United States
Environmental Protection
Agency
Robert S. Kerr Environmental
Research Laboratory
Ada, OK 74820
EPA/600/2-90/006
February 1990
Research and Development
&EPA
Enhanced
Bioremediation Utilizing
Hydrogen Peroxide as a
Supplemental Source of
Oxygen
A Laboratory and Field
Study
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EPA/600/2-90/006
February 1990
ENHANCED BIOREMEDIATION UTILIZING
HYDROGEN PEROXIDE as a SUPPLEMENTAL SOURCE Of OXYGEN:
A LABORATORY AND FIELD STUDY
by
Scott G. Ruling
Bert E. Bledsoe
Extramural Activities and Assistance Division
Robert S. Kerr Environmental Research Laboratory
U.S. Environmental Protection Agency
Ada, Oklahoma 74820
and
Mark V. White
NSI Technology Services Corp.
P.O. Box 1198
Ada, Oklahoma 74820
nents! Protection
sS [^!:r.-iv\ird, 12th FSoof
60604-3590
Robert S. Kerr Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Ada, Oklahoma 74820
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DISCLAIMER NOTICE
The information in this document has been funded by the
United States Environmental Protection Agency. It has been
subjected to the Agency's peer and administrative review, and it
has been approved for publication as an EPA document. Mention of
trade names or commercial products does not constitute
endorsement or recommendation for use.
11
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FOREWORD
EPA is charged by Congress to protect the Nation's land, air,
and water systems. Under a mandate of national environmental
laws focused on air and water quality, solid waste management and
the control of toxic substances, pesticides, noise, and
radiation, the Agency strives to formulate and implement actions
which lead to a compatible balance between human activities and
the ability of natural systems to support and nurture life.
The Robert S. Kerr Environmental Research Laboratory is the
Agency's center of expertise for investigation of the soil and
subsurface environment. Personnel at the Laboratory are
responsible for management of research programs to:
(a) determine the fate, transport and transformation rates of
pollutants in the soil, the unsaturated and the saturated zones
of the subsurface environment; (b) define the processes to be
used in characterizing the soil and subsurface environment as a
receptor of pollutants; (c) develop techniques for predicting the
effect of pollutants on groundwater, soil, and indigenous
organisms; and (d) define and demonstrate the applicability and
limitations of using natural processes, indigenous to the soil
and subsurface environment, for the protection of this resource.
This report describes research conducted to investigate the
efficacy of utilizing hydrogen peroxide as a supplemental source
of oxygen in the enhanced bioremediation of aviation gasoline
contaminated aquifer material in both laboratory-scale and field-
scale studies.
Clinton W. Hall
Director
Robert S. Kerr Environmental
Research Laboratory
111
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ABSTRACT
Remedial actions at hazardous waste sites involving in-situ
treatment are widely recognized as a preferred treatment option.
Bioremediation, a treatment technology which can be implemented
in-situ, utilizes available oxygen to metabolize organic
contaminants. Laboratory and field scale studies were conducted
to investigate the feasibility of using hydrogen peroxide as a
supplemental source of oxygen for the bioremediation of an
aviation gasoline fuel spill.
Field samples of aviation gasoline contaminated aquifer
material collected from a spill site in Traverse City, Michigan
were artificially enhanced with nutrients to promote
microbiological degradation of fuel carbon in a laboratory column
experiment. Oxygen provided from hydrogen peroxide decomposition
was utilized biologically in the columns. However, the rapid rate
of hydrogen peroxide decomposition at 100.0 mg/1 resulted in the
production of oxygen gas. An oxygen mass balance indicated that
approximately 44.0% and 45.0% of the influent oxygen was
recovered in aqueous and gaseous phases respectively. Reduced
rates of oxygen consumption during this period indicated that
microbial inhibition may have occurred.
A mass balance of the fuel carbon indicated that
approximately 36% of the initial mass leached out in the aqueous
phase, 10.0% remained, and 54.0% degraded. The ratio of oxygen
consumed to aviation gasoline degraded was greater than that
predicted by the ideal stoichiometric conversion. Hydrogen
peroxide breakthrough in the column effluent never exceeded 11.0%
of the influent concentration. The influent hydrogen peroxide
concentration in triplicate columns (18 cm. in length) was 50.0,
100.0, and 200.0 mg/1.
Ground-water data from the enhanced in-situ bioremediation
pilot field study indicates that hydrogen peroxide successfully
increased the concentration of available oxygen downgradient. In
this study, however, it was observed that there was a measurable
increase of oxygen in the soil gas in the area where hydrogen
peroxide was injected. This indicated that a significant fraction
of hydrogen peroxide rapidly decomposed to oxygen gas and escaped
into the unsaturated zone.
IV
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CONTENTS
Foreword
Abstract
Figures
Tables
Acknowledgements
Section 1.
Section 2.
Section 3.
Section 4.
Section 5.
Section 6.
Section 7.
Section 8.
Section 9.
Section 10.
Section 11.
Introduction
Conclusions
Recommendations for process and
applications research
Methods and materials - Laboratory Study
Results
Field study - background
Methods and materials - Field study
Results
Discussion
References
Appendix
Field Data - Available Oxygen in ground water,
sampling port Nos. 7A-C, 31, 48A, 50B-G, 62,
83A-C, 108
ill
iv
vi
vii
viii
1
5
6
8
10
18
24
25
30
32
36
v
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FIGURES
Number Page
1. Schematic of Soil Columns 8
2. Oxygen Response Curve, Column A 11
3. Oxygen Response Curve, Column B 11
4. Oxygen Response Curve, Column C 11
5. Cumulative Oxygen Demand, Column A 13
6. Cumulative Oxygen Demand, Column B 13
7. Cumulative Oxygen Demand, Column C 13
8. Aviation Gasoline Plume, U.S. Coast Guard Station 19
9. U.S. Coast Guard Air Station, Traverse City Mich. 20
10. Cross Section Of Pilot Study, Field-Scale Wells 21
11. Percent Oxygen In The Unsaturated Zone, 26
3 ft level
12. Percent Oxygen In The Unsaturated Zone, 27
6 ft level
13. Percent Oxygen In The Unsaturated Zone, 28
9-10 ft level
VI
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TABLES
Number Page
1. Column Influent and Effluent Flux of 12
Available Oxygen in Aqueous and Gaseous Phases
2. Hydrocarbon Mass Balance 15
3. Conversion Ratios (O0 (ing)/Aviation Gasoline (mg)) 16
f»
4. Hydrogen Peroxide Breakthrough 17
5. Vertical Distribution of Contaminants 50 ft 18
Downgradient from the Injection Wells
6. Oxygen - Hydrogen Peroxide Injection Schedule 22
7. Oxygen Concentration Profile Downgradient 26
of the Injection Area
VII
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ACKNOWLEDGEMENTS
The authors wish to thank Dorene Meyer and Michelle Hester of
EPA at the Robert S. Kerr Environmental Research Laboratory
who performed much of data entry associated with this study. We
would also like to thank the Traverse City Group, Inc. staff,
namely, James Russell, Bill Newman, and Robert Douglas, who
provided several of the figures used in this report and much of
the ground water data from the field-scale study at the U.S.
Coast Guard Station in Traverse City Michigan.
Vlll
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SECTION 1
INTRODUCTION
The Superfund Amendments and Reauthorization Act (SARA) of
1986 directed EPA to prefer remedial actions involving treatment
that would permanently and significantly reduce the volume and
toxicity, or mobility of hazardous substances, pollutants, and
contaminants over remedial actions not involving such treatment.
Therefore, the off-site transport and disposal of hazardous
substances or contaminated materials without treatment is the
least favored remedial action where practicable alternative
treatment technologies are available [9,20].
Bioremediation is a relatively new treatment technology that
can be implemented in-situ in which microorganisms metabolize
organic contaminants generally into harmless byproducts. Aerobic
bioremediation has been reported to degrade a wide variety of
organic contaminants such as alkylbenzenes (benzene, toluene,
xylene (BTX)), polynuclear aromatic hydrocarbons, heterocyclic
organic compounds, and some of the simpler chlorinated compounds
[22b,7]. Recently, researchers have found that transformation of
trichloroethylene by methane-oxidizing bacteria under aerobic
conditions is possible [22a].
In aerobic respiration, free molecular oxygen accepts
electrons from an electron donor, usually carbon, and is reduced
to a lower oxidation state. An important aspect of these
biochemical redox reactions is their irreversibility; therefore,
dissolved oxygen is always consumed and never produced as a
result of bacterial metabolism [13]. Oxygen, if not present in
adequate concentration, will limit the ability of aerobic
microorganisms to degrade contaminants. In one field experiment
where BTX was injected in a sandy aquifer, researchers reported
that an irregular persistence of BTX occurred in a near-zero
dissolved oxygen environment [2]. Therefore, the rate of aerobic
biotransformation, and thus, contaminant persistence, was
reported to be controlled by the transport of oxygen into the
BTX-contaminated water. At another site, the low level of
dissolved pxygen in creosote contaminated ground water was
identified as the probable factor limiting biodegradation [lla].
Due to the dissolved oxygen sink in biologically active
contaminated aquifer systems, oxygen supplementation is required
to maintain aerobic conditions. Several methods have been
developed to increase and maintain the concentration of dissolved
oxygen in the ground water.
Air sparging is a process that involves diffusing compressed
air into water that is subsequently infiltrated or injected into
the contamination zone. Oxygen will diffuse into the water at a
rate proportional to the deficit of oxygen below maximum
solubility. This,method of oxygen supply is limited by the
relatively low solubility of oxygen in water from air, typically
8-10 mg/1, and the rapid depletion of oxygen by bacteria
[4a,llb].
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Ozone, which rapidly decomposes to oxygen in aqueous
solutions containing impurities, has been injected into ground
water for the purpose of increasing the concentration of
dissolved oxygen [1]. Due to the highly oxidative nature of
ozone, this gas is also capable of oxidizing organic material.
Information concerning ozone injection and subsequent subsurface
microbial toxicity is limited.
Soil venting is used to recover volatile organic vapors in
highly permeable formations [5], Researchers have suggested that
since air contains approximately twenty times more oxygen on a
volume basis than water, and is less viscous, then soil venting
could increase the available oxygen in the unsaturated zone for
biological activity [22c]. Information concerning this method of
ground water oxygenation is also limited.
Liquid or gaseous oxygen has been introduced into water and
injected into the subsurface. This method takes advantage of the
increased oxygen solubility, typically 40-45 mg/1, that can be
obtained when using pure oxygen [8].
Hydrogen peroxide injection into the ground water has
recently become a popular method of introducing oxygen to
targeted contaminated low dissolved oxygen zones. Hydrogen
peroxide decompostion reactions, ideally, yield one mole of water
and one mole of oxygen (equation 1), thereby introducing pure
oxygen into ground water. Hydrogen peroxide is highly soluble and
potentially highly mobile, thus offering numerous operational
advantages in the field. However, relatively little information
concerning its utilization in a biologically active contaminated
aquifer system is currently available.
Hydrogen peroxide decomposition can be characterized by the
net result reaction [14]:
2H202 > 2H20 + (X, (1)
The most important aspect of the reaction is the liberation of
one mole of oxygen. The reaction product, oxygen, is the basis
for injecting hydrogen peroxide due to the subsequent
replenishment of oxygen in the ground water. The stoichiometry of
eqn. (l) indicates that 47.1% by weight of decomposed hydrogen
peroxide will be pure oxygen. The two main mechanisms for
hydrogen peroxide decomposition are enzymatic and non-enzymatic
reactions. Enzymatic decomposition reactions are catalyzed by
hydroperoxidases (catalases and peroxidases) which are found in
most bacterial cells and are characterized by the following
reactions:
catalase
2H2°2 > 2H2° + °2 (2)
peroxidase
H202 + XH2 > 2H20 + X (3)
where X is a biological reductant [3]. Many scientific
observations have been reported concerning catalysts; however,
the greatest attention has been centered on the enzyme, catalase
[14]. Catalase, found in most bacteria, is primarily responsible
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for catalytically decomposing cell synthesized hydrogen peroxide,
thus preventing the accumulation of hydrogen peroxide to a toxic
level. Catalase is outstandingly effective in this process, being
active at low hydrogen peroxide concentrations and at a rate far
exceeding that of most other catalysts [14]. Furthermore,
researchers have reported that the hydrogen peroxide
decomposition observed in an infiltration gallery at an enhanced
bioremediation pilot study was largely attributed to the catalase
driven reaction [16].
One reviewer of non-enzymatic iron decomposition reactions
[14] indicated the most notable are those in the presence of iron
salts and the generally accepted mechanism is a series of complex
chemical reactions involving hydroxyl and perhydroxyl radical
intermediates and both ferric and ferrous iron as illustrated by
the following reactions:
Fe+2 + HO > Fe+3 + OH~ -i- OH* (hydroxyl radical) (4)
€* £n
OH* + H-0- > HO + H+ + 02"~ (superoxide radical) (5)
o2*~ + H2o2 > o2 + OH" + OH* (6)
Fe+3 + H_0_ > Fe+2 + 2H+ + O *~ (7)
£» ft £t
Fe+3 + 02*~ > Fe+2 + O2 (8)
The overall stoichiometry for both catalase and iron
decomposition of hydrogen peroxide is equivalent to that
described in equation 1.
Non-enzymatic decomposition of hydrogen peroxide was
investigated in laboratory studies to determine the effects of a
potassium phosphate "stabilizer" and pH [3]. Hydrogen peroxide
decomposition was not observed to be significantly effected by
pH. However, the presence of a 0.01M solution of Potassium
Phosphate (monobasic) was observed to significantly inhibit
hydrogen peroxide decomposition. Phosphate inhibition of hydrogen
peroxide decomposition is fortuitous since phosphate is also an
important microbial nutrient.
Hydrogen peroxide is well known for its bactericidal
properties. Three percent hydrogen peroxide is cytotoxic and
commonly used as a general antiseptic. In a laboratory study
where hydrogen peroxide provided the main source of oxygen for
hydrocarbon degrading bacteria, plate counts were used as an
indicator of microbiological activity [3], These researchers
reported that the maximum concentration tolerated by a mixed
culture of gasoline degraders was 0.05% hydrogen peroxide. The
tolerance was increased to 0.2% by incrementally raising the
hydrogen peroxide concentration. Tolerance was determined to
occur when the number of colony forming units in the test column
were essentially.the same for the control column. One important
observation made during this study was that non-viable cell
material catalyzed the decomposition of hydrogen peroxide as well
as viable cell material. Field reports indicated that 100-500
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mg/1 hydrogen peroxide have been injected into contaminated
aquifers [2^,4b] and unpublished reports of 1000-10,000 mg/1 are
not uncommon.
The objectives of the laboratory study were to confirm that
hydrogen peroxide can be used to supply oxygen in the
bioremediation process, assess the tolerance of the system to
hydrogen peroxide, and estimate the overall oxygen demand based
on stoichiometric degradation of hydrocarbon. A field scale in-
situ bioremediation pilot study in which hydrogen peroxide and
nutrients were injected into contaminated aquifer material
provided the opportunity to confirm laboratory observations in
the field.
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SECTION 2
CONCLUSIONS
LABORATORY STUDY
Hydrogen peroxide was shown to rapidly decompose and produce
pure gaseous oxygen. Due to precautions taken to minimize non-
enzymatic decomposition in this study, the data indicate that
hydrogen peroxide decomposition to oxygen and water was the
result of enzymatic catalysts. Oxygen provided by the hydrogen
peroxide decomposition reaction was consumed in the columns. It
was not possible to distinguish between abiotic and biotic oxygen
demand in this study.
The injection of hydrogen peroxide at 100.0 mg/1 had two
observed notable effects. The rapid rate of decomposition
resulted in a high rate of oxygen gas production. The rate
of oxygen gas production far exceeded the demand, and although
the solubility of dissolved oxygen had not been exceeded, gas
bubbles appeared to have insufficient time to diffuse from the
gaseous phase into the aqueous phase. Approximately 45% of the
available oxygen injected into the columns was transferred into
the gaseous phase. Secondly, the rate of oxygen consumption
decreased indicating that bacterial inhibition may have occurred.
Mass balances of both oxygen and hydrocarbon was calculated
to quantify the mass of oxygen consumed and the mass of
hydrocarbon degraded. The ratio of estimated oxygen consumed to
aviation gasoline degraded was found to be greater than the
stoichiometric prediction.
Hydrogen peroxide, introduced into the biologically active
columns at 50.0, 100.0, and 200.0 mg/1, never exceeded 11%
breakthrough although the columns were only 18 cm in length.
FIELD STUDY
Injecting hydrogen peroxide into the aquifer at the pilot
study area resulted in; increasing the concentration of available
oxygen in downgradient wells; rapid decomposition of hydrogen
peroxide; and the liberation of oxygen gas into the unsaturated
zone resulting in a concentration much greater than background.
The rate of hydrogen peroxide decomposition at the site was
unknown but was expected to be rapid due to the concentration of
oxygen gas measured in the pilot study area.
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SECTION 3
RECOMMENDATIONS
RECOMMENDATIONS for PROCESS and APPLICATIONS RESEARCH
This study has focused on investigating the feasibility of
utilizing hydrogen peroxide as a supplemental source of oxygen
for the enhanced bioremediation of contaminated (aviation
gasoline) aquifer material. Clearly, injection of hydrogen
peroxide into the ground water will increase the concentration of
dissolved oxygen which can be used as an electron acceptor in the
bioremediation process. However, the rapid decomposition of
hydrogen peroxide as observed in this study, and the subsequent
liberation of the oxygen gas to the unsaturated zone will
limit the effectiveness of hydrogen peroxide to supply oxygen to
the saturated zone. The following recommendations are suggested
to further evaluate the feasibility of utilizing hydrogen
peroxide as a source of oxygen.
1. Research designed to differentiate between biotic and
abiotic mechanisms of hydrogen peroxide decomposition will offer
the opportunity to more completely understand the role of
biological and chemical variables in this reaction. The
application of this information could then be used to develop
methods to control or minimize decomposition reactions.
Understanding these processes may also help identify chemical and
biological subsurface conditions that are not conducive to this
method of oxygen supplementation.
2. The results of the laboratory column study found hydrogen
peroxide at 100.0 mg/1 to decrease the oxygen utilization rate. A
decline in the oxygen utilization rate indicated that bacterial
inhibition may have occurred. While other research has found the
hydrogen peroxide microbial toxicity threshold to be much higher,
these are usually based on bacterial enumeration. The oxygen
utilization rate is a parameter which offers feedback on the
performance of the biodegradation process. The concentration of
hydrogen peroxide identified in this research which indicated
bacterial inhibition had occurred has paramount importance since
it is process oriented and is relatively low. Additional research
is necessary both to verify this observation and to more closely
examine the toxicity effect from a process perspective.
3. The feasibility of using hydrogen peroxide as a
supplemental source of oxygen at a bioremediation site must
consider also the economics and safety of this method compared to
other candidate methods. Included in this evaluation are: the
cost of the hydrogen peroxide; operation and maintenance costs of
the equipment to store, mix, and deliver the hydrogen peroxide;
the fraction of oxygen actually delivered to the saturated zone;
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toxicity; and safety. A comprehensive feasibility evaluation is
necessary to identify the technical and economic benefits of
using various techniques of oxygen supplementation.
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SECTION 4
MATERIALS and METHODS
LABORATORY STUDY
The contaminated aquifer material, characterized as a fine to
medium grained sand, was retrieved from a thick glacial deposit
aquifer in Traverse City, Michigan [18,10]. An aseptic,
undisturbed aquifer sample was collected from the heart of an
aviation gasoline plume using a modified hollow stem auger
drilling tool [10]. Approximately 476 g. of wet, contaminated
soil was placed in each column. An abiotic control column was not
used in this experiment. A schematic of the laboratory apparatus
is shown in Figure 1. The glass columns were approximately 18 cm
long (4 cm I.D.). Glass wool was placed in the top and bottom
followed by 1.5 cm of coarse sand. Soil columns were kept in a
constant temperature chamber at 12 C.
Figure 1. Schematic of soil columns. (1) feed water; (2) nutrient solution; (3) peroxide
solution; (4) peristaltic pump; (5) mixing coil; (6) teflon septa sampling port; (7) glass
syringe; (8) syringe pump; (9) gas trap; (10) waste collection.
8
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A mixture of feed water, nutrients, and hydrogen peroxide was
pumped (peristaltic pump) through the columns. The columns were
operated in a continuous upflow mode. Feed solutions were mixed
in an in-line mixing coil prior to introduction to the columns.
Effluent samples from the column were retrieved in-line using a
syringe pump. This enabled the retrieval of an aqueous sample in
a closed system without losing volatiles and without
aerating/deaerating the column effluent. An inverted centrifuge
tube was installed in-line to capture and quantify the gas
produced from the column.
Chemical analyses were performed in accordance with EPA
methods [6]. Available oxygen (eqn. 9) from both the hydrogen
Available oxygen = ([DO] + 0.471 [H2O2])
(9)
where; [DO] = dissolved oxygen, mg/1
[H2O2] = hydrogen peroxide concentration^ mg/1
peroxide and the dissolved oxygen (DO) was measured using the
Winkler azide modification method (EPA Method No. 360.2).
Hydrogen peroxide analysis was determined using a peroxytitanic
acid colorimetric procedure. The columns were pretreated with a
phosphate rich nutrient solution (128.0 mg/1 Orthophosphate as P)
prior to the introduction of hydrogen peroxide. This pretreatment
step was a precaution taken to prevent iron decomposition of
hydrogen peroxide. The influent phosphate concentration was
decreased (89.2 mg/1 O-P as P) after 20 hours of pretreatment
when 98% breakthrough of O-P (as P) had occurred. The influent
nutrient concentrations to the columns was 400.0 mg/1 Ammonium
Chloride, 200.0 mg/1 Potassium Phosphate (monobasic), 200.0 mg/1
Sodium Phosphate, and 100.0 mg/1 Magnesium Sulfate. Hydrogen
peroxide was introduced at 15.0 mg/1.
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SECTION 5
RESULTS
LABORATORY STUDY
Due to the low oxygen demand observed during the first eight
days of operation, the flow rate was reduced from 80.0 ml/hr to
45.0 ml/hr. The increased hydraulic residence time in the column
resulted in greater oxygen consumption and increased the accuracy
in determining the oxygen demand. The oxygen demand exerted on
the influent was calculated as follows:
Oxygen demand = (Influent [DO] + 0.471[H2O2]) (10)
- Effluent [DO]
where the effluent DO concentration, as determined by the Winkler
method, detects both DO and oxygen from hydrogen peroxide.
Approximately two weeks was required before significant oxygen
consumption was observed in all three columns, (Figures 2-4).
This response was interpreted as characteristic of microbial
acclimation to a new chemical or physical environment. The
concentrations of nitrates and nitrites in the column effluent
were consistently equivalent to background concentration (<1.0
mg/1) found in the feed water.
Hydrogen peroxide was increased from 15.0 mg/1 to 30.0 mg/1
after the oxygen demand exceeded approximately 80% of the
available oxygen. This increase corresponded to an additional 7.1
mg/1 available DO. The effluent oxygen concentration increased
indicating a response to the increase in hydrogen peroxide
concentration. Hydrogen peroxide was increased to 100.0 mg/1
after the oxygen demand exceeded approximately 80% of the
available oxygen. Initially, the oxygen demand appeared to
increase greater than 50% from the previous hydrogen peroxide
concentration. However, bubbles were observed in the column
effluent line indicating that a loss of oxygen from the system
was occurring.
During a period of fifteen days following the hydrogen
peroxide injection of 100.0 mg/1, effluent DO remained constant
(DO avg. = 24.6 mg/1, n = 29, st. dev. = 1.25 mg/1) in all three
columns. In-line gas traps were used to capture and quantify the
gas produced from the columns (Fig. 1). The average rate of gas
generation during this period from columns B and C was 1.17
ml/hr. Gas chromatograph analysis of the captured gas indicated
that the gas composition was approximately 65%-70% oxygen and
30%-35% nitrogen.
A mass balance was performed on the influent and effluent
available oxygen.in the system. The influent mass of oxygen was
calculated as follows:
10
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Fig. 2 Oxygen Response Curve, Column A
Conta i * ialed Aqufer Material
[1001
[] = Hydrogen Peroxide
Cor ictif Af altun, ing/l
B Effluert Avatebte Oxygen Influent Avatebte Oxygen
Fig. 3 Oxygen Response Curve, Column B
Contaminated AquFer Material
[100]
[] = Hydrogen Peroxide
Concentration, mg/l
mo mo
® Effluent Available Oxygen Influent Available Oxygen
Fig. 4 Oxygen Response Curve, Column C
Contaminated Aqufer Material
[100]
[] = Hydrogen Peroxide
Coi met 4jot!un, mo/l
I 1 1 1 1 1 1 1 "•' I 1 1 1—=~l
Q Effluent AvaJabie Oxygen influent Available Oxygen*
11
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Mt,i = QT [DO]..^ + 0.471 QR [H2O2] (11)
where; Mt,i = total influent oxygen, mg/hr
QT = total flow, 1/hr
[DO] . = influent dissolved oxygen, avg.
concentration @ 12 deg. C, 9.35 mg/L,
QH = Hydrogen peroxide flow, 1/hr
The effluent mass of oxygen is calculated as follows:
Mt,e = QT [D0]e + f 02gas (12)
where; Mt,e = total effluent oxygen, mg/hr
[DO]e = effluent available oxygen, mg/1
includes DO + .471 [H2O2]
O2gas = average rate of O_gas generated, 1/min
f = fraction of oxygen in mixture (.675)
Mass balance results were converted to moles/hr and are included
in Table 1. The oxygen mass balance indicates that roughly 44.0%
and 45.0% of the influent oxygen was recovered in the aqueous and
gaseous phases respectively for a total recovery of 89%. The
unrecovered oxygen was assumed to be consumed both biotically and
abiotically. The cumulative total and cumulative adjusted oxygen
demand curves for each column are presented in Figures 5-7. The
cumulative adjusted oxygen demand curve is the difference between
the cumulative total oxygen demand and the oxygen lost from
Table 1 - Column Influent and Effluent Flux of Available
Oxygen' ' ' in Both Aqueous and Gaseous Phases
INFLUENT
aqueous
EFFLUENT
aqueous
gaseous
A
7.78E-5
3.41E-5
(43.8%)
3.5E-5<3>
(45.0%)
COLUMNS
B
7.78E-5
3.4E-5
(43.7%)
3.71E-5
(47.7%)
C
7.78E-5
3.42E-5
(44.0%)
3.29E-5
(42.3%)
(1) Flux rate, moles oxygen/hr.
(2) Values in parentheses indicate percent effluent of total
influent flux.
(3) Average of columns B and C.
12
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8
x
3»
a
6
I
o
g
6
Figure 5. Cumulative Oxygen Demand, Column A
Total and Adjusted Oxygen Demand
20.0
40.0
60.0
800
100.0
1200
140.0
Time (Days)
D Total Oxygen Demand
O Adjusted Oxygen Demand
Figure 6. Cumulative Oxygen Demand, Column B
Total and Adjusted Oxygen Demand
200
40.0
60.0
80.0
100.0
120.0
140.0
Time (Days)
D Total Oxygen Demand
O Adjusted Oxygen Demand
Figure 7. Cumulative Oxygen Demand, Column C
Total and Adjusted Oxygen Demand
200
400
600
800
1000
1200
1400
Time (Days)
D Total Oxygen Demand
13
O Adjusted Oxygen Demand
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the system due to degassing. The total and adjusted oxygen demand
curves demonstrated the potential of hydrogen peroxide, at 100.0
mg/1 to rapidly decompose resulting in the production of pure
oxygen. The slopes of the cumulative adjusted oxygen demand
curves (Figures 5-7) during the 100.0 mg/1 hydrogen peroxide
injection period is less than the slope at lower hydrogen
peroxide concentration periods during the study. A decrease in
the oxygen consumption rate indicates that inhibition of
bacterial respiration during this period may have occurred. The
hydrogen peroxide concentration was reduced to 30.0 mg/1 due to
the inefficient use of available oxygen and the apparent
reduction in the rate of oxygen consumption.
Effluent available oxygen concentration during the 100.0 mg/1
hydrogen peroxide injection averaged 24.6 mg/1. The aqueous
solubility of pure gaseous oxygen at 12 C is approximately 43.0
mg/1. The results of the column study suggested that the oxygen
bubbles did not have sufficient time to diffuse from the gaseous
phase into the aqueous phase.
In an attempt to optimize the utilization of oxygen in the
system, an oxygen mass balance on the columns was used to compute
an influent hydrogen peroxide concentration (69 mg/1) below which
degassing would not occur. This approach assumed that maximum
solubility of dissolved oxygen could be achieved. Influent
hydrogen peroxide concentration was increased to 60.0 mg/1.
Shortly thereafter, gas bubbles were observed in the effluent
line. As discussed previously, this data indicated that the
retention time of the oxygen bubble in the system was inadequate
for oxygen gas to diffuse into the aqueous phase.
During the later stages of the study, degassing was noted to
occur at hydrogen peroxide concentrations that previously did not
result in degassing. It appears that this may have been due
primarily to enzymatic decomposition associated with the
additional biomass in the system and the short retention time of
the bubbles in the column. Influent hydrogen peroxide
concentration during the remainder of the experiment was
incrementally adjusted as the oxygen demand changed with time.
The average cumulative total oxygen demand from the columns
was 1940 + 127 mg oxygen and the average cumulative total oxygen
demand, adjusted for the oxygen degassing was 1360 + 67 mg O2.
During the various operating scenarios (i.e. varying influent
hydrogen peroxide concentration) of this study, degassing
accounted for approximately 30% of the total oxygen demand.
The slope of the cumulative adjusted oxygen demand curve in
Figures 5-7 represents the overall rate of oxygen consumption
during the study period. Linear regression analysis of the
cumulative adjusted oxygen demand versus time, after the 100.0
mg/1 hydrogen peroxide injection, are as follows:
2
Column Slope fmg oxygen/day) r
A 11.4 0.99
B 10.4 0.99
C 13.5 0.99
14
-------
Gas chromatograph analysis of the initial and final aquifer
material [19] and the column effluent was performed to calculate
an approximate mass balance of hydrocarbons in the system, (Table
2). Based on the mass of aquifer material in each column, the
initial and final average fuel carbon (FC) concentrations, and an
estimate of the effluent FC, the amount of FC degraded was
estimated using equation 13. Based on the average of all three
columns, 36% of the initial mass of fuel carbon leached from the
Table 2 - Hydrocarbon Mass Balance
COLUMNS
ABC
Aquifer Material Analyses
Mass (kg) 0.479 0.475 0.474
Initial [FC] ^ (mg/kg) 906.0 906.0 906.0
Initial mass FC^ (mg) 434.0 430.0 429.0
(Mj)
Final [FC] soil^3* 136.0 60.0 76.0
(mg/kg)
Mass FC final^4^(mg) 65.0 29.0 36.0
(MF>
Column Effluent Analyses
Effluent FC aqueous (mg) 154.0 150.0 161.0
(ME)
Estimated FC Degraded
Mass FC degraded (mg) 215.0 251.0 232.0
(MD)
(1) Average of triplicate analyses of contaminated aquifer
material from which the column material was derived, (790.0,
1045.0, and 884.0 mg/kg) initial fuel carbon concentration in
column aquifer material = 906.0 mg/1.
(2) Mass FC initial = 906.0 (mg/kg) X Soil mass (kg).
(3) Average of replicate analyses for each column of fuel carbon
in the final aquifer material.
(4) Mass FC final = Final [FC] mg/kg X Soil mass(kg).
(5) Estimated FC in column effluent.
(6) Mass FC biodegraded, M - M - M .
JL j? Ji
15
-------
aquifer material, 10% remained on the aquifer material, and 54%
degraded.
MD = MI - MF - ME
where; MQ = fuel carbon biodegraded;
M.J. = fuel carbon initial;
MF = fuel carbon final; and
= fuel carbon in column effluent.
The empirical carbon and hydrogen content of the aviation
gasoline was determined to be approximately 2.16 parts hydrogen
per part carbon, or roughly 85% carbon and 15% hydrogen [12]. The
ideal stoichiometric biological conversion of hydrocarbon to
carbon dioxide and water is approximately 3.48 parts oxygen per
part hydrocarbon as described in the following equation:
CH2.16 + 1>54 °2 > C02 + 1'08 H2° (14)
The ratio of the estimated oxygen consumed to estimated aviation
gasoline degraded in this study was greater than the
stoichiometric conversion ratio, (Table 3). Measured conversion
ratios greater than the stoichiometric prediction was likely to
occur due to errors in the mass balance analysis and the abiotic
oxygen demand. It was not possible to differentiate between
biotic and abiotic oxygen demand in this study.
Table 3 - Conversion Ratios (O2(mg) / Aviation Gasoline (mg))
COLUMNS
A B C
Mass O2 consumed^1) 1322.0 1307.0 1434.0
(mg)
Mass Aviation gasoline' ' 253.0 295.0 274.0
degraded (mg)
Conversion Ratio 5.23 4.43 5.23
mg O2/mg Av. gasoline
(1) Adjusted Cumulative Oxygen Demand, Figures 5-7
(2) Mass Aviation gasoline degraded = Mass FC Degraded/(0.85)
16
-------
Colorimetric hydrogen peroxide analysis of the column
effluent was performed to determine the persistence of hydrogen
peroxide in the contaminated aquifer material. Prior to
terminating the experiment, hydrogen peroxide was injected at
50.0, 100.0, and 200.0 mg/1. These concentrations were injected
for 7, 10, and 13 hours, respectively, prior to collecting
effluent samples. Breakthrough of hydrogen peroxide, for all
three concentrations, was less than 11% (Table 4). The
introduction of phosphate as a nutrient into the columns was
expected to minimize the non-enzymatic catalysis of hydrogen
peroxide. Therefore, the rapid decomposition of hydrogen peroxide
in this system appeared to be due to enzymatic catalysis,
demonstrating that the column media was biologically active.
Table 4 - Hydrogen Peroxide Breakthrough
COLUMNS
[H202]i
(mg/i)
[H202]e
(mg/1)
H202 Break-
through (%)
ABC
50.0
ND ND ND
<10 <10 <10
A B
100.
9.6 10.
9.6 10.
0
4
4
C
2.5
2.5
A B
200.
16.5 17.
8.3 8.
0
0
5
C
9.3
4.7
[H2O2]i, [H2O2]e - influent and effluent hydrogen peroxide
concentration, respectively
Detection limits:
[H202J
ioo.o, 200.0
17
-------
SECTION 6
FIELD STUDY
BACKGROUND
Twenty years ago, aviation gasoline (25,000 gal.) spilled
into a shallow, sandy, water table aquifer at the U.S. Coast
Guard Station in Traverse City, Michigan. The aviation gasoline
migrated to the water table and spread laterally. Soluble
components of the hydrocarbon plume migrated longitudinally in
the direction of ground water flow and eventually moved off the
Coast Guard Station and contaminated a large number of domestic
water wells in a residential area, refer to Figure 8. The spill
site was cored extensively to determine the distribution of
contamination in the subsurface. The majority of the
contamination was found to be distributed within a narrow
interval between 15 and 17 feet below the land surface (Table 5)
[22d] corresponding to the seasonal low and high water table at
the site.
Table 5 - Vertical Distribution of Contamination 50 feet
Downgradient From The Injection Wells
Depth Interval
(feet below surface)
Fuel
Hydrocarbons
(mg/kg aquifer)
15.1-15.5
15.5-15.8
15.8-16.2
16.2-16.5
16.5-17.2
17.2-17.5
18.0-18.3
< 11
39
2370
8400
624
< 13
< 13
In 1988, the U.S. Coast Guard and the U.S. EPA began the
operation of a pilot scale in-situ bioremediation project in the
area of the original spill [15,17a-f]. A series of five deep
wells (11-15) were used to inject clean water beneath the plume
area in an effort to raise the water table and subsequently
saturate the contaminated "smear zone". Raising the water table
was performed in order to allow the delivery of soluble nutrients
to the targeted zones of contamination. Five chemical feed wells
(CF1-CF5) were used to inject nutrients and hydrogen peroxide in
the shallow, contaminated layer (Figures 9,10). A series of
downgradient monitoring wells (DG-8, -25, -37, -49B, -61, -109)
18
-------
EAST
-------
DG—1O9
•
BD—ioa
BD-83A
0
I
15
BD-83B
UJ
oc
u.
UJ
I
o
o
30
I I I I I I
SCALE IN FEET
BD-62
DG—49A
O
TP-4
BD-83C
DG-61
BO-50Q. .
BD— SOB DG— 49C
DG-49B
BD-48A
DG-37
•
BD-31
•
DG-25
O
2
Q
5
m
2
O
F
<
a:
H
to
2
a:
u
o
z
BD-7C
*
DG-.8,BD-7BCF-5
•BD-7A
CF—
CF-Z
CF-1-t
I-2
1-1
Figure 9 - U.S. Coast Guard Station, Traverse City,
Michigan. Pilot Scale Aerobic Biodegradation
Project, Monitoring and Injection Wells
UG—41
20
-------
Figure 10 - Cross Section Of Pilot Study Wells
ELE
IN
615-
610-
600-
595-
590-
585-
VX
-E
U
XT|ON INJECTION
ET WELLS v
G 41 V^
D
\
m
I
Q
CD
I
I
)
I
G-8 D
n — "
I ^^^^Cc
Go e DG —
.^. «_j
DG-37
m
^-
I
o
m
•— — •
i
^
i
( — '•
%%
i — .
>
0* 1C
I f It 1 Mil
— — — — —
%%%
)' 20'
1 1 1 1 1 1 1 1 1 1
•49B
CO
o
m
o
m
Y//Y///
> ••" " " •
l>
DG— 61
D
m
/
i . _j
tfffiffifflft
) \_ Illl 1 II '
l\ c
m oo
K) O
CO r-
| 1
O Q
m 00
^— ZONE OF
REMEDIATION
> (
> <
^— INITIAL ZONE OF
CONTAMINATION
WATER TABLES
4/20/88 HI
INITIAL
WATER TABLE
HORIZONTAL SCALE
-------
and subsurface sampling lines (BD-7A,B,C, BD-31, BD-48A, BD-
50A,B,C, BD-62, 83-A,B,C, and BD-108) were installed to monitor
the performance of bioremediation. The sampling lines have
several vertical sampling ports (1 foot stainless steel screens)
at one foot intervals. The sampling ports are numbered
sequentially starting at one and increasing with depth (i.e. BD-
7B1, BD-7B2, BD-7B3...).
Nutrient and oxygen injection began in March 1988. Nutrient
enriched water was injected at a total flow rate of approximately
11 gpm in the five chemical feed wells. The nutrients in the
injected water contained approximately 380 mg/1 ammonium
chloride, 190 mg/1 disodium phosphate, and 190 mg/1 potassium
phosphate. A liquid oxygen source was used to inject
approximately 40 mg/1 dissolved oxygen. Approximately 3 months
later (June 1988), hydrogen peroxide was injected according to
the schedule given in Table 6. Prior to hydrogen peroxide
injection, phosphate breakthrough had occurred in the nested
monitoring wells. This was necessary to complex the iron found in
the aquifer material with phosphates and therefore, minimize the
iron catalyzed hydrogen peroxide decomposition reaction. Due to
problems associated with the chemical feed system, including
hydrogen peroxide stratification in the feed tank, the
concentration of hydrogen peroxide that was injected varied
considerably. Therefore, it was difficult to compare the
concentration of dissolved oxygen in the injected water with
parameters measured in the monitoring wells.
Table 6 - Oxygen - Hydrogen Peroxide Injection Schedule
Date Time(days)
3/2/88
6/2/88
6/7/88
6/14/88
8/17/88
12/3/88
90
5
7
64
106
179
(2)
Cumulative
Time(days)
90
95
102
166
272
451
Oxygen Source Concentrat ion
Liquid Oxygen
Hydrogen Peroxide
ii it
40
50
110
250
500
750
(1)
(1) Concentration as dissolved oxygen
(2) 179 days as of 5/31/89
Both soil gas and ground water analyses were used to
investigate the fate of hydrogen peroxide in the in-situ
bioremediation field scale pilot study. Results of the laboratory
study indicated that a significant fraction of hydrogen peroxide
injected into the subsurface may decompose prematurely and result
in the liberation of oxygen gas into the unsaturated zone. This
22
-------
was evaluated in the field by analyzing soil gas in the injection
area for the concentration of oxygen and comparing it to the
background soil oxygen concentration. Soil gas samples were
collected at various depths and locations in the vicinity of the
chemical injection wells.
23
-------
SECTION 7
MATERIALS and METHODS
FIELD STUDY
Soil gas was sampled in the vicinity of the injection area
and analyzed for the oxygen concentration. Soil gas samples were
obtained using a series of stainless steel tubes (3/8 in. I.D.)
that could be coupled together and driven into the subsurface to
various depths. Due to problems associated with driving and
retrieving the coupled sampling tubes, soil gas sampling mainly
occurred in the 0-10 ft range. Soil gas was pumped into a sample
vessel which contained an oxygen detector using a hand held
positive displacement pump. The oxygen detector is a GasTech
Model LO2 OxyTechTor galvanic cell which measures the
concentration of oxygen from 0-100% + 5% of the reading. Oxygen
was also measured in the headspace in ground-water monitoring
wells by lowering the detector to various levels within the well
Ground-water analyses for available oxygen (i.e. [DO] +
0.471[H202]) performed throughout the pilot study [15,17a-f]
offered the opportunity to evaluate the performance of the
bioremediation system. Available oxygen from both the dissolved
oxygen and the hydrogen peroxide was measured using the Winkler
azide modification method (EPA Method No. 360.2)
24
-------
SECTION 8
RESULTS
FIELD STUDY
During the field investigation (8/89), hydrogen peroxide was
injected (11 gpm) into ground water at 750 mg/1. The water table
in the injection area was approximately 13.5-14.5 feet below
grade. There were several impervious areas (asphalt, concrete)
around the injection area that limited the locations where soil
gas samples could be collected. Nevertheless, numerous soil gas
samples were retrieved and analyzed for the concentration of
oxygen. This data was used to map the horizontal distribution of
oxygen as a function of depth (3, 6, 9-10 ft.) (Figures 11-13).
The concentration of oxygen in the unsaturated zone, as indicated
in these figures, was clearly greater than both atmospheric and
background soil oxygen concentrations, 20.9% and 20.7%,
respectively. This indicated that a significant amount of oxygen
was lost from the system and was not available for bioremediation
of hydrocarbon in the ground water. These figures also indicated
that the oxygen concentration increases with depth. Unlike the
injection area, the oxygen concentration in areas further
downgradient decreased with depth (Table 7). The X and Y
coordinates in Table 7 are based on a cartesian coordinate system
with the ordinate at injection well 1-3.
The concentration of oxygen in the headspace of the wells was
obtained by lowering the oxygen detector into the monitoring
wells. Although the concentration of oxygen in the monitoring
wells may not be representative of the concentration of oxygen in
the unsaturated zone, elevated oxygen concentrations demonstrate
the rapid rate of hydrogen peroxide decomposition. The same
general trend occurred in the wells as in the soil gas; the
oxygen concentration in the injection area increased with depth,
and the oxygen concentration downgradient of the injection area
decreased with depth.
The concentration of available oxygen in ground water
downgradient from the injection zone clearly indicated that
oxygen was being delivered to the system. The concentration of
available oxygen in downgradient sampling ports, plotted as a
function of time, are presented in Appendix A. It was difficult
to predict the rate at which hydrogen peroxide decomposed or the
fraction of injected oxygen that was liberated from the saturated
zone. This was largely due to the variability of the influent
hydrogen peroxide concentration as a function of time.
25
-------
Table 7 - Oxygen Concentration Profile Downgradient of the
Injection Area
Location^ '
Sample No. Xfft) Yfft) Depth (ft) Oxvaen
1 55 0 3 18.9
6 17.7
9 17.6
2 61 26 6 8.6
10 4.4
14 1.2
3 109 0 3.28 14.5
6.56 11.6
9.84 8.5
13.12 5.1
4 280 0 1 19.9
2 13.3
3 12.0
4 10.2
6 8.1
(1) X and Y coordinates indicate both downgradient and lateral
distances, respectively from injection wells.
26
-------
to
Figure 11. Percent Oxygen in the Unsaturated Zone,
In-Situ Bioremediation Pilot Study,
Aviation Gasoline Fuel Spill, (3 ft.)
Traverse City, Mich., (8/89)
60.0 -
Q)
(D
(D
O
C
D
Q
40.0 -
i \i i i i
20.0 -
20.0 40.0 60.0
Distance (feet)
60.0
40.0
- 20.0
0.0
80.0
-------
N)
03
Figure 12. Percent Oxygen in the Unsaturated Zone
In-Situ Bioremediation Pilot Study,
Aviation Gasoline Fuel Spill, (6 ft.)
Traverse City, Mich., (8/89)
60.0 -
CD
CD
CD
O
C
D
00
40.0 -
20.0
0.0
20.0 40.0 60.0
Distance (feet)
- 60.0
40.0
^ectio
Gro
flow
- 20.0
80.0
-------
Figure 13. Percent Oxygen in the Unsaturated Zone
In-Situ Bioremediation Pilot Study,
Aviation Gasoline Fuel Spill, (9-10 ft.)
Traverse City, Mich., (8/89)
60.0
(D
CD
40.0
CD
O
c
D
—
5
20.0
0.0
0.0
Injection wells
Ground water
flow direction-
Soil Gas at 9-10N
ow grade
i i i
i i i i i i i
60.0
40.0
20.0
20.0 40.0 60.0
Distance (feet)
o.o
80.0
-------
SECTION 9
DISCUSSION
Results of the field investigation support observations from
the laboratory study: hydrogen peroxide decomposed resulting in
the liberation of oxygen at a rate faster than the oxygen could
be utilized biologically and solubilized into aqueous phase.
Subsequently, oxygen gas was liberated from the ground water into
the unsaturated zone. The oxygen gas which was liberated into the
unsaturated zone could be considered an oxygen sink from the
biodegradation process in the saturated zone. This sink
introduces a considerable element of uncertainty in estimating
how much oxygen is actually delivered to the system and utilized
in the biodegradation process. Consequently, predicting the
amount of hydrocarbon degraded based on the amount of hydrogen
peroxide delivered to the system is inaccurate. Additionally, the
data from this study clearly dispells the concept that hydrogen
peroxide will only decompose as a function of the biological
demand.
Similar to the laboratory study, precautions were taken in
the field scale pilot study to minimize iron driven decomposition
reactions of hydrogen peroxide by introducing disodium phosphate
and potassium phosphate. Therefore, decomposition of hydrogen
peroxide was expected to be attributed mainly to catalase, (i.e.
enzymatic decomposition).
Two areas addressed in the laboratory study that were not
investigated in the field study are microbial inhibition due to
hydrogen peroxide and the stoichiometry of the degradation of
hydrocarbon based on the amount of oxygen consumed. An accurate
mass balance of oxygen and hydrocarbon is critical to make an
assessment of both processes. Neither an oxygen nor a hydrocarbon
mass balance could be accurately achieved at field scale.
Therefore these two areas could not be investigated. An important
note to make however, is that the conversion ratios found in the
column study represent minimum values due to the oxygen and
hydrocarbon mass balance of a carefully controlled system. In a
field scale system, it is speculated that the amount of oxygen
required will be significantly greater due to short circuiting of
the oxygen with repect to the contaminant plume.
The decision to use hydrogen peroxide as a supplemental
source of electron acceptor in bioremediation is an issue of
economics and safety. Historically, many bioremediation
practitioners have utilized hydrogen peroxide under the
assumption that it does not rapidly decompose and that the entire
amount of oxygen injected into the subsurface contributes to
bioremediation. Prior to selection of hydrogen peroxide as a
source of oxygen for bioremediation systems, alternative sources
should be considered. These alternatives include liquid oxygen
and gaseous oxygen either shipped in or produced on-site, i.e.
oxygen generation via molecular sieve. Additionally, when
30
-------
estimating the costs associated with using hydrogen peroxide,
consideration should be given to the fraction of oxygen that is
lost from the system.
31
-------
SECTION 10
REFERENCES
1. Amdurer, A., R. T. Fellman, J. Roetzer, and C. Russ.
Systems to Accelerate In Situ Stabilization of Waste
Deposits. Hazardous Waste Engineering Research Laboratory.
Office of Research and Development, U.S. EPA, Cincinnati,
OH. Sept. 1986.
2. Barker, J. F., G. C. Patrick, and D. Major. Natural
Attenuation of Aromatic Hydrocarbons in a Shallow Sand
Aquifer. Ground Water Monitoring Review 7:64-71. (1987).
3. Britton, L. N., and Texas Research Institute. Feasibility
Studies on the Use of Hydrogen Peroxide to Enhance
Microbial Degradation of Gasoline. Publication No. 4389,
API, Washington, D.C. May 1985.
4a. Brown, R. A., R. D. Norris, and R. L. Raymond. Oxygen
Transport in Contaminated Aquifers with Hydrogen Peroxide.
Proceedings, Petroleum Hydrocarbons and Organic Chemicals
in Ground Water - Prevention, Detection, and Restoration,
Nov. 1984, Houston, Texas, NWWA, Worthington, Ohio,
p. 421, 1984.
4b. Brown, R. A. and R. D. Norris. Field Demonstration of
Enhanced Bioreclamation. Proceedings of the Sixth National
Symposium and Exposition on Aquifer Restoration and Ground
Water Monitoring, May 19-22, 1986, Ohio State Univ.,
Columbus, Ohio, NWWA, Dublin, Ohio, p. 438-456.
5. Crow, W. L., E. P. Anderson, and E. M. Minugh. Subsurface
Venting of Vapors Emanating from Hydrocarbon Product on
Ground Water. Ground Water Monitoring Review v. 7, no.l,
p. 51-57. (1987).
6. EPA Methods for Chemical Analysis of Water and Waste.
(1979).
7. Harrison, E. M., and J. F. Barker. Sorption and Enhanced
Biodegradation of Trace Organics in a Groundwater
Reclamation Scheme - Gloucester Site, Ottawa, Canada. J.
Contam. Hydrol. l:A49-373. (1987).
8. Kampbell, D. Personal Communication. E.P.A. RSKERL, Ada,
OK. 1988.
9. Kovalic, J. M., and J. F. Klucsik. Loathing for Landfills
Sets Stage for Innovative Hazardous Waste Treatment
Technology. Haz. Materials & Waste Management
5:8,17-18. (1987).
32
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10. Leach, L. E., F. P. Beck, J. T. Wilson, and D. H. Kampbell.
Aseptic Subsurface Sampling Techniques for Hollow-Stem
Auger Drilling. Proceedings of the 2nd National Outdoor
Action Conference on Aquifer Restoration, May 23-26,
1988, NWWA, Dublin, Ohio, Vol. 1:31-51.
lla. Lee, M. D. and C. H. Ward. Microbial Ecology of a
Hazardous Waste Disposal Site: Enhancement of
Biodegradation. Paper Presented at 2nd International
Conference on Ground Water Quality Research, Oklahoma State
University, Tulsa, OK. 1984.
lib. Lee, M. D., and C. H. Ward. Biological Methods for the
Restoration of Contaminated Aquifers. Environ. Toxicol.
Chem. 4:743-750. (1985).
12. Powell, R. M., D. H. Kampbell, B. E. Bledsoe, R. W.
Callaway, J. T. Michalowski, S. A. Vandegrift, M. V.
White, and J. T. Wilson. Comparison of Methods to
Determine Bioremediation Oxygen Demand of a Fuel
Contaminated Aquifer. International J. of Environmental and
Analytical Chemistry, Vol. 34, p. 253-266, 1988.
13. Rose, S. and A. Long. Monitoring Dissolved Oxygen in
Ground Water: Some Basic Considerations. Ground Water
Monitoring Review 8:93-97. (1988).
14. Schumb, W. C., C. N. Satterfield, and R. L. Wentworth.
Hydrogen Peroxide. Reinhold Publishing Corp. NY. 1955.
15. Solar Universal Technologies, Inc., Coordination Meeting
Traverse City Bioremediation Projects Hydrogen Peroxide
Biodegradation Project (BIO I) Oklahoma City, OK., Feb. 3,
1989.
16. Spain, J. C., J. D. Milligan, D. C. Downey, and J. K.
Slaughter. Excessive Bacterial Decomposition Of H2O During
Enhanced Biodegradation. Ground Water, Vol. 27, No. 2,
(March-April 1989).
17a. Traverse Group, Inc., Quarterly Report, USCG/EPA Robert S.
Kerr Environmental Research Laboratory, Pilot Scale
Biodegradation Project USCG Air Station, Traverse City,
Michigan, March 1988.
17b. Traverse Group, Inc., Quarterly Report, USCG/EPA Robert S.
Kerr Environmental Research Laboratory, Pilot Scale
Biodegradation Project USCG Air Station, Traverse City,
Michigan, June 1988.
33
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17c. Traverse Group, Inc., Quarterly Report, USCG/EPA Robert S.
Kerr Environmental Research Laboratory, Pilot Scale
Biodegradation Project USCG Air Station, Traverse City,
Michigan, September 1988.
17d. Traverse Group, Inc., Quarterly Report, USCG/EPA Robert S.
Kerr Environmental Research Laboratory, Pilot Scale
Biodegradation Project USCG Air Station, Traverse City,
Michigan, December 1988.
17e. Traverse Group, Inc., Quarterly Report, USCG/EPA Robert S.
Kerr Environmental Research Laboratory, Pilot Scale
Biodegradation Project USCG Air Station, Traverse City,
Michigan, March 1989.
17f. Traverse Group, Inc., Quarterly Report, USCG/EPA Robert S.
Kerr Environmental Research Laboratory, Pilot Scale
Biodegradation Project USCG Air Station, Traverse City,
Michigan, June 1989.
18. Twenter, F. R., T. R. Cummings, and N. G. Grannemann. USGS
Water Resources Investigation Report, "Ground-Water
Contamination in East Bay Township, Michigan." Water
Resources Investigation Report 85-4064. 1985.
19. Vandegrift, S. A. and D. H. Kampbell. Gas Chromatographic
Determination of Aviation Gasoline and JP-4 Jet Fuel in
Subsurface Core Samples. J. of Chromatographic Sci.
26:566- 569. (1988).
20. Webster, W. C. In Situ Stabilization of Hazardous Wastes.
Haz. Materials & Waste Management 5:18-20. (1987).
21. Wilson, B. H. and B. E. Bledsoe. Biological Fate of
Hydrocarbons at an Aviation Gasoline Spill Site. Presented
at "Petroleum Hydrocarbons and Organic Chemicals in Ground
Water: Prevention, Detection and Restoration" Conference
and Exposition presented by NWWA and API. Houston, TX.
November 12-14, 1986.
22a. Wilson, J. T. and B. H. Wilson. Biotransformation of
Trichloroethylene in Soil. Appl. Environ. Microbiol. 49:
242-243. (1985).
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Technique. Ground Water Monitoring Review. 6:56-64. (1986)
22c. Wilson, J..T. and C. H. Ward. Opportunities for
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Hydrocarbons. Dev. Ind. Microbiol. 27:109-116. (1987).
34
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22d. Wilson, J. T., L. E.Leach, J. Michalowski, S. Vandergrift,
and R. Galloway. In-Situ Bioremediation of Spills from
Underground Storage Tanks: New Approaches For Site
Characterization, Project Design, and Evaluation of
Performance. EPA/600/2-89/042 July 1989.
23. Yaniga, P. M. and W. Smith. Aquifer Restoration via
Accelerated In Situ Biodegradation of Organic Contaminants.
The 7th National Conference on Management of Uncontrolled
Hazardous Waste Sites, Dec. 1-3, 1986, Wash. D.C.,
Hazardous Materials Controls Research Institute, p. 333-
338.
35
-------
SECTION 11
APPENDIX
Field Data - Available Oxygen in Ground Water
FIGURES
Figure A.I - Available Oxygen, Sampling Port 7A
Figure A.2 - " " 7B
Figure A.3 - " " 7C
Figure A.4 - " "31
Figure A.5 - " " 48A
Figure A.6 - " " 50B
Figure A.7 - " " 50C
Figure A.8 - " "62
Figure A.9 - " " 83A
Figure A.10 - " " 83B
Figure A.11 - » " 83C
Figure A.12 - " " 108
PAGE
37
38
39
40
41
42
43
44
45
46
47
48
36
-------
CO
I
I
I
Fig. A.1 - Available Oxygen, Sampling Port 7A
Traverse City, Mich., Aviation Gas Spill
B level 2
level 3
TIME (days)
o level 4
level 5
x level 6
-------
u
03
0>
O)
I
280
Fig. A.2 - Available Oxygen, Sampling Port 7B
Traverse City, Mich., Aviation Gas Spill
100.0
200.0
300.0
400.0
H level 2
level 3
TIME (days)
o level 4
level 5
x level 6
-------
CO
vo
I
1
260
Fig. A.3 - Available Oxygen, Sampling Port 7C
Traverse City, Mich., Aviation Gas Spill
o.o
100.0
200.0
300.0
400.0
level 2
TIME (days)
level 3 o level 4
level 5
level 6
-------
g
1
o
I
•(3
90 -r
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10 -
Fig. A.4 - Available Oxygen, Sampling Port 31
Traverse City, Mich., Aviation Gas Spill
100.0
level 2
200.0
TIME (days)
+ level 3
300.0
400.0
o level 4
-------
-0)
O)
.2
I
1
Fig. A.5 - Available Oxygen, Sampling Port 48A
Traverse City, Mich., Aviation Gas Spill
60.0
10.0
0.0
D level 1
+ level 2
TIME (days)
o level 3
A level 4
-------
to
0)
_
3
I
Fig. A.6 - Available Oxygen, Sampling Port SOB
Traverse City, Mich., Aviation Gas Spill
50.0
0.0
a level 1
100
+ level 2
200
TIME (days)
o level 3
300
400
A level 4
x level 5
-------
U)
0>
O)
.
i
I
Fig. A.7 - Available Oxygen, Sampling Port 50C
v.
Traverse City, Mich., Aviation Gas Spill
70.0
60.0 -
50.0 -
40.0 -
30.0 -
20.0 -
10.0 -
0.0
100
200
300
400
B level 1
+ level 2
TIME (days)
o level 3
A level 4 x levels
-------
0)
I
<£
3
I
Fig. A.8 - Available Oxygen, Sampling Port 62
Traverse City, Mich., Aviation Gas Spill
40.0
35.0 -
30.0 -
25.0 -
20.0 -
15.0 -
10.0 -
100
200
300
400
m level 2
TIME (days)
+ level 3
o level 4
-------
Fig. A.9 - Available Oxygen, Sampling Port 83A
Traverse City, Mich., Aviation Gas Spill
45.0
40.0 -
35.0 -
30.0 -
25.0 -
20.0 -
15.0 -
10.0 -
5.0 -
0.0
100
B level 2
200
TIME (days)
+ level 3
300
400
o level 4
-------
45.0
Fig. A.10 - Available Oxygen, Sampling Port 83B
Traverse City, Mich., Aviation Gas Spill
0.0
100
level 2
200
TIME (days)
+ level 3
300
400
o level 4
-------
0)
O)
i
'S3
40.0
35.0 -
30.0 -
25.0 -
20.0 -
15.0 -
10.0 -
5.0 -
0.0
Fig. A.11 - Available Oxygen, Sampling Port 83C
Traverse City, Mich., Aviation Gas Spill
400
TIME (days)
+ level 3
o level 4
-------
90tOO/6SI-8f ^ 0661 :30lddO DNIiNIHd 1N3WNU3A03
Available Oxygen (mg/I)
3
to
I
CO
m
w
O
I
ar
I.
------- |