times more
than the value for the semicrystalline iron oxide. This differ-
ence largely disappears when it is normalized to surface area,
as seen by comparing the surface area normalized rate con-
stants. ksur!
k _ kobo _ kmu•
(2)
our! - SA. - SAm
where SA. = surface area per unit of water volume; and SAm
= surface area per unit mass of oxide. The values of k.ur! are

<al (a)
H:7.01 <-> HOI + Jr (1)
_ ferrlhydrlte 250 mg oxlde/L
10M + H:7.01->.r + OM" + oOH (2) _ • aemI-ayatalline 500 mg oxlde/L
~+HO£->tIM+oH01 (3) - &- - goethite 2500 mg oxlde/L

H:7.01 + oOH - > H:7.0 + oH01 (4)

oH01 <-> H+ + 00£ <~l

_M+ + 0Oz.- ->tIM+01 (6)

.M+oH01->~+HO£ (7)

H:7.01+ 0Oz.--> 00H+OM"+01 (8)

H:7.01 + oHOz.-> oOH + H:7.0+01 (9)

-30·t...................-5OO~ ...................,.1000:l::-....................,.,15OO~ .......---~
Timelmln\
(b)
_ ferrlhydrlte 250 mg oxIde/L
a _ - aemI-ayatalllne 500 mg oxIde/L

~
QuInoline ~ - .. -goethIte2500mgoxlde/L
~,
---~_.=.~. ~-+~ ·1 ~ .........

i
·OH Produeta

OH:;.O; / .5 ·2
'II
,o "
"-
~HP H,~ .CH/!...
and and
-3 O~-'-"""'"'-:!500~"""""""'":1-f.OOO:::"----""""~15OO~""""""~2000.
TIme(mln)

FIG. 2. Change of Hydrogen Peroxide Concentration In Pree-

FIG. 1. Propoaed Scheme for Surface Catalyzed Hydrogen ence and Abaence of Quinoline at pH 7.7; Carbonate Alkalinity 5
Peroxide Decomposition and Reaction of Quinoline [Adapted mEqIL, and Initial Hydrogen Peroxide Concentration 500 mg/L:
from Miller (1995)]: (a) Reaction Mechanism; (b) Reaction <a) pH 7.7 without Quinoline; (b) pH 7.7 with Quinoline Doee10
Scheme Diagram mg/L

TABLE 2. Hydrogen Peroxide Decomposition Rate Constante In Presence of Iron Oxides at pH 7.0 (95% Confidence Intervals
Shown); Initial Hydrogen Peroxide 500 mg/L

Oxide concentration Rate Constant

Alkalinity
Oxide type mglL mEqlL Form" Without quinoline With 10 mglL quinoline
(1 ) (2) (3) (4) (5) (6)
Ferrihydrite 500 0.6 ~ (7.6 :!: 0.6) x lO 3 (1.0 :!: 0.001) x lO-2
k.._ (15.1 :!: 1.2) x lO-· (20.3 :!: 0.02) x lO-·
k.... (52.2 :!: 4.1) x lO-· (70.0 :!: 0.05) x 10-·
Semicrystalline 500 0.6 ~ (2.6 :!: 0.4) x lO-3 (3.5 :!: 0.3) x 10-'
k..- (5.25 :!: 0.89) x 10-· (6.94 :!: 0.96) x 10-·
k.... (47.6 :!: 8.1) x 10-· (62.9 :!: 6.3) x 10-·
Goethite 2.500 0.6 k o... (3.7 :!: 0.3) x 10- 3 (3.4 :!: 0.3) x 10- 3
k..- (1.47 :!: 0.12) x 10-· (1.38 :!: 0.12) x 10-·
k.... (25.1 :!: 2.1) x 10-· (23.5 :!: 2.0) x lO-'
Ferrihydrite 500 7.8 ~ (2.9 :!: 0.4) x 10- 3 (2.9 :!: 0.3) x 10- 3
k..- (5.71 :!: 0.77) x 10-· (5.74 ± 0.59) x 10-·
k."" (19.7 :!: 2.7) x lO-' (19.8 :!: 2.0) x 10-·
Semicrystalline 500 7.8 ~ (8.8 :!: 0.7) x 10-' (1.2 :!: 0.1) x 10- 3
k..- (1.76 :!: 0.13) x 10-· (2.40 :!: 0.26) x 10-·
k.... (15.9 :!: 1.2) x 10-· (21.8 :!: 2.4) x 10-·
Goethite 2.500 7.8 k"... (2.3 :!: 0.2) x 10- 3 (1.7 :!: 0.1) x 10- 3
k..- (0.91 :!: 0.08) x 10-· (0.69 :!: 0.04) x 10-·
k.... (15.5 :!: 1.3) x 10-· (11.7 + 0.7) x 10-·
.~ = mm '.
. -'(mg oXldeJL)- '. k.ud = I1lln '(m'lL) '; k..- =
k..... = I1lln ~/(oxide mass per unit volume of water); k...r = ~/(total surface area per
unit volume of water).

JOURNAL OF ENVIRONMENTAL ENGINEERING / JANUARY 1998 I 33

J. Environ. Eng., 1998, 124(1): 31-38

 TABLE 3. Hydrogen Peroxide Decomposition Rate Constants In Presence of Iron Oxides at pH 7.7 (95% Confidence Intervals
Shown); Carbonate Alkalinity 5 mEqlLj Initial Hydrogen Peroxide 500 mglL
Oxide Rate Constant
Concentration
Type mg/L Form" Without quinoline With 10 mg/L quinoline
(1) (2) (3) (4) (5)
Ferrihydrite 250 (3.8 :t 004) x 10- 3 (4.3 :t 0.3) x 10- 3
*-
k..... (1.5 :t 004) X 10-' (1.7 :t 0.1) x 10-'
k.un (5.2 :t 0.5) x 10-' (5.9 :t 004) x 10-'
Ferrihydrite 500 kobo (6.9 :t 0.4) X 10- 3 (7.3 :t 0.5) x 10- 3
k..... (1.4 :t 0.1) X 10-' (1.5 :t 0.1) X 10-'
k.un (4.8 :t 0.3) X 10-' (5.0 :t 0.3) x 10-'
Ferrihydrite 1,250 k"", (1.5 :t 0.1) x 10- 2 (2.2 :t 0.1) x 10- 2
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k..... (1.2 :t 0.2) x 10-' (1.7 :t 0.1) x 10-'

k.un (4.1 :t 0.4) x 10-' (6.0 :t 0.2) x 10-'
Semicrystalline 500 k""" (9.9 :t 1.3) x 10-' (1.6 :t 0.1) x 10- 3
k,.... (2.0 :t 0.2) x 10-· (3.3 :t 0.1) x 10-·
k.un (1.8 :t 0.1) x 10-' (2.9 :t 0.1) x 10-'
Goethite 500 kobl (4.4 :t 0.6) x 10-' (4.6 :t 004) x 10-'
k..... (8.9 :t 1.1) x 10- 7 (9.2 :t 0.8) x 10- 7
k.un (1.5 :t 0.2) x 10-' (1.6 :t 0.1) x 10-'
Goethite 2,500 k""" (2.6 :t 0.3) x 10- 3 (2.8 :t 0.1) x 10- 3
k..... (1.0 :t 0.1) x 10-· (1.1 :t 0.1) x 10- 0
k.un (1.8 :t 0.2) x 10-' (1.9 :t 0.1) x 10-'
Goethite 12,500 k""" (1.3 :t 0.05) X 10- 2 (1.3 :t 0.1) x 10- 2
k..... (1.0 :t 0.1) X 10- 0 (1.1 :t 0.1) X 10- 0
k.un (1.7 :t 0.1) X 10-' (1.8 :t 0.1) X 10-'
Goethite 2,500 k""" (2.6 :t 0.3) X 10- 3 (1.6 :t 0.1) X 1O- 3b
k..... (1.0 :t 0.1) X 10- 0 (0.64 :t 0.04) X IO- ob
k.un (1.8 :t 0.2) X 10-' (10.8 :t 0.7) X IO- ob
"k""" = min " ka.... = min '(mg oxide/L) " k.un = min '(m2/L)-'.
bWith 50 mgIL quinoline rather than 10 mgIL quinoline.

TABLE 4. Hydrogen Peroxide Decomposition Rate Constants In Goethite Suspensions at pH 7.0 (95% Confidence Intervals Shown);
Initial Hydrogen Peroxide 500 mgILj Goethite 2,500 mg OxldeIL
Components Present Rate Constant
Alkalinity Phosphate Humic
mEq/L mg/L mg/C/L Form" Without quinoline With 10 mg/L quinoline
(1) (2) (3) (4) (5) (6)
0.2 0 0 k..... (1.35 :t 0.05) X 10-0 (1.03 :t 0.14) X 10-·
k, urf (23.1 :t 0.9) X 10-· (7.8 :t 204) X 10-·
0.6 0 0 k..... (1.47 :t 0.12) X 10-· (1.38 :t 0.12) X 10-·
k.un (25.1 :t 2.1) X 10- 0 (23.5 :t 2.0) X 10-·
7.8 0 0 k..... (0.91 :t 0.08) X 10-· (0.69 :t 0.04) X 10- 0
k.un (15.5 :t 1.3) X 10-· (11.7 :t 0.7) X 10-·
0.6 6.3 0 k..... (0.64 :t 0.03) X 10-· (0.56 :t 0.03) X 10-·
k. un (10.9 :t 0.5) X 10-· (9049 :t 0.57) X 10- 0
0.6 0 13.0 k..... (1.96 :t 0.29) X 10-· (2.32 :t 0.21) X 10-·
k. urf (33.3 :t 4.9) X 10-· (39.5 :t 3.6) X 10-·
0.6 0 65.3 k..... (0.78 :t 0.07) X 10-· (0.71 :t 0.08) X 10-·
k.un (13.3 :t 1.2) X 10-· (12.1 :t 104) X 10- 0

nearly all within a factor of 2, indicating that concentration
and intrinsic reactivity of the sites are similar for all three of
these particular oxides.
Previous work (Wang and Valentine 1993; Wang 1996) sug-
gests that adsorption of quinoline could result in deactivation
of the catalytic sites, complicating kinetic analysis, The
amount of quinoline adsorbed was small, as the presence of
iron oxides did not measurably reduce its concentration. Even
if 10% of the 10 mg/L dosage was adsorbed, no significant
reduction in site concentration would be expected based on
the consideration of available area. The addition of 10 mg/L
of quinoline did not significantly affect the rate of hydrogen
peroxide decay in the presence of ferrihydrite or goethite. but
did appear to somewhat increase the decomposition rate from
8.7 X 10-4 to 15.4 X 10-4 min- 1 in the presence of semi-
crystalline material. The effect in the presence of the semi-
crystalline material is difficult to explain. Quinoline would not
34/ JOURNAL OF ENVIRONMENTAL ENGINEERING / JANUARY 1998
likely increase the overall rate of hydrogen peroxide decom-
position because of its low relative concentration compared to
that of hydrogen peroxide, and because the rate limiting step
involves hydrogen peroxide reacting at the oxide surface.
Quinoline Oxidation
The oxidation of quinoline was studied at various oxide
concentrations, including those where the total surface area
available in each oxide solution was similar in order to ensure
that the overall catalytic activity in each solution was also
similar. Fig. 3 compares quinoline loss in the presence of the
three oxides at concentrations where the observed rate of hy-
drogen peroxide loss was comparable (Table 3). Experiments
were conducted using a ferrihydrite concentration of 250 mg
oxidelL. a semicrystalline concentration of 500 mg oxidelL,
and a goethite concentration of 2,500 mg oxidelL. The last

J. Environ. Eng., 1998, 124(1): 31-38

 0
which had been aged for 48 h and dosed with more hydrogen
Ii 0 A
/j'/j
C
'6 111.11. peroxide. The quinoline concentration was monitored. No sig-
~

j 0.8 C
C nificant water phase reactions were observed.

!
C
To more clearly discern the relative reactivities of each ox-
0.6 ide, three sequential dosages of hydrogen peroxide were added
.......
I 0.4
into the reaction suspensions. The change of quinoline and
hydrogen peroxide concentration is shown in Fig. 4. The same
! 0.2
0
A
C
ferrlhydrlte 250 mg oxIde/L
oemi-erysta11lne 500 mg oxIde/L
goethite 2500 mg oxIde/L
trend was observed as when a single dosage was applied. but
the overall losses were significantly greater. Again. the small-
o0 0.2 0.4 0.6 0.8 est loss of 10% occurred in the ferrihydrite suspension, an
ll\OJ/IHP,!. intermediate loss of 30% occurred in the presence of semi-
crystalline material. and the largest loss of 70% occurred with
FIG. 3. Change of Quinoline versus Change of Hydrogen Per- goethite.
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oxide Concentration In Oxide Mixtures at pH 7.7; Carbonate Al-

kalinity 5 mEq/L, Initial Hydrogen Peroxide Concentration 500
mgIL, Initial Quinoline Concentration 10 mgIL, and Final
Hydrogen Peroxide Concentration 100 mgIL at Last Data Point
Shown for Each Oxide
(e)
It is not clear why these three iron oxides exhibited different
catalytic activity toward quinoline oxidation. As discussed in
other works (Wang 1996; Wang and Valentine 1993, unpub-
lished paper, 1997). all three oxides exhibited similar reactivity
toward hydrogen peroxide decomposition and showed similar
phosphate adsorption on a surface-area basis. The difference
in catalytic activity may be related to the structural differences.
Ferrihydrite has more vacant Fe sites and OH groups than does
goethite (Dzombak and Morel 1990), which might affect rad-
ical scavenging.
The difference in oxidation activity may also relate to the
amount of quinoline adsorbed if it is surface-adsorbed quino-
line that is most reactive. and if its affinity toward goethite
was the greatest. The amount of quinoline adsorbed by each
oxide could not be quantified in detail because so little was
adsorbed. Clearly. the amount adsorbed could not exceed more
than 10% of the total amount of quinoline, which is a value
close to the method-detection limit. If reaction with surface
adsorbed quinoline was the primary mechanism by which
quinoline was lost, then the amount of loss would likely in-
crease in the presence of increased iron oxide concentrations
if the adsorbed quinoline was reacting with a radical formed
in solution. If. however. it was reacting with an adjacently
formed radical. then no oxide concentration effect would be

~....
0.8
0.6
j. expected because the surface concentration of quinoline would
be the same under these reaction conditions. Since goethite

~
o
o 500 1000
TIme (min)
-+

1500 2000
0
0.4
0.2
I
6'"
exhibited the greatest activity toward quinoline loss, further
experiments focused on its catalytic activity.

Oxidation of Quinoline In Goethite Suspensions

FIG. 4. Change of Quinoline and Hydrogen Peroxide Concen-
trations In Iron Oxide Suspension at pH 7.0 with Three Sequen-
tial Additions of 500 mgIL Hydrogen Peroxide: Initial Quinoline
10 mgIL and Carbonate Alkalinity 0.6 mEq/L: (a) with Ferrlhy-
drlte 500 mg OxldeIL; (b) with Semicrystalllne 500 mg OxldeILj
(c) with Goethite 2,500 mg OxldeIL
points shown for each oxide type represent samples taken after
nearly the same hydrogen peroxide loss of 400 mg/L; they,
therefore, can be directly compared. No measurable decrease
in quinoline concentration was observed with ferrihydrite,
while a 10% reduction in quinoline concentration was ob-
served with semicrystalline material. Goethite showed the
greatest catalytic effect on quinoline loss, causing a reduction
of approximately 30%. The catalytic activity of ferrihydrite
was further examined at a concentration up to 1.250 mg oxide/
L. which greatly increased the observed hydrogen peroxide
decay rate. Even at this concentration. no significant loss in
quinoline was observed. Watts et aI. (1994) also observed that
goethite catalyzed the degradation of hexachlorobenzene by
hydrogen peroxide.
The loss of quinoline could involve both surface and water
phase reactions. To determine the importance of water phase
reactions. samples filtered through a 0.2 IJ.m membrane were
taken from quinoline-hydrogen peroxide-goethite mixtures,
The relationship between quinoline loss and goethite con-
centration was studied at goethite concentrations of 500;
2,500; and 12.500 mg oxidelL containing similar quinoline
and hydrogen peroxide dosages. Over this range, the rate of
hydrogen peroxide decomposition increased by a factor of 25.
The amount of quinoline reacted was. however, approximately
35% for each oxide concentration for the same amount of hy-
5J:?=!~::z=t~::;::t:::!j""""""""'r""""'''''''''''''''''''''''''''"''""l
o 500 mg ox!de/L
A 25OOmgoxide/L
C 12500 inS oxlde/L
ojo:l:::.............~..........:A::..200,.J.,-.............'"'300L...4-.........""""':"400~ ........~5OO
6{H202] (mg/L)
FIG. 5. Relationship between Loss of Quinoline and Loss of
Hydrogen Peroxide In Goethite Suspensions at pH 7.7; Carbon-
ate Alkalinity 5 mEqIL, Initial Quinoline Concentration 10 mglL,
and Hydrogen Peroxide 500 mgIL; Standard Deviation Shown
by Error Bars

JOURNAL OF ENVIRONMENTAL ENGINEERING / JANUARY 1998/35

J. Environ. Eng., 1998, 124(1): 31-38

 drogen peroxide decomposed (Fig. 5). The operationally de- added to regulate hydrogen peroxide decay to better control
fined stoichiometric efficiency, E oxygen delivery in the subsurface environment. Adsorption of
these substances is believed to result in the inactivation of
..:1[quinoline] catalytic sites (Wang and Valentine 1993). Furthermore, Miller
E=-"-"---~ (3)
2 2] ..:1[H 0 (1995) found that adding 0.4 mM phosphate to 0.5 g/mL aq-
uifer sand increased the efficiency of quinoline loss by 65%,
of approximately 2.7 mg quinoline for 400 mg hydrogen per- while it reduced the rate of hydrogen peroxide decay by 50%
oxide decomposed is 3.75 X 10- 3 mg/mg, indicating a rela- presumably through the reduction of surface scavenging sites.
tively low efficiency at these reaction conditions. Reaction The catalytic activity toward hydrogen peroxide decompo-
with surface bound quinoline would lead to increased effi- sition can be greatly reduced in the presence of phosphate. A
ciency with increased oxide concentrations, because more phosphate dose of 6.3 mg PIL at pH 7.0 to a solution contain-
quinoline would reside on the surface. It is therefore concluded ing goethite at a concentration of 2,500 mg oxidelL reduced
that the reaction mechanism does not involve the reaction of the decay rate by 50%, approximately the fraction of catalytic
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surface bound quinoline with a radical produced in solution.
Miller and Valentine (1995) and Miller et al. (1995) showed
that inclusion of radical scavenging reactions on the surface
of metal oxide coated aquifer sand was necessary to model
the oxidation of quinoline; they also explained why the effi-
ciency of organic oxidation decreased significantly with in-
creasing sand concentration in batch reactors. The absence of
a measurable oxide concentration effect on the apparent stoi-
chiometric efficiency does not necessarily demonstrate that
surface scavenging of the intermediates is unimportant.
Clearly, the efficiency of the overall reactions is low, and
therefore relatively few radicals are reacting with quinoline. A
kinetic formulation for the loss of quinoline based on the re-
actions shown schematically in Fig. 1 indicates that the effi-
ciency of quinoline degradation should be independent of ox-
ide concentration, provided the rate of scavenging and other
radical reactions greatly exceeds the rate at which quinoline
reacts. This is consistent with the observed low efficiency.
Effect of Surface Complexing Constituents
Substances that adsorb to iron oxides could affect hydrogen
peroxide decay kinetics as well as the efficiency of quinoline
oxidation. These include natural substances such as carbonate
and humic substances, but also phosphate, which is sometimes
(a)
o 0.8
~
"" 0.6
sites occupied by phosphate (Table 4). Fig. 6(a) presents the
change of quinoline concentration with the change in hydrogen
peroxide concentration in the presence of phosphate. Approx-
imately 80% of the quinoline was removed by three 500 mgl
L doses of hydrogen peroxide. This can be compared to results
obtained without phosphate [Fig. 4(c»), which shows a similar
70% loss of quinoline. The addition of phosphate therefore did
not significantly affect the reaction efficiency, which remained
quite low.
The effect of carbonate was also studied because, like phos-
phate, this ubiquitous constituent may be a significant surface
complexing agent, and because it is a known hydroxyl radical
scavenger. Fig. 6(b) presents the change of quinoline and hy-
drogen peroxide concentration at pH 7.0 with a carbonate al-
kalinity of 7.8 mEqIL and a goethite concentration of 2,500
mg/L. The 90% removal of quinoline realized after three
sequential doses of 500 mg/L hydrogen peroxide is nearly the
same as that obtained in the presence of 0.6 mEq/L alkalinity
[Fig. 4(c»). The addition of carbonate therefore did not signif-
icantly affect the reaction efficiency. There is no evidence that
radical scavenging by carbonate is affecting quinoline loss.
The primary effect of carbonate appears to be like that of phos-
phate, which deactivates a catalytic site upon its adsorption.
(a) 1 0 . - - - - - - - - - - - - r......-,-,.....,...,.....,
~ 6 carbonate alkalinity 0.2 mEq/L
.~ 8 0 carbonate a1lcalinity 0.6 mEq/L
~ C carbonate alkalinity 7.8 mEq/L
6 • phosphate dOle 6,3 mg P IL
I 4 b-........:..--=---------'
0.8 i- !
0.6 f
~ <l
2

~ 0.4 0.4
~
~.

0.2 0.2
f
0-
(b)
::i'
4 ...-----------,-"T'""'T"'T""r-T"".....,....,
0 carbonate alkalinity 0.6 mEq/L
...... c carbonate alkalinity 7.8 mEq/L
1 3 phosphate dOle 6.3 ms P IL __'
1-_..:..-...:.....
•
o OL................500.l.-..........~I-:1.:000~~I-::\500-::!-'~2llOO*:-'-''''":2500~~ ....~
Time (min)
I 2

(b) ! 1

<l 0 --:::::t::i:...,"'="..::............,200::!::-...............300:;;!;;-................7.400~ ........""""';;;(500

0.8 0.8 i- (c)

AlH,0~ (ms/L)

4.------------r.....-T.,..,....,....,.....,...,
0.6 ! ~
1
o carbonate alkalinity 0.6 mEq/L
C carbonate alkalinity 7.8 mEq/L

0.4 i- I
3

2
• phosphate dOle 6.3 ms P IL
I--.:...--=----~---'

f
0.2 0-
! 1

00L.................L...................J..,I-.........~~~~ ..........~2500== ........"'":3llOO;;;'0, <l 0 ....:::::t::i:...,"'=-'...............,:±-...............:;;!;;-................~..................~500

500 1000 1500 2llOO
Time (min)

FIG. 6. Change of Quinoline and Hydrogen Peroxide Concen- FIG. 7. Relationship between Loss of Dose Hydrogen Perox-
tration In Goethite Suspensions In Presence of Complexlng LI- Ide and Loss of Quinoline In Goethite Suspensions at pH 7.0
gands at pH 7.0 with Three sequential 00sege8 of 500 mgIL Hy- with Three Sequential Doses of 500 mgIL Each of Hydrogen Per-
drogen Peroxide; Goethite Concentration 2,500 mg OxldeiL and oxide; Goethite 2,500 mg oxldelL, Initial Quinoline Concentra-
Initial Quinoline Concentration 10 mgIL: (a) with Phosphate tion 10 mg/L; Standard Deviation Shown by Error Bars: (a) First
Dose 6.3 mg PIL; (b) with Carbonate Alkalinity 7.8 mEqIL Dose; (b) Second Dose; (c) Third Dose

36/ JOURNAL OF ENVIRONMENTAL ENGINEERING / JANUARY 1998

J. Environ. Eng., 1998, 124(1): 31-38

 The effects of carbonate and phosphate are compared in Fig.
7, which shows the cumulative loss of quinoline as a function
of hydrogen peroxide loss for each sequential dose of hydro-
gen peroxide. The change in quinoline concentration for a
given loss in hydrogen peroxide is approximately the same
regardless of which complexing constituent is present. The op-
erationally defined stoichiometric efficiency, E, however, de-
creased from an average value of (9.2 :!: 2.0) X 10- 3 mg
quinoline/mg H20 2 for the first hydrogen peroxide dose and
(4.5 :!: 1.0) X 10- 3 mg quinoline/mg H 20 2 for the second dose
to (3.9 :!: 1.2) X 10- 3 mg quinoline/mg H20 2 for the third
dose. This decrease is expected because of the decrease in
quinoline concentration at the time of each hydrogen peroxide
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in a decrease in the amount reacted for a given amount of
hydrogen peroxide decomposition. Also consistent with this,
it was observed that increasing the initial amount of quinoline
by a factor of 5 from 10 mg/L to 50 mg/L increased the stoi-
chiometric efficiency from (5.5 :!: 1.3) X 10- 3 to (3.6 :!: 0.1)
X 10- 2 mg quinoline/mg H 20 2 , also a factor of 5 (Fig. 8).
Humic substances are another ubiquitous constituent of wa-
ter; their presence may affect the rate and extent of hydrogen
peroxide and contaminant loss. They may play several differ-
ent roles, including roles as a radical scavenger, radical chain
promoter, and adsorbate that deactivates the catalytic sites. The
net effect could be to increase or decrease hydrogen peroxide
and quinoline loss, depending on what role is dominant (Wang

addition. Based upon the hypothesized mechanism, the quin- and Valentine 1993). The presence of 65.3 mg CIL Aldrich
oline reaction rate should be first order in both the quinoline humic acid reduced the rate of hydrogen peroxide decay by
and hydrogen peroxide concentration 50% and the amount of quinoline lost to only about 10% of
the initial amount, compared to 70% in its absence [Fig. 9(a)].
d[quinoline] . Interestingly, the presence of 13.0 mg CIL humic acid· exhib-
dt = k[qulDoline][H 0 2 2] (4)
ited no measurable effect on quinoline loss, while it increased
the rate of hydrogen peroxide decay by 30%. The net effect
Therefore, a reduction in the amount of quinoline should result of the humic acid at 65.0 mg CIL appears to be a result of its
action as an effective surface site deactivator and competitive
14 r;:::==:::r:;:;::::::;:I;:::;;:::=:;r-............,...,..........j
;J'
12 -
-
10 mg/L quinoline
• 50 mg/L quinoline
I "/
scavenger of reactive intermediates. At the lower concentra-
tion, it is facilitating hydrogen peroxide decomposition pos-
rIO / sibly through solution phase reactions, which compensate for
any reduction in surface catalyzed initiation that could occur
]'8 ~
due to adsorption and site deactivation.
!
<1
6
4 /
Y
SUMMARY AND CONCLUSIONS

:k~£~~o:::;J:~:::=~::=::=~j
100 200 300 400 500
The catalytic activity of iron oxides toward quinoline oxi-
dation was highest for goethite, much less for the semicrys-
talline material, and essentially negligible in the presence of
AlH,OJ (mg/L)
ferrihydrite, both on a mass and surface-area basis. We con-
FIG. 8. Stoichiometric Relationship between Loss of Quino- clude that, of these oxides, goethite is mostly likely to be in-
line and Hydrogen Peroxide Decomposed In Various Goethite volved in the abiotic loss of contaminants in the subsurface
Suspensions at pH 7.7; Carbonate Alkalinity 5 mEqIL, Goethite environment.
Concentration 2,500 mg OxldeIL, and Initial Hydrogen Peroxide
Concentration 500 mgIL Common surface and ground-water constituents can affect
reaction rates and reaction stoichiometry by adsorption to sur-
(a) face active sites or through effects on solution chemistry. The

~
....
0.8

0.6
- 0.8

0.6
i-
I....
operationally defined stoichiometric efficiency relating quino-
line loss to hydrogen peroxide decomposition was neither a
function of oxide concentration nor the presence of carbonate
or phosphate, although they greatly reduced the rate of hydro-
gen peroxide decomposition and the rate of quinoline loss.
This is presumably due to their inability to affect the relative
~
0.4
0.4 J. rate at which reactive intermediates are scavenged by the sur-
0.2 0.2
face. The stoichiometric efficiency characterizing quinoline
0 loss could be reduced to zero in the presence of humic acid
0 0 at a sufficiently high concentration, even though the rate of
0 400 800 1200 1600 2000
TIme(mln) hydrogen peroxide decay was reduced by only 50%. It was
(b) unaffected at a lower humic concentration that increased the
rate of hydrogen peroxide decay by 30%. The difference in
behavior with humic concentration may be attributable to the
0.8 0.8 f several different roles that the humic material may play, in-

~
cluding roles as a radical scavenger, radical chain promoter,
0.6 0.6 .!.... and catalytic site inhibitor.
....
~
0.4

0.2
-+ 0.4

0 0
0 200 400 600
TIme(mln)
FIG. 9. Change of Quinoline and Hydrogen Peroxide Concen-
trations In Goethite Suspensions with Three Sequential Hydro-
gen Peroxide Doses of 500 mgIL and Added Aldrich Humic Acid;
pH of 7.0, Varbonate Alkalinity 0.6 mEqIL, and Initial Quinoline
Concentration 10 mgIL: (a) 65.3 mg CIL Aldrich Humic Acid; (b)
13.0 mg CIL Aldrich Humic Acid
0.2
f
0
In summary, this work has demonstrated that quinoline is
abiotically transformed by mineral catalyzed reaction with hy-
drogen peroxide. By extension, other contaminants may also
react, but the extent and mechanisms may be quite different.
Differences in reactivity due to the characteristics of the con-
800 1000 1200
taminant are expected, as well as differences attributable to
specific mineral characteristics. The presence of complexing
agents will also affect the rate and importance of these pro-
cesses. This work suggests that abiotic loss of contaminants in
the subsurface may occur when hydrogen peroxide is used to
supply oxygen to facilitate aerobic microbial processes. If
reactivity is significant enough, then the addition of hydrogen
JOURNAL OF ENVIRONMENTAL ENGINEERING / JANUARY 1998/37

J. Environ. Eng., 1998, 124(1): 31-38

 peroxide to specifically degrade some compounds may be war-
ranted. Finally, this work suggests that goethite may be of use
as a catalytic material in an above-ground fixed-bed reactor
designed to destroy organic contaminants using hydrogen per-
oxide. This approach may have several advantages over the
use of traditional Fenton's reagent, in that one need not add
soluble iron or lower the pH.
ACKNOWLEDGMENTS
This research was supported through grants from the Environmental
Protection Agency (EPA) Hazardous Substance Research Center for
Regions 7 and 8, and the EPA Office of Exploratory Research (R823402).
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APPENDIX II. NOTATION
The following symbols are used in this paper:
E = operationally defined stoichiometric efficiency;
kmu• = normalized rate constant based on (oxide), mass of iron
oxide per unit volume of water;
kobo observed first-order rate constant of hydrogen peroxide
decay;
k.urf = normalized rate constant based on surface area per unit
volume of water;
SAm = specific surface area, surface area per unit mass of iron
oxide; and
SA. = total surface area per unit volume of water.