v>
United States
Environmental Protection
Agency
                       Office of Research and
                       Development
                       Washington, DC 20460
Office of Solid Waste and
Emergency Response
Washington, DC 20460
EPA 540 R-95 534a
September 1995
Manual
Bioventing Principles and
Practices
Volume I: Bioventing Principles

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                                                 Figures
Figure                                                                                              Page

1-1    Hydrocarbon distribution at a contaminated site	1
1-2   Schematic of a typical bioventing system	       	2
2-1    Historical perspective on the development of bioventing.      	5
2-2   Locations of Bioventing Initiative sites	7
3-1    Distribution of fine-grained soils (silt and clay) at Bioventing Initiative sites	       .... 11
3-2   Sorption isotherms	13
3-3   Relationship between sorbed contaminant concentrations and vapor- or aqueous-phase
      concentrations	14
3-4   Soil moisture content measurements at Bioventing Initiative sites	16
3-5   Direct correlation between oxygen utilization rates and soil moisture content at Bioventing
      Initiative sites       	16
3-6   Oxygen and carbon dioxide concentrations before and after irrigation at Twentynine Palms, California   17
3-7   Soil pH measurements at Bioventing Initiative sites. .  .      	18
3-8   Correlation between oxygen utilization rate and soil pH at Bioventing Initiative sites	18
3-9   Soil temperature versus oxygen  utilization and biodegradation rate at Site 20,  Eielson AFB, Alaska. . .  .19
3-10  TKN measurements at Bioventing  Initiative sites	20
3-11  Correlation between oxygen utilization rate and TKN at Bioventing Initiative sites	21
3-12  Total phosphorus measurements at Bioventing Initiative sites	21
3-13  Correlation between oxygen utilization rate and total phosphorus at Bioventing Initiative sites	21
3-14  Iron concentration measurements at Bioventing Initiative sites	21
3-15  Correlation between oxygen utilization rates and iron content at Bioventing Initiative sites	22
3-16  Relationship between contaminant physicochemical properties and potential for bioventing     	23
3-17  Relationship between contaminant pressure and aerobic biodegradability	24
3-18  Results of soil analysis before and after venting from Plot V2 at Tyndall AFB, Florida	     	  25
3-19  Contaminant distribution at Bioventing Initiative sites	25
4-1   Cumulative hydrocarbon removal and the effect of moisture and nutrient addition at
      Site 914, Hill AFB, Utah	        	28
4-2   Results of soil analysis before and after treatment at Site 914, Hill AFB, Utah	29
4-3   Cumulative percentage of hydrocarbon removal and the effect of moisture and nutrient
      addition at Tyndall AFB, Florida	           	30
4-4   Schematic showing locations of soil gas monitoring points, surface monitoring points, and
      injection wells at Site 20, Hill AFB, Utah   	31
4-5   Geologic cross-section showing  known geologic features and soil TPH concentrations (mg/kg) at
      Site 280,  Hill AFB, Utah	         	32
4-6   Site average initial and final BTEX soil sample results at Site 280, Hill  AFB, Utah	33
4-7   Site average initial and final TPH soil sample  results at Site 280, Hill AFB, Utah	34

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                                          Figures (continued)

Figure                                                                                                Page

4-8   Cross-section showing geologic features and typical construction details of the active
      warming test plot, Site 20, Eielson AFB, Alaska	      	35
4-9   Soil temperature in four test plots and the background area at Site 20, Eielson AFB, Alaska	  35
4-10  Biodegradation rates in four test plots at Site 20, Eielson AFB, Alaska	36
4-11  Site average initial and final BTEX soil sample results at Site 20, Eielson AFB, Alaska	 37
4-12  Site average initial and final TPH soil sample results at Site 20, Eielson  AFB, Alaska	37
4-13  Hydrogeologic cross-section of the Fire Training Area, Battle Creek, ANGB, Michigan	38
4-14  Initial and final soil gas concentrations at the Fire Training Area, Battle Creek, Michigan	39
4-15  Initial and final soil concentrations at the Fire Training Area, Battle Creek,  Michigan	40
5-1   Soil gas BTEX concentrations at Bioventing Initiative sites: initial and 1-year data	42
5-2   Soil gas TPH concentrations at Bioventing Initiative sites: initial and 1-year data	42
5-3   Soil BTEX concentrations at Bioventing Initiative sites: initial and  1-year data	42
5-4   Soil TPH concentrations at Bioventing Initiative sites: initial and 1-year data	43
5-5   Average soil and soil gas BTEX and TPH concentrations at Bioventing Initiative sites: initial
      and 1 -year data	43
5-6   Initial and final soil sampling results at Site 3, Battle  Creek ANGB, Michigan	43
5-7   Average BTEX concentrations  at Bioventing Initiative sites	44
5-8   Use of piecewise analysis of oxygen utilization data from Site FSA-1, AFP 4,  Texas.  .       	46
5-9   Oxygen utilization rates, oxygen to carbon dioxide rate ratios, element concentrations,
      moisture content, pH, and alkalinity site average correlation scatterplot	47
5-10  Oxygen utilization rates, oxygen to carbon dioxide rate ratios, contaminant concentrations,
      temperature, and moisture content site average correlation scatterplot	48
5-11  Oxygen utilization rates, oxygen to carbon dioxide rate ratios, particle size, moisture  content,
      and soil gas permeability site average correlation scatterplot	49
5-12  Element concentrations and particle size site average correlation scatterplot	50
5-13  Contaminant concentrations and particle size site average correlation scatterplot	51
5-14  pH, alkalinity, and particle size  site average correlation scatterplot	52
5-15  Actual versus model-predicted  oxygen utilization rates	54
5-16  Variation of pH and the effect on oxygen utilization to carbon dioxide rate  ratio based on model
      predictions with average levels of other parameters	55
5-17  Soil gas permeability, moisture content, and particle  size site average correlation scatterplot	56
5-18  Variation of clay and the effect  on soil gas permeability based on model predictions	57
                                                     VI

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                                                 Tables
Table                                                                                             Page

2-1   Oxygen Requirements Based on Supplied Form	3
2-2   Summary of Reported in Situ Respiration Rates and Bioventing Data	8
3-1   Values for Key Properties of Select Petroleum Hydrocarbons	13
4-1   Cost Analysis of Soil Warming Techniques at Site 20, Eielson AFB, Alaska	36
5-1   Data Parameters Included in the Statistical Analyses	45
5-2   Parameters That Distinguish the Seven Sites With High Oxygen Utilization Rates
      From the Remaining Sites	46
B-1   Bioventing Initiative Results: Soil Chemical Characterization	67
B-2   Preliminary Bioventing Initiative Results: Average BTEX and TPH Soil Concentrations	70
B-3   Preliminary Bioventing Initiative Results: BTEX and TPH Soil Gas Concentrations	74
B-4   In Situ Respiration Test Results at Bioventing Initiative Sites	78
                                                   VII

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                                         List of Examples
Example                                                                                        Page

2-1    Calculation of Air-Saturated Water Mass That Must Be Delivered To Degrade Hydrocarbons	  3
3-1    Moisture Content Change During Air Injection and Water Generated During Biodegradation	17
3-2    Calculation of the van't Hoff-Arrhenius Constant From Site Data	19
3-3    Estimation of Nutrient Requirements in Situ	20
                                                VIII

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                                   List of Symbols and Acronyms
AFB
AFCEE

AL/EQ

ANGB
AVGAS
BTEX

cfm
DNAPL
EPA

LNAPL
NAS
NLIN
PAH
PCB
RD&A

SAS
SVE
TCE
TKN
TPH
TVH
UST
VOC
Cs
Air Force Base
U.S. Air Force Center for
Environmental Excellence
Armstrong Laboratory Environics
Directorate
Air National Guard Base
aviation gas
benzene, toluene, ethylbenzene,
and xylenes
cubic feet per minute
dense nonaqueous phase liquid
U.S. Environmental Protection
Agency
less dense nonaqueous phase liquid
Naval Air Station
nonlinear regression procedure
polycyclic aromatic hydrocarbon
polychlorinated biphenyl
Research, Development, and
Acquisition
Statistical Analysis System
soil vacuum extraction
trichloroethylene
total Kjeldahl nitrogen
total petroleum hydrocarbon
total volatile hydrocarbon
underground storage tank
volatile organic carbon
quantity sorbed to the solid matrix
cw
k
kd
KS
kT

MW
Pv

R
t
Tabs
%
X
Y
volumetric concentration in the
vapor phase
saturated vapor concentration
volumetric concentration in the
aqueous phase
activation energy
organic carbon fraction
maximum rate of substrate utilization
endogenous respiration rate
baseline biodegradation rate
biodegradation rate
sorption coefficient
octanol/water partition coefficient
Monod half-velocity constant
temperature-corrected
biodegradation rate
molecular weight
vapor pressure of pure contaminant
at temperature T
gas constant
radius of influence
concentration of the primary
substrate (contaminant)
solubility in water
time
absolute temperature (°K)
mole fraction
concentration of microorganisms
cell yield
                                                  IX

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Conversion Factors
To convert . . .
cubic feet
cubic feet
cubic inches
cubic yards (tons)
cubic yards (tons)
darcy
darcy
degrees Fahrenheit
degrees Fahrenheit
feet
horsepower
inches
kilocalories
millimeters of mercury (°C)
parts per million
parts per million
pounds
pounds per square inch
square inches
tons
U.S. gallons
to...
cubic meters
liters
cubic centimeters
cubic meters
kilograms
square centimeter
square meter
degrees Celsius
degrees Kelvin
meters
kilowatts
centimeters
joules
Pascals
milligrams per liter
grams per liter
kilograms
kiloPascals
square centimeters
metric tons
liters
multiply by ...
0.02831685
0.03531
610.2
0.7646
907.1843
9.869233 x10'9
9.869233 x10'13
toC = (t°F-32)/1.8
t.K = (t°F - 523.67)71 .8
0.3048
0.7457
2.54
4,186.8
133.322
1
1,000
0.45354237
6.895
6.4516
0.90718474
3.785

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                                  Acknowledgments
This manual was prepared by Andrea Leeson and Robert Hinchee of Battelle Memorial Institute,
Columbus, Ohio, for the U.S. Environmental Protection Agency's (EPA's) National Risk Management
Research Laboratory, Cincinnati, Ohio; the U.S. Air Force Environics Directorate of the Armstrong
Laboratory, Tyndall AFB,  Florida; and the U.S. Air Force Center for Environmental  Excellence,
Technology Transfer Division, Brooks AFB, Texas.

The project  managers for this manual were Lt. Colonel Ross Miller, U.S. Air  Force Center for
Environmental Excellence; Gregory Sayles, EPA National Risk Management Research Laboratory;
and Catherine Vogel, U.S. Air Force Environics Directorate, Armstrong Laboratory. These individuals
also contributed to the content of the manual.

The manual  was peer reviewed by:

  Ryan Dupbnt, Utah State University
  Chi-Yuan Fan, U.S. EPA National  Risk Management Research Laboratory
  Paul Johnson, Arizona State University
  Jack van Eyck, Delft Geotechnic
Acknowledgments are also given to  the following individuals who contributed to this document:

  Bruce Alleman, Battelle Memorial  Institute
  Douglas Downey, Parsons Engineering Science
  Gregory Headington, Battelle Memorial Institute
  Jeffrey Kittel, Battelle Memorial Institute
  Priti Kumar,  Battelle Memorial Institute
  Say Kee Ong, Iowa State University
  Lawrence Smith, Battelle Memorial Institute

Eastern Research Group,  Inc., Lexington, Massachusetts, copy edited and prepared camera-ready
copy of this manual.
                                           XI

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This document is a product of the bioventing research and development efforts sponsored by the
U.S. Air Force Armstrong Laboratory, the  Bioventing Initiative sponsored by the U.S. Air Force
Center for Environmental Excellence (AFCEE) Technology Transfer Division, and the Bioremedia-
tion Field Initiative sponsored by the U.S. Environmental Protection Agency (EPA).
The Armstrong Laboratory Environics Directorate (AL/EQ), an element of the Air Force Human
Systems Center, began its bioventing research and development program in 1988 with a study at
Hill Air Force Base (AFB), Utah.  Follow-up efforts included field research studies at Tyndall AFB,
Florida; Eielson AFB, Alaska; and F.E. Warren AFB, Wyoming, to monitor and  optimize process
variables. The results of these research efforts led to the Bioventing Initiative and are discussed in
this document.
The AFCEE's Bioventing  Initiative has involved  conducting field treatability studies to evaluate
bioventing feasibility at over 125 sites throughout the United States. At those sites where feasibility
studies produced positive results, pilot-scale bioventing systems were installed and operated for 1
year. Results from these pilot-scale studies culminated in the production of this document.

EPA's Bioremediation Field Initiative was established to provide EPA and state project managers,
consulting engineers, and industry with timely information regarding  new developments in the
application of bioremediation at hazardous waste sites. This program has sponsored field research
to enable EPA laboratories to more fully document newly developing bioremediation technologies.
As part of the  EPA Bioremediation Field Initiative, EPA has contributed to the Air Force Bioventing
Initiative in the development of the test plan for conducting the pilot-scale bioventing studies and
assisted in the development of this manual.

The results from bioventing research  and development efforts and from the pilot-scale bioventing
systems have been used to produce this two-volume manual. Although this design manual has been
written based on extensive experience with petroleum hydrocarbons (and thus, many examples use
this contaminant), the concepts here should be applicable to any aerobically biodegradable com-
pound. The manual provides details on bioventing principles; site characterization; field treatability
studies; system design, installation, and operation;  process monitoring; site closure; and optional
technologies to combine with bioventing if warranted. This first volume describes basic principles
of bioventing. The second volume focuses on bioventing design and process monitoring.
                                           XII

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                                               Chapter 1
                                             Introduction
Bioventing is the process of aerating soils to stimulate
in  situ biological activity and promote  bioremediation.
Bioventing typically is applied in situ to the vadose zone
and is applicable to any chemical that can be aerobically
biodegraded but to date  has primarily been imple-
mented at petroleum-contaminated sites. Through the
efforts of the U.S. Air Force Bioventing Initiative and the
U.S. EPA Bioremediation Field Initiative, bioventing has
been implemented at over 150 sites and has emerged
as one of the most cost-effective, efficient technologies
currently available for vadose zone remediation of pe-
troleum-contaminated sites. This  document is a culmi-
nation of the experience gained  from these sites and
provides specific guidelines on the principles and prac-
tices of bioventing.

Much of the hydrocarbon residue at a fuel-contaminated
site  is found in  the vadose zone soils,  in the capillary
fringe, and  immediately below the water table (Figure
1-1). Seasonal water table fluctuations typically spread
residues in  the area immediately above and below the
water table. In the past, conventional physical treatment
involved pump and treat systems, where ground water
was  pumped  out of the  ground, treated, then  either
  Water  Residual
  Table saturation
discharged or reinjected. Although useful for preventing
continued migration  of  contaminants,  these systems
rarely achieved typical cleanup goals. Bioventing sys-
tems are designed to remove the contaminant source in
the vadose zone, thereby preventing future and/or con-
tinued contamination of the ground water.
Atypical bioventing system is illustrated in Figure 1-2.
Although bioventing  is related to  the process  of soil
vacuum extraction (SVE), these processes have differ-
ent primary objectives. SVE is designed and operated
to maximize the  volatilization of low-molecular-weight
compounds, with some  biodegradation occurring.  In
contrast, bioventing is designed to maximize biodegra-
dation of aerobically biodegradable compounds, regard-
less of their molecular weight, with some volatilization
occurring. The major distinction between  these tech-
nologies is that the objective of SVE (also called soil
venting)  is to optimize removal by volatilization, while
the objective of bioventing is to optimize biodegradation
while  minimizing volatilization and capital and utility
costs. Although both technologies involve venting of air
though the subsurface, the different objectives result in
different design and operation of the remedial systems.
The following chapters provide an overview of the prin-
ciples of bioventing in relation to physical, chemical, and
microbial processes occurring in the field. An overview
of the  development  of bioventing, including develop-
ment of the Bioventing Initiative, is provided as a basis
for the  data  presented in  this document. Data  from
Bioventing Initiative sites are used throughout this docu-
ment to illustrate principles of bioventing as determined
from field testing.
Figure 1-1. Hydrocarbon distribution at a contaminated site.

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                                  0
                                                 Blodegradatlon
                                                   of Vapors
                                              Soil Gas
                                              Monttoring
                                                                                 Low Rate
                                                                                Air Injection
                                                                             i
                                                                                          Contaminated Soil
Figure 1-2.   Schematic of a typical bioventing system.

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                                              Chapter 2
                                   Development of Bioventing
This chapter provides a framework for the document, de-
scribing this development and structure of the Bioventing
Initiative,  and ultimately,  of this document. This chapter
provides an overview of bioventing, covering oxygen sup-
ply in situ (the dominant issue in the evolution of biovent-
ing), early bioventing studies that led to development of the
Bioventing Initiative, final structure of the treatability stud-
ies and bioventing system design used for the Bioventing
Initiative,  and finally, emerging techniques that are being
investigated as modifications to the conventional biovent-
ing design described in this document.

2.1    Oxygen Supply to Contaminated
       Areas

One driving force behind the development of bioventing
was the  difficulty  of delivering oxygen in situ. Many
contaminants, especially the petroleum hydrocarbons
found  in  fuels, are biodegradable in the presence of
oxygen.  Traditionally, enhanced bioreclamation proc-
esses  used water to carry oxygen  or an  alternative
electron acceptor to the contaminated zone. This proc-
ess was common, whether the contamination was pre-
sent in the ground water or  in the  unsaturated zone.
Media  for adding oxygen to contaminated areas have
included pure-oxygen-sparged water, air-sparged water,
hydrogen peroxide, and air.

In all cases where water is used, the solubility of oxygen
is the limiting factor. At standard conditions, a maximum
of 8 mg/L to 10 mg/L of oxygen can be obtained in water
when aerated, while 40 mg/L to 50 mg/L can be obtained
if  sparged with pure oxygen, and up to  500 mg/L of
oxygen theoretically can be supplied  using 1,000 mg/L
of hydrogen peroxide. The stoichiometric  equation
shown in Equation 2-11 can  be  used to  calculate the
quantity of water that must be delivered to provide suf-
ficient oxygen for biodegradation.

           C6H14 + 9-502 -> 6CO2 + 7H2O    (Eq 2_^ j


An example of calculating the mass of water that must
be delivered for hydrocarbon degradation is shown in
Example 2-1. Table 2-1 summarizes oxygen  require-
ments based on the supplied form of oxygen.
Example 2-1. Calculation of Air-Saturated Water Mass
That Must Be Delivered To  Degrade Hydrocarbons:
Based on Equation 2-1 , the stoichiometric molar ratio of
hydrocarbon to oxygen is 1:9.5. Or, to degrade 1 mole
of hydrocarbons,  9.5 moles  of oxygen must  be con-
sumed. On a mass basis:
                   1 mole O2    86 g C6H14
                             /\
     1  mole C6H14
     9.5 molesO2 ~  32 g O2  ~ 1 moleC6H14

              86 g C6H14 _ 1 g C6H14
               304 gO2  ~ 3.5 gO2

Given an average concentration  of 9 mg/L of oxygen
dissolved in water, the amount of air-saturated water
that must be delivered to degrade 1 g of hydrocarbon is
calculated as follows:

           3.5 g O2 required     390 L H2O
          9mgO2      1 g
          1LH2O   1,000mg

or, to degrade 1 Ib:

    390 L H2O   1 gal   1,000 g
     1 g C6H14 X 3.8 L X 2.2 Ib
                               1 9 C6H14
                                47,000gal H2O
                                  1 Ib C6 H14
Table 2-1. Oxygen Requirements Based on Supplied Form
Oxygen Form
                                        Volume to
                        Oxygen         Degrade 1  Ib
                   Concentration In H2O   Hydrocarbon
1 See Section 3.2 for development of this equation.
Air-saturated H2O     8 mg/L to 10 mg/L


Oxygen-saturated H2O 40 mg/L to 50 mg/L

Hydrogen peroxide    Up to 500 mg/L


Air                NA (21% vol./vol. in air)  170 ft3 (4,800 L)
NA = not applicable.
                                      47,000 gal
                                      (180,000 L)

                                      11,000 gal
                                      (42,000 L)

                                      1,600 gal
                                      (6,100 L)

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Because of the low aqueous solubility of oxygen, hydro-
gen peroxide has been tested as an oxygen source in
laboratory studies and at several field sites (Hinchee et
al., 1991 a; Aggarwal etal., 1991; Morgan and Watkinson,
1992). As shown in Table 2-1, if 500 mg/L of dissolved
oxygen can be  supplied via hydrogen peroxide, the
mass of water that must be delivered decreases by more
than an order of magnitude. Initially, these calculations
made the use of hydrogen peroxide appear to  be an
attractive alternative to injecting air-saturated water.

Hydrogen peroxide is miscible in water and decomposes
to release water and oxygen as shown in Equation 2-2:
                                          (Eq. 2-2)
Many substances commonly present in ground water
and soil act as  catalysts for the decomposition of
peroxide. Important among these are aqueous spe-
cies of  iron and  copper as well as the  enzyme
catalase (Schumb et al., 1955), which has significant
activity in situ (Spain et al., 1989). If the rate of oxygen
formation from hydrogen peroxide decomposition ex-
ceeds the  rate of microbial oxygen utilization, gase-
ous oxygen may form because of its limited aqueous
solubility. Gaseous oxygen  may form bubbles, which
may not be  transported efficiently in ground water,
resulting in ineffective oxygen delivery.

Phosphate is commonly used in nutrient formulations to
decrease the rate of peroxide decomposition in ground-
water applications  (Britton,  1985). The  effectiveness,
however, of phosphate addition in stabilizing peroxide
injected into an aquifer has not been well established,
and different researchers have reported conflicting re-
sults (American Petroleum Institute, 1987; Brown et al.,
1984; Downey  et al., 1988;  EPA, 1990; Morgan and
Watkinson, 1992).

Hinchee et al. (1991 a) conducted  a field experiment to
examine the effectiveness of  hydrogen peroxide as an
oxygen source for in situ biodegradation. The study was
performed at a JP-4 jet fuel-contaminated site at Eglin
AFB, Florida. Site soils consisted of fine- to coarse-
grained quartz sand with ground water at a depth of 2 ft
to 6 ft (0.61 m to 1.8 m). Previous studies by Downey et
al. (1988) and Hinchee et al. (1989) at the same site had
shown that rapid  decomposition of hydrogen peroxide
occurred, even with the  addition  of  phosphate as  a
peroxide  stabilizer.  In subsequent studies, hydrogen
peroxide  was injected at a concentration of 300 mg/L,
both with and without the addition  of a phosphate-con-
taining nutrient solution. As in previous studies, hydro-
gen peroxide decomposition was rapid,  resulting in poor
distribution  of oxygen in ground water. Addition of the
phosphate-containing nutrient solution did not appear to
improve hydrogen peroxide stability.
Other attempts have been made to use hydrogen per-
oxide as an oxygen source.  Although  results  indicate
better hydrogen  peroxide stability than achieved by
Hinchee et al. (1989), researchers concluded that most
of the hydrogen  peroxide decomposed rapidly (EPA,
1990). Some degradation of aromatic hydrocarbons ap-
pears to have occurred; however,  no  change in  total
hydrocarbon  contamination levels was detected in the
soils (Ward, 1988).
In contrast to hydrogen peroxide use, when air is used
as an oxygen source in unsaturated soil, 170 ft3 (4,800
L) of air must be delivered  to  provide the minimum
oxygen required to degrade 1 Ib (0.45 kg) of hydrocar-
bon (Table 2-1). Because costs associated with water-
based delivery of oxygen can  be relatively high, the use
of gas-phase delivery significantly reduces the  cost as-
sociated with supplying oxygen.2
An additional advantage of using a gas-phase  process
is that gases have greater diffusivity than liquids. At
many sites, geological heterogeneities  cause fluid that
is pumped through the formation to be channeled  into
.more permeable pathways (e.g., in an alluvial soil with
interbedded sand and clay, all fluid flow initially takes
place in the sand). As a result, oxygen must be delivered
to the less permeable clay lenses through diffusion. In
a gaseous system (as found  in unsaturated soils),  this
diffusion can  be expected to take place at rates at least
three orders of magnitude greater than rates in a liquid
system (as is found in saturated soils).  Although diffu-
sion cannot realistically be expected to aid significantly
in water-based bioreclamation, diffusion of oxygen  in a
gas-phase system is a significant  mechanism  for oxy-
gen delivery to less permeable zones.
Given the advantages of using air rather than water as
the oxygen source, several investigators began explor-
ing the feasibility of an air-based oxygen supply system
as a remedial option. A summary of the results  of these
investigations is presented in  the following section.

2.2    Bioventing Research and
       Development

Figure 2-1  provides a historical perspective of bioventing
research and development. To the authors' knowledge, the
first documented  evidence of unsaturated-zone biode-
gradation  resulting from forced aeration was reported
by the Texas  Research  Institute, Inc., in a 1980 study
for the American Petroleum Institute. A large-scale
model experiment was conducted  to test the effective-
ness  of a surfactant treatment to enhance the recovery
of spilled gasoline. The  experiment accounted for only
8 gal  (30  L)  of  the 65 gal  (250  L) originally spilled
and  raised questions about  the fate of the gasoline.
2 See Chapter 5 of Volume II for a comparison of costs associated
  with hydrogen peroxide use versus air (bioventing).

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                     1984
1985   1986
                                         1987
                    1988    1989    1990    1991
1992
1993
Figure 2-1. Historical perspective on the development of bioventing.
Subsequently, a column study was conducted to deter-
mine a diffusion coefficient for soil venting. This column
study evolved  into a  biodegradation study  in which
researchers concluded that  as  much  as 38 percent
of the fuel hydrocarbons were biologically mineralized.
Researchers also  concluded that venting  not  only
would  remove  gasoline  by physical means  but  also
would enhance microbial activity and promote biodegra-
dation of the gasoline (Texas Research Institute, 1980,
1984).

To the authors'  knowledge, the  first actual field-scale
bioventing experiments were conducted  by Jack van
Eyk for Shell Research. In 1982,  at van Eyk's direction,
the Shell Laboratory in Amsterdam, The  Netherlands,
initiated a series of experiments to investigate the effec-
                          tiveness of bioventing for treating hydrocarbon-contami-
                          nated soils. These studies were reported in a series of
                          papers  (Anonymous, 1986; Staatsuitgeverij, 1986; van
                          Eyk and Vreeken, 1988, 1989a, and 1989b).

                          Wilson  and Ward (1986) suggested that using air as a
                          carrier for oxygen could be 1,000 times more efficient
                          than using water, especially in deep, hard-to-flood  un-
                          saturated  zones. They made the connection between
                          oxygen supply via soil venting  and biodegradation  by
                          observing that "soil  venting uses the same principle to
                          remove volatile components of the  hydrocarbon." In a
                          general overview of the soil venting process, Benned-
                          sen et  al. (1987) concluded that soil venting provides
                          large quantities of oxygen to the unsaturated zone, pos-
                          sibly stimulating aerobic degradation. They suggested

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that  water and  nutrients also would  be required for
significant degradation and encouraged additional in-
vestigation into this area.

Biodegradation enhanced by soil venting has been ob-
served at several field sites. Investigators claim that at
a soil venting site for remediation of gasoline-contami-
nated soil, significant biodegradation occurred (meas-
ured by a temperature  rise)  when  air was supplied.
Investigators pumped pulses of air through a pile  of
excavated soil  and observed  a  consistent rise in tem-
perature, which they attributed to biodegradation. They
claimed that the pile was  cleaned up during the summer
primarily by biodegradation (Conner, 1989). They did
not,  however, control for natural volatilization from the
aboveground pile, and insufficient data were published
to critically review their biodegradation claim.

Researchers at Traverse  City,  Michigan, observed a de-
crease in the toluene concentration in unsaturated zone
soil  gas, which  they  measured  as an indicator of fuel
contamination in the unsaturated zone. They assumed that
advection had not occurred and attributed the toluene loss
to biodegradation. The investigators concluded that be-
cause toluene concentrations decayed near the oxygen-
ated  ground  surface,  soil  venting  is  an attractive
remediation alternative for biodegrading light volatile hy-
drocarbon spills (Ostendorf and Kampbell, 1989).

The U.S. Air Force initiated its research and development
program in bioventing in 1988 with a study at Site 914,3
Hill AFB, Utah. This site  was  initially operated as  a soil
vapor extraction unit  but was modified to a bioventing
system  after 9 months of operation because of evidence
that  biodegradation was occurring and also as part of an
attempt to decrease costs by reducing off-gas. Moisture
and  nutrient addition were studied at this site; however,
although moisture addition appeared to improve biodegra-
dation, nutrient addition did not. Final soil sampling dem-
onstrated that  benzene,  toluene,  ethylbenzene,  and
xylenes (BTEX)  and total petroleum hydrocarbon (TPH)
levels decreased to below regulatory levels, and this site
became the first Air Force site that was closed through in
situ bioremediation. This  study revealed that bioventing
had great potential for remediating JP-4 jet fuel-contami-
nated soils. The study also showed, however, that addi-
tional research  would be  needed before the technology
could be routinely applied in the field.

Following the Site 914, Hill AFB study, a more controlled
bioventing study was completed at Tyndall AFB,4 Flor-
ida. This study was designed to monitor specific process
variables and the subsequent effect on biodegradation
of hydrocarbons. Several important findings  resulted
from this study, including the effect of air flow rates on
removal by biodegradation and volatilization, the effect
of temperature on biodegradation rates, the lack of mi-
crobial stimulation  from the addition of moisture and
nutrients, and the importance of natural nitrogen supply
through nitrogen fixation.  In addition, initial and final
contaminant  measurements showed over 90  percent
removal of BTEX. This study was short-term but illus-
trated the effectiveness of bioventing.

The studies  conducted at Hill  and Tyndall AFBs pro-
vided valuable information on bioventing. These stud-
ies  also showed,  however, that long-term,  controlled
bioventing studies were necessary to fully evaluate and
optimize the  technology. In 1991, long-term bioventing
studies were initiated at Site 280, Hill AFB,  Utah, and
Site 20j Eielson AFB, Alaska.5 These studies were joint
efforts between EPA and the U.S. Air Force Envjronics
Directorate of the Armstrong Laboratory. These studies
have involved intensive monitoring of several process
variables,  including the  effect  of soil temperature on
biodegradation rates, surface emission analyses, and
optimization of flow rate.

Based on  the success of  these previous  studies, in
1992, AFCEE initiated the Bioventing Initiative, where
pilot-scale bioventing systems were installed at 125 con-
taminated  sites  located  throughout  the continental
United States and in Hawaii, Alaska, and Johnston Atoll
(Figure 2-2). Sites varied  dramatically  in climatic and
geologic conditions. Contaminants typically were petro-
leum hydrocarbons from  JP-4 jet  fuel,  heating oils,
waste oils, gasoline, and/or diesel;  however, some fire
training areas also  were studied where significant con-
centrations of solvents were present. This manual rep-
resents the culmination of this study and is the product
of the data collected from these sites and other projects.

In addition to these studies,  other bioventing studies have
been conducted by several researchers. A summary of
data from some sites where bioventing has been  applied
is shown in Table 2-2.6 The scale of application and con-
taminant type is given, as well as the biodegradation rate,
if known. The studies listed in Table 2-2 are limited to those
where the study was conducted in situ, where no inoculum
was added to site soils, and where flow rates were opti-
mized for biodegradation, not volatilization. A distinction
must be made between bioventing and SVE systems.
Bioventing systems operate at flow rates optimized for
biodegradation, not volatilization, although some volatili-
zation  may occur. SVE systems operate at  flow rates
optimized for volatilization, although some biodegrada-
tion may occur. Therefore, flow  rates and configurations
of the two systems are significantly different.
3 See Section 4.1 for a detailed discussion of this study.

4 See Section 4.2 for a detailed discussion of this study.
5 See Sections 4.3 and 4.4, respectively, for a detailed discussion of
 these studies.
6 Only select Bioventing Initiative sites are included in this table. A
 presentation of data from all Bioventing Initiative sites is provided in
 Section 4.1.

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                            •• Johnston Atoll
Figure 2-2.  Locations of Bioventing Initiative sites.

The following section describes the basic structure for
field studies conducted as part of the Bioventing Initia-
tive. Data from these studies were used to generate this
document.

2.3   Structure of Bioventing Initiative
       Field Treatability Studies and
       Bioventing  System  Design

The design  of  the field  treatability studies and final
bioventing system was developed based on experience
from previous studies at Hill, Tyndall, and Eielson AFBs.
The Test Plan and Technical Protocol for a Treatability
Test for Bioventing (Hinchee et al., 1992) was written to
standardize all field methods, from treatability tests to
well installations. This allowed for collection of consis-
tent data from 125 sites, which  provided a strong data-
base for evaluating bioventing potential. At all sites, the
following activities were conducted:
•  Site characterization, including a small-scale soil gas
   survey and collection of initial soil and soil gas sam-
   ples for analysis of  BTEX,  TPH, and soil  physico-
   chemical characteristics.
•  Field treatability studies, including an in situ  respira-
   tion test and a soil gas  permeability test.
•  Identification of a background, uncontaminated area
   for comparison with the contaminated area  of back-
   ground respiration  rates and  nutrient levels.
• Installation of a blower for 1  year of operation (typi-
  cally configured for air injection), if results  of field
  treatability studies were positive.

• Conduct of 6-month and  1-year in situ  respiration
  tests at sites where a blower was installed.

• Collection of final soil and soil gas samples for analy-
  ses of BTEX and TPH.

Of particular significance were the use  of  the in situ
respiration test to measure microbial activity and the use
of air injection instead of extraction for air delivery.

The  in situ  respiration test was  developed to  rapidly
measure aerobic biodegradation rates in situ at discrete
locations.7 Biodegradation  rates calculated from the in
situ  respiration test are useful for (1) assessing  the
potential application of bioremediation at a given site, (2)
estimating the time required for remediation at a given
site, and (3) providing a measurement tool for evaluating
the effects  of  environmental parameters on microbial
activity and ultimately on bioventing performance. The
actual effect of individual parameters on microbial activ-
ity is difficult to assess in the field because  of interfer-
ence and interactions among these parameters. The in
situ  respiration test  integrates all factors  to  assess
whether the microorganisms are metabolizing  the fuel.
 7 See Section 1.4 of Volume II for methods for conducting the in situ
  respiration test and analyses of test data.

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Table 2-2.  Summary of Reported in Situ Respiration Rates and Bioventing Data
Site
Scale of Application    Contaminant
                                                                     In Situ Respiration
                                                                     Rates (mg/kg-day
                                                                     Unless Marked)
Reference
Albemarle County, VA
Eielson AFB, AK

Fallon NAS, NE
Galena AFS, AK, Saddle Tank
Farm
Hill AFB, Utah, Site 914
Hill AFB, Utah, Site 280
Eglin AFB, FL
Kenai, Alaska, Site 1-33
Kenai, Alaska, Site 3-9
Massachusetts
Minnesota
The Netherlands
The Netherlands
The Netherlands
Patuxent River NAS, MD
Prudhoe Bay
St. Louis Park, MN, Reilly Tar
Site
Seattle, WA
Southern CA
Tinker AFB, OK
Tyndall AFB, FL
Undefined
Undefined
Undefined
Valdez, Site A
Pilot scale
Pilot scale

In situ respiration test
Pilot scale

Full scale, 2 years
Full scale
Full scale
Pilot scale
Pilot scale
Full scale
Full scale
Full scale
Undefined
Field pilot, 1 year
In situ respiration test
Pilot scale
Pilot scale
Full scale
Full scale
In situ respiration test
Field pilot, 1-year and
in situ respiration test
Full scale
Full scale
Full scale
Pilot scale
Acetone, toluene,
benzene, naphthalene
JP-4 jet fuel

JP-5 jet fuel
Diesel

JP-4 jet fuel
JP-4 jet fuel
Gasoline
Crude oil, petroleum
Crude oil
Gasoline
Gasoline
Gasoline
Undefined
Diesel
JP-5 jet fuel
Diesel
PAH
Diesel
Gasoline, hydraulic oil
JP-4 and mixed fuels
JP-4 jet fuel
Gasoline and diesel
Diesel
Fuel oil
Crude oil
1 .5-26
0.82-8.2

4.2
11-30

Up to 8.5
0.27 (site average)
4.0
2.7-25
0.64-12
Not measured
15, 4.9, 3.1, 0.20
570 kg of
hydrocarbon
removed during
2-year study
1 .6-4.2
6.9
2.6
8.6-11
0.55-2.2 mg
PAH/kg-day
6.0
0.14
2.3-15
1.6-16
50 kg/(well day)
100 kg/(well day)
60 kg/(well day)
0.90-15.6
Leeson et al., 1994
Hinchee and Ong, 1992
Leeson etal., 1995
EPA, 1994c
Hinchee et al., 1991b
Ong et al., 1 994

Hinchee et al., 1994
Battelle, 1994
EPA, 1991b
Downey etal., 1994
Hinchee, unpublished
data
Hinchee, unpublished
data
Brown and Crosbie, 1994
Newman et al., 1993
van Eyk, 1994
Urlings etal., 1990
van Eyk and Vreeken,
1989b
Hinchee et al., 1991b
Ong et al., 1994
Alleman et al., 1995
Baker etal., 1993
Zachary and Everett, 1 993
Hinchee and Smith, 1991
Miller, 1990
Hinchee et al., 1991b
Ely and Heffner
Ely and Heffner, 1988
Ely and Heffner, 1988
Hinchee, unpublished data
Data from the in situ respiration test and site measure-
ments were used to conduct a statistical analysis of the
observed effects of the site measurements on microbial
activity in the  field. The statistical analysis was con-
structed to  account for parameter interactions. These
results are discussed in detail in Chapter 5.

Also of note is that  120 of the 125 bioventing systems
installed were  configured for air injection. Before the
bioventing studies  conducted at Hill (Site 280) and
                              Eielson AFBs, bioventing systems were typically oper-
                              ated  in the  extraction  configuration,  similar to  SVE
                              systems. Research at Hill and Eielson AFB's, however,
                              demonstrated that air injection was a feasible, more effi-
                              cient alternative to air extraction,  resulting in a greater
                              proportion of hydrocarbon biodegradation  rather than
                              volatilization and reduced air emissions.8 Therefore, the
                               3 See Section 2.1 of Volume II for a discussion of air injection versus
                                extraction considerations.

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air injection configuration was selected  for the basic
bioventing system at Bioventing Initiative  sites.

The results generated from the Bioventing Initiative are
summarized in detail in Chapter 5 but also are used to
illustrate basic principles of  bioventing and  microbial
processes discussed in Chapter 3. The design guide-
lines presented in this manual are the result primarily of
the information gained from installing and operating the
125 Bioventing Initiative sites. These design guidelines
represent the basic bioventing system, which is applica-
ble to the majority of sites suitable for bioventing. The
following section addresses  emerging techniques for
modifying the basic bioventing system for use at sites
that are not amenable to standard bioventing  methods.

2.4    Emerging Techniques for
       Modifications to Bioventing Systems
Several techniques are being investigated as a means of
modifying the conventional bioventing system described in
this document. These techniques have not been tested
extensively in the field; therefore, their potential feasibility
is unknown. These techniques are briefly presented in this
section to illustrate their potential application.
The  bioventing  modifications being  investigated  are
designed to address specific challenges in bioventing
including:
• Injection of pure  oxygen instead of air for  treatment
  of low-permeability soils: Because only low flow rates
  are possible in low-permeability soil, injection of pure
  oxygen  may  be useful for providing larger oxygen
  concentrations for a given volume than is possible
  with air  injection.

• So/7  warming for bioventing in  cold climates: Soil
  warming can  be used to increase  biodegradation
  rates, thus decreasing remediation times. This tech-
  nique has been studied in detail at Site 20, Eielson
  AFB, Alaska9 but would only be an option in extreme
  environments.

• Remediation   of  recalcitrant  compounds  through
  ozonation: Ozonation may be used to partially oxidize
  more  recalcitrant contaminants,  making them  more
  susceptible to biodegradation.  This technique would
  not be  necessary at  petroleum-contaminated sites
  but may be considered at sites  contaminated with
  compounds such as  polycyclic  aromatic  hydrocar-
  bons (PAHs)  or pesticides.

• Remediation  of contaminated saturated soils through
  air sparging:  Air sparging  is being investigated as a
  means of aerating saturated soil  to enhance biode-
  gradation and volatilization. Studies to date, however,
  have been inconclusive concerning its effectiveness
  because the  studies lacked adequate  controls and
  measurement techniques.
The techniques described above  represent potential fu-
ture  areas of investigation  in the bioremediation field.
The  following  chapters describe  the  principles of
bioventing, which also apply to the techniques  described
in this section.
                                                       9 See Section 4.4 for a discussion of this site and the cost benefits of
                                                        soil warming.

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                                               Chapter 3
                                      Principles of Bioventing
In this  chapter, basic  principles fundamental to the
bioventing process are discussed  to provide a  clear
understanding of  the many physical, chemical, and
biological processes that affect the ultimate feasibility of
bioventing. Recognizing the significance of these dif-
ferent processes will  lead to more  efficient bioventing
design and operation. Specific topics addressed in this
chapter include:

• Soil gas permeability, contaminant diffusion and dis-
  tribution, and zone  of oxygen  influence.

• Environmental  factors  that  affect microbial  proc-
  esses, such as electron acceptor conditions, moisture
  content, pH, temperature, nutrient supply, contami-
  nant concentration, and bioavailability.

• Subsurface distribution of an immiscible liquid.

• Compounds targeted for removal  through bioventing.

• BTEX versus TPH removal during petroleum bioventing.

3.1   Physical Processes  Affecting
      Bioventing

Three primary physical characteristics affect bioventing.
These include soil gas permeability, contaminant  diffu-
sion and distribution, and zone of oxygen  influence.
Each of these parameters is discussed in the following
sections.

3.1.1   Soil Gas Permeability

Assuming contaminants are present that are amenable
to bioventing, geology probably is  the most  important
site characteristic for a successful bioventing application.
Soils must be sufficiently permeable to allow movement
of enough soil gas to  provide  adequate oxygen  for
biodegradation,  approximately 0.25 to 0.5  pore vol-
umes per day.

Soil gas permeability  is a function of soil structure and
particle  size,  as  well as  moisture  content.  Typically,
permeability  in excess of 0.1  darcy is adequate  for
sufficient air exchange. Below  this level, bioventing
certainly is possible, but field testing may be required
to establish feasibility.
When  the  soil gas  permeability  falls  below approxi-
mately 0.01 darcy, soil gas flow is primarily through
either secondary porosity (e.g., fractures) or any more
permeable strata that may be present  (e.g., thin sand
lenses). Therefore, the feasibility  of bioventing in low-
permeability soils is a function of the distribution of flow
paths and  diffusion of  air to and from the flow  paths
within the contaminated area.

In a soil that is of reasonable permeability, a minimum
separation  of  2 ft  to 4 ft  (0.61 m to 1.2 m) between
vertical and horizontal flow paths and contaminant may
still result in successful treatment because of oxygen
diffusion. The degree of treatment, however, will be very
site-specific.

Bioventing  has been successful in some low-permeabil-
ity soils,  such as a silty clay site at Fallen Naval Air
Station (MAS), Nevada  (Kittel et at., 1995), a clayey site
at Beale AFB, California (Phelps et al., 1995), a silty site
at Eielson AFB, Alaska (Leeson et al., 1995), a silty clay
site in Albemarle County, Virginia (Leeson et al.,  1994),
and many Bioventing Initiative sites. Grain size analysis
was conducted on several samples from each site in the
Bioventing  Initiative. The  relative distribution of fine-
grained soils is illustrated in Figure 3-1. Sufficient soil
gas permeability has been demonstrated at many sites
with silt and clay  contents exceeding 80  percent by
weight. Approximately  50 percent of the  sites  tested
       0-10
                 10-25
                          25-50
                       % Silt + Clay
                                   50-75
75-100
                                                       Figure 3-1.  Distribution of fine-grained soils (silt and clay) at
                                                                 Bioventing Initiative sites.
                                                    11

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contained greater than 50 percent clay and silt fractions.
Oxygen distribution has generally been adequate in
soils where permeability values  exceeded 0.1 darcy,
with oxygen detected at ambient levels in all nine of the
monitoring points installed. Few sites had permeability
less than 0.1 darcy; therefore, data are limited for analy-
sis. The greatest limitation to bioventing at Bioventing
Initiative sites has been excessive soil moisture. A com-
bination of high soil moisture content and fine-grained
soils has  made bioventing impractical  at only  three of
the 125 test sites, however.
In general, our calculated soil gas permeability values
have exceeded suggested values reported in Johnson
et al. (1990) for silt and clay soils. This is  probably
because  of the  heterogeneous nature of most soils,
which contain lenses of more permeable material or
fractures that aid in air distribution.

3.1.2  Contaminant Distribution
Another  important  factor  affecting  the feasibility of
bioventing is contaminant distribution throughout the
site. Because bioventing is in essence an air delivery
system designed to efficiently provide sufficient oxygen
to contaminated soils, a clear understanding of subsur-
face contaminant distribution is a necessity. Many  sites
at which bioventing can be applied  are contaminated
with immiscible  liquids,  such as petroleum hydrocar-
bons. When a fuel release occurs,  the contaminants
may be  present in any or all of four phases in the
geologic media:

•  Sorbed to the  soils  in  the vadose zone.
•  In the vapor phase  in  the vadose zone.

•  In free-phase form floating on the water table or as
   residual saturation in the vadose zone.

•  In the aqueous phase dissolved in pore water in the
   vadose  zone or dissolved in the ground water.

Of the four phases,  dissolved petroleum contaminants
in ground  water frequently are  considered to be of
greatest concern due  to the  risk  of humans being ex-
posed to  contaminants  through drinking water.  The
free-phase and sorbed-phase hydrocarbons, however,
act as feed stocks for ground-water contamination, so
any remedial technology aimed  at  reducing  ground-
water contamination must address these sources of
contamination. Also, hydrocarbons in the vadose zone
can produce a volatile organic carbon  (VOC) threat in
subsurface buildings or structures.

Immiscible liquids are classified  as  less dense  non-
aqueous phase liquids (LNAPLs)  if their density is less
than water  or  dense  nonaqueous   phase  liquids
(DNAPLs) if their density is greater than water. In  gen-
eral, most petroleum hydrocarbons, such as gasoline,
are LNAPLs, whereas most chlorinated solvents, such
as trichloroethylene (TCE), are DNAPLs. Because of
these  differences  in  densities,  subsurface spills of
LNAPLs and DNAPLs behave differently at a given site,
with  LNAPLs distributed primarily in the vadose zone
and  DNAPLs distributed in both the unsaturated  and
saturated  zones. Because bioventing  is  primarily  a
vadose zone treatment process, this discussion focuses
on the behavior of LNAPLs.
When  a large-enough fuel spill occurs, the fuel is.re-
tained  within approximately 10  percent to 20 percent of
the pore volume of the soil  and  may eventually come to
rest  on the water table.  Contaminants  then  partition
among the various phases existing within the subsur-
face  environment. Fluids can move through the subsur-
face  via various  mechanisms,  such as advection  and
diffusion.  LNAPLs are likely to migrate through  the
vadose zone relatively uniformly  until they reach the
capillary fringe. The LNAPLs will then spread laterally
along the  saturated zone.  Water table fluctuation may
result  in  LNAPL below the water table; however, an
LNAPL will not permeate the water-saturated zone un-
less  a critical capillary pressure is exceeded, which is a
function of the porous medius pore sizes.
In the  vadose zone, components of the LNAPL may
partition into the vapor phase  or the aqueous phase
(pore water), sorb onto solids, or remain in the  free
product. Contaminants in free product may partition into
the vapor phase, depending on  their vapor pressures at
the temperature  and pressure existing in the vadose
zone. Once in the vapor phase,  these contaminants can
migrate in response to advection and diffusion. Raoult's
Law  is used to describe partitioning at equilibrium be-
tween an immiscible and a vapor phase:
                           •'vsat
                                          (Eq.
where:
  Cv = volumetric concentration of the contaminant
       (x) in the vapor phase (gx/Lvapor)
   % = mole fraction of the contaminant
       (dimensionless)
Cvsat = saturated vapor concentration of the
       contaminant (gx/Lvapor)
Cvsat is further defined as:
(MWX) Pv
  RT
                                          (Eq. 3-2)
                            abs
where:
MWX = molecular weight of the contaminant
       (gx/molex)
   Pv F vapor pressure of pure contaminant at
       temperature T (atm)
   R = gas constant (L-atm/mole-°K); and
 Tabs = absolute temperature (°K)
                                                  12

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Free product in contact with ground water may leach
contaminants  into the ground water, or contaminants
may dissolve into pore water in the vadose zone, de-
pending on the solubility of specific components. Once
in the ground water, contaminants can migrate through
the subsurface in response to a gradient in the aqueous-
phase total potential (i.e.,  advection) or by a difference
in the  aqueous-phase chemical  concentrations.  The
equilibrium relationship between  the aqueous and the
immiscible phases is described as:
                         =  sx
(Eq.  3-3)
where:
  Cv = volumetric concentration of the contaminant x
       in the aqueous phase (gx/Laqueous)
   X = mole fraction of the contaminant
       (dimensionless)
   sx = solubility of pure contaminant x in water
       (9x/LWater)
Sorption of contaminants is a complex process involving
several different phenomena, including coulomb forces,
London-van derWaals forces, hydrogen bonding, ligand
exchange, dipole-dipole forces, dipole-induced dipole
forces, and hydrophobic forces. In the case of hydrocar-
bons, because of their nonpolar nature,  sorption most
often occurs through  hydrophobic  bonding to  organic
matter.  Hydrophobic bonding often is a dominant factor
influencing the fate of  organic chemicals in the  subsur-
face (DeVinny et  al.,  1990).  The  degree of sorption
generally is empirically related by the organic content of
the soil and the octanol-water  partition coefficient of a
particular compound.
Sorption isotherms generally follow one of three shapes:
Langmuir, Freundlich,  or linear (Figure 3-2). The Lang-
muir isotherm describes the sorbed contaminant  con-
centration as increasing linearly with concentration, then
                                           Linear
                                           FreundPch
                                           Langmuir
             Dissolved Concentration, C, (pig/ml)

Figure 3-2.  Sorption isotherms.
leveling off as the number of sites available for sorption
are filled. This isotherm accurately describes the situation
at or near the  contaminant source,  where concentra-
tions are high. The Freundlich isotherm assumes  an
infinite number of sorption sites, which would accurately
describe an area some distance from the contaminant
source, where concentrations are dilute. The mathematical
expression contains a chemical-specific coefficient that
may alter the linearity of the isotherm. The linear iso-
therm is relatively simple and is valid for dissolved
compounds at less than one-half  of their solubility (Ly-
man  et al., 1992). This isotherm is typically valid to
describe hydrocarbon sorption.

The  linear isotherm is expressed mathematically as:

                     Cs = Kd Cw             (Eq. 3-4)

where:
  Cs = quantity of  contaminant x sorbed to the  solid
       matrix (gx/gSOii)
  Kd = sorption coefficient (Laqueous/gsoi,)
  Cw = volumetric concentration of contaminant x  in
       the aqueous phase (gx/Laqueous)
The  sorption coefficient may be determined experimen-
tally, estimated based on values published in the litera-
ture   or  estimated using the  octanol/water  partition
coefficient (Kow) and the organic carbon fraction (foc) of
the soil. The sorption coefficient can be estimated using
the following mathematical expression:
                                         '
                                                       (Eq. 3-5)
            Some values for Kow are provided in Table 3-1.

            In practice,  at equilibrium, the concentration of most
            petroleum hydrocarbon compounds  of interest in  the
            aqueous or  vapor phases is driven by the immiscible
            phase, if present, and  the sorbed phase, if the  immis-
            cible phase  is not present.  If no immiscible  phase is
            present, and all sorption sites on the solid soil matrix are

            Table 3-1.  Values for Key Properties of Select Petroleum
                     Hydrocarbons
            Compound
                            Solubility   Vapor Pressure
                    Kow      (mg/L)      (mm Hg)a
Benzene
Ethylbenzene
Heptane
Hexane
Toluene
oxylene
m-xylene
p-xylene
131.82
1,349
—
—
489.9
891
1,585
1,513.6
1,750b
152b
50
20
537°
152b
158b
198b
75
1079°F
40
150
2065°F
7
9
9
              Vapor pressure at 68°F unless noted.
            b Calculated at 20°C.
            c Calculated at 20°C.
                                                    13

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not occupied,1 the vapor- or aqueous-phase concentra-
tion is a function of the sorbed concentration. This rela-
tionship is illustrated in Figure 3-3.

This relationship typically follows a Langmuir type curve.
If the concentration in the soil is in excess of the sorption
capacity of the soil,2 the  aqueous-phase and the vapor-
phase concentrations are Raoult's  Law-driven and are
independent of the hydrocarbon concentration in the
soil. This is an important concept in attempting to inter-
pret soil gas or ground-water data. For example, in a
sandy site at which free product has been detected, the
highest soil  hydrocarbon concentrations may exceed
25,000 mg/kg. Yet, 99 percent remediation to 250 mg/kg
may not affect the equilibrium soil gas or ground-water
hydrocarbon concentrations.

In terms of contaminant distribution, difficulties in ap-
plying bioventing arise  when significant quantities of
the contaminant are in the capillary fringe or below the
water table because of  ground-water fluctuations.
Treatment of  the capillary  fringe is possible, and
screening of venting wells  below the water table is
recommended to ensure treatment of this area.3 The
ability of bioventing to aerate the capillary fringe and
underlying water table has not been evaluated, how-
ever.  Limited oxygenation is anticipated because of
water-filled pore space.  If significant contamination ex-
ists below the water table, dewatering should be consid-
ered as a means  of exposing any contaminated soil to
injected air. Alternatively, a combination of air sparging
and bioventing may provide more efficient air delivery to
the capillary fringe; however, air sparging has not been

                    F.
                        Raoult's Law Concentration
            Immiscible Phase
            Absent, Sorption Driven
Immiscible Phase Present,
Raoulfs Law Driven
                        100-1,000 mg/kg
                     Soil Concentration (mg/kg)

Figure 3-3.  Relationship between sorbed contaminant concen-
           trations and vapor- or aqueous-phase concentrations.
1 In most soils, this is probably at a concentration of less than 100
 mg/kg to 1,000 mg/kg.
2 In most soils, this is probably at a concentration of less than 100
 mg/kg to 1,000 mg/kg
3 See Section 2.5 of Volume II for a discussion of vent well construction.
 well documented,  and many  parameters are  still  un-
 known concerning  its applicability and effectiveness.

 3.1.3  Oxygen Radius of Influence

 An estimate of the oxygen radius of influence (R|) of venting
 wells is an important element of a full-scale bioventing de-
 sign. This measurement is used to design full-scale sys-
 tems,  specifically to space venting wells, to size blower
 equipment,  and to  ensure that the entire site  receives a
 supply of oxygen-rich air to sustain in situ biodegradation.

 The radius  of oxygen influence is defined as  the radius
 to which oxygen has to be supplied to sustain maximal
 biodegradation. This definition of radius of influence is
 different than is typically used  for SVE, where radius of
 influence is defined as  the maximum distance from the
 air extraction or injection well where vacuum or pressure
 (soil gas movement) occurs. The oxygen radius of influ-
 ence  is a function  of both air flow rates and  oxygen
.utilization rates, and therefore  depends on site geology,
 well design, and microbial activity.

 The radius of influence is a function of soil properties but
 also is dependent on the configuration of the venting well,
 extraction or injection flow rates, and microbial activity, and
 also is altered by soil stratification. In soils with less per-
 meable lenses adjacent to more permeable soils, injection
 into the permeable layer produces a  greater radius of
 influence than could be achieved in homogeneous soils.
 On sites with shallow contamination, the radius  of influ-
 ence also may be  increased  by impermeable  surface
 barriers such as asphalt or concrete. Frequently, however,
 paved surfaces do not act as vapor barriers. Without a tight
 seal to the  native soil surface,4 the pavement does  not
 significantly affect soil gas flow.

 Microbial  activity affects the oxygen radius of  influence.
 As microbial activity increases, the effective treated area
 decreases.  Therefore, a desirable approach  is to esti-
 mate the oxygen radius of influence at times of peak
 microbial  activity and to design the bioventing  system
 based on these measurements.

 3.2   Microbial  Processes  Affecting
       Bioventing

 Biological treatment approaches rely on organisms to
 destroy or  reduce  the toxicity of contaminants. The
 advantages of  chemical and physical treatment ap-
 proaches generally are outweighed by the  ability of
 microorganisms to mineralize contaminants, thereby
 eliminating  the process  of transferring contaminants
 from one  medium (i.e.,  soil and soil vapor) into another
 medium (i.e., activated carbon) that will still  require treat-
 ment.  In addition, microbial processes allow treatment of
                        4 Based on the author's experience, this seal does not occur at most
                         sites.
                                                     14

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large areas relatively inexpensively and with relatively
noninvasive techniques. This section discusses kinetics
of microbial metabolism and environmental parameters
that affect the microbial processes bioventing is depend-
ent upon, thereby potentially affecting the efficacy of
bioventing.

3.2.7   Microbial Kinetics

In biological  processes,  microorganisms degrade or-
ganic compounds either directly to obtain carbon and/or
energy, or fortuitously in a cometabolic process with no
significant benefit to the microorganism. As an example,
a stoichiometric equation  describing degradation of
n-hexane is shown:

           C6H14 + 7.875O2 + 0.25NO3 -»

              CH2O0 5N0 25(biomass) +

                   5CO2 + 6H2O           (Eq. 3-6)

In the  case of bioventing,  where microorganisms are
stimulated in situ, the microorganisms are at equilibrium,
and  little net biomass  growth occurs. In other  words,
biomass  decay  approximately  balances  biomass
growth. Consequently,  where no net biomass  is pro-
duced, Equation 3-6  reduces to:

           C6H14 + 9.5O2 -> 6CO2 + 7H2O   (Eq. 3-7)

Based on  Equation 3-7,  9.5  moles of oxygen are re-
quired  for every mole of hydrocarbon consumed, or, on
a weight basis, approximately 3.5  g of oxygen are re-
quired  for every 1 g of hydrocarbon consumed.

Predicting the amount of time needed to bioremediate
a site requires an understanding of the microbial kinet-
ics of  substrate  (contaminant)  utilization.  Most  sub-
strate  utilization falls  under the heading  of primary
substrate utilization, in  which  growth  on a carbon
source supplies most of the carbon and  energy for the
microorganism. In cases where a contaminant does not
supply the primary source or cannot be used for carbon
and   energy,  secondary   substrate   utilization  or
cometabolism may occur. During the bioventing proc-
ess, primary substrate utilization generally describes
the kinetics of the reactions taking place; however, in
some instances, cometabolic processes also may oc-
cur. For example, at sites contaminated with both fuels
and  solvents, such  as TCE,  cometabolic  bioventing
may account for degradation of TCE.

Primary substrate utilization  has been described through
an empirical approach by the Monod expression:

                   _ dS _  kXS           (Eq. 3-8)
                     dt  ~ rC +  S
where:
   S = concentration of the primary substrate
       (contaminant) (gs/L)
    t = time (minutes)
   k = maximum rate of substrate utilization (gs/9x-
       min)
   X = concentration of microorganisms (gx/L)
  Ks = Monod half-velocity constant
At high substrate concentrations (S is greater than Ks), the
rate of substrate  utilization is at a maximum, limited  by
some other factor such as oxygen, nutrients, or the char-
acteristics of the microorganism. In this instance, the rate
of substrate utilization is first-order with respect to cell
density but zero-order with respect to substrate concentra-
tion.  Conversely,  when the primary substrate concentra-
tion is very low (S is less than Ks), the substrate utilization
rate  is first-order with respect to  both cell density and
substrate concentration. In a well-designed bioventing sys-
tem,  kinetics based on oxygen utilization are zero-order.
The  rate based on petroleum or  other contaminant  re-
moval may be described, however, by Monod or inhibition
kinetics.
Monod  kinetics have  been widely applied to  conven-
tional wastewater treatment, where the compounds be-
ing  treated generally are  bioavailable  and  readily
degradable. Bioventing typically is applied to aerobically
biodegradable compounds; however, the maximum rate
of biodegradation (k) is much lower than for most wastes
in conventional  wastewater treatment. For  example,
Howard et  al. (1991) estimated  that  benzene has  an
aerobic half-life (dissolved in ground water) of 10 days
to 24 months, whereas ethanol (a compound more typi-
cal of conventional wastewater treatment) is estimated
to have a half-life of 0.5 to 2.2 days. Bioventing kinetics
are further complicated by bioavailability of the contami-
nants, driven at least in part by solubilization. Because
microorganisms exist in pore water, contaminants must
partition into the pore water to be  available for degrada-
tion.  Although high soil contaminant concentrations may
be present, the  actual  concentration  of  hydrocarbon
dissolved in the pore water and available to the micro-
organisms may be low.

In practice, oxygen  utilization rates tend to decline
slowly with time during remediation. At many sites, this
trend may be difficult to follow over periods of less than
1 to 3 years because of other variables affecting the rate,
such as temperature and soil moisture. This decline may
not  be  indicative of  true  first-order kinetics but may
simply be the result of selective early removal of more
degradable compounds, such as  benzene.

3.2.2   Environmental Parameters Affecting
        Microbial Processes

Bioventing depends upon providing microorganisms op-
timal conditions for active growth. Several factors may
                                                   15

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affect a  microorganism's ability to degrade contami-
nants, including:

• Availability and type of electron acceptors

• Moisture content

• Soil pH

• Soil temperature

• Nutrient supply

• Contaminant concentration

• Bioavailability and relative biodegradation

Each of these parameters was measured at Bioventing
Initiative sites. The actual effect of individual parameters
on  microbial activity  is  difficult to assess  in the field
because of interference and interactions among these
parameters. The in situ  respiration test was used as a
measurement tool that integrates all factors to  assess
whether the microorganisms are metabolizing the fuel.
Data from the in situ respiration test and site  measure-
ments were used to conduct a statistical analysis of the
observed effects of the site measurements on microbial
activity  in the  field. The statistical analysis  was con-
structed to  account for  parameter interactions. These
results  are  discussed in detail in Chapter 5. A more
general discussion of the significance of each of these
parameters and its effect on microbial  activity is pro-
vided in Sections 3.3.2.1 through 3.3.2.7.

3.2.2.1    Electron Acceptor Conditions

One of the most important factors influencing the biode-
gradability of a compound is the type and availability of
electron acceptors. Following a hydrocarbon spill,  for
example, the microbial  degradation of  biodegradable
hydrocarbons results in  oxygen depletion and thus an-
aerobic conditions in the subsurface soil. Although hy-
drocarbons  may undergo limited biodegradation under
anaerobic conditions (Bilbo et al., 1992; Mormile et al.,
1994), aerobic conditions generally are most suitable for
relatively rapid remediation of petroleum hydrocarbons.
Therefore, oxygen supply is crucial to the success of a
bioventing system. In  field studies, oxygen  has been
found to be the most important factor in determining the
success of a bioventing system (Hinchee et  al., 1989;
Miller et al., 1991). The  Bioventing Initiative confirmed
this conclusion, finding  that  oxygen was the primary
factor limiting microbial  activity at all  but three  sites
(Miller et al., 1993).

3.2.2.2   Moisture Content

Soil moisture content may affect the bioventing process
by its effect on microorganisms or soil gas permeability.
Microorganisms require  moisture  for metabolic proc-
esses and for solubilization of energy and nutrient sup-
plies. Conversely, soil  moisture content directly affects
soil permeability, with high moisture content resulting in
poor distribution of oxygen. In practice, soil moisture has
been found to directly limit biodegradation  rates only
where bioventing  has been implemented in  very dry
desert environments. A more common influence of mois-
ture is that excess moisture has led to  significant reduc-
tions in soil gas permeability. One major objective of the
Bioventing Initiative was to assess the effects of mois-
ture on biodegradation.
The range of soil moisture content measured at Biovent-
ing Initiative sites is shown in Figure 3-4. The lowest soil
moisture content measured was 2 percent by weight,
and microbial activity still was observed in these soils.
Figure 3-5 illustrates the observed relationship between
soil moisture  and oxygen utilization rates. To date,  a
strong correlation has not been recorded between mois-
ture content and oxygen utilization rate, although a slight
positive relationship has been observed.5
        <5     5-10     10-15     15-20     20-25     >25

                   Moisture Content (% by weight)
Figure 3-4.  Soil moisture content measurements at Bioventing
           Initiative sites.
3 20
5
                         •     •
           5      10      15      20     25

                   Moisture Content (% by weight)
                                            30
Figure 3-5.  Direct correlation between oxygen utilization rates
           and  soil moisture content at Bioventing Initiative
           sites.
6 See Section 5.2 for a discussion of the statistical relationship be-
 tween moisture content and oxygen utilization rates.
                                                     16

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At a desert site at the Marine Corps Air Ground Combat
Center, Twentynine Palms, California, soil moisture con-
tent appeared to detrimentally affect microbial activity.
Soil moisture content ranged from 2 percent to 4 percent
by weight and, although the site was contaminated with
jet fuel, significant oxygen limitation was not observed.
An irrigation system was installed at the site in  an effort
to enhance microbial activity. The site was irrigated for
1 week, then bioventing was initiated for 1 month before
conducting an in situ respiration test. In situ respiration
rates  measured after irrigation were significantly higher
than those measured before irrigation (Figure 3-6). In
addition, before irrigation, oxygen was not consumed
below approximately 17 percent before microbial activity
stopped. After irrigation, activity continued until oxygen
was completely consumed to less than 1 percent. These
results demonstrated that in extreme cases, moisture
addition  may improve  the performance  of bioventing
systems through enhanced microbial activity.

Air injection bioventing may dry out the soil to a point
that would be detrimental to microbial growth,  necessi-
tating humidification of the injection air. A simple calcu-
lation, however,  as shown in Example 3-1, illustrates
that moisture loss is minimal over a 3-year period. Dry-
ing and moisture loss as a result of bioventing usually
are only a problem very near the vent well or if very high
air injection  rates are  used (typically not the case in
properly designed  bioventing systems).  Sites  typically
have  several moisture sources that also  make drying
due to air injection  negligible,  such as rain and snow,
and water as a by-product of mineralization (generated
at a rate of 1.5 kg of water for every 1 kg of hydrocarbon
degraded).6
                            Example 3-1. Moisture Content Change During Air In-
                            jection  and Water Generated During Biodegradation:
                            For this test:
                               Vapor pressure (Pwater) =  17-5 mm Hg
                                        Flow rate (Q) =  1  pore volume/day
                                                        (typical of bioventing)
                                 Volume of treatment =  12,300 m3
                                             area (V)
                              Biodegradation  rate (kB) =  3  mg/kg-day
                               Initial moisture content =  15 percent by weight
                                     Soil bulk density =  1,440 kg/m3

                            Assume worst case of 0  percent humidity and no
                            infiltration.

                            To calculate the total water at the site initially, the mass
                            of soil is first calculated:


                                    12,300 m3 x 1|44° kg = 1.8 x 107 kg soil
                                                  m3

                            Therefore, the initial mass of water is:

                                  (1.8 x 107 kg soil) x 0.15 = 2.7 x 106 kg H2O
                            Because the flow rate is equivalent to 1 pore volume/day,
                            the mass of water removed per day will be equal to the
                            mass of water in the vapor phase of the treated area, which
                            can be calculated using the Ideal Gas Law:
6 See Equation 3-7 for the stoichiometry of this calculation.
                 20
                  5 f-
             Oxygen
             Carbon Dioxide
                                               Air Injection Initiated	1—
                   Irrigation Initiated
                   (11/8 and 11/29-12/5)
                  0
                  June
July     August  September  October  November   December,,  January
                                               1994                                1995

Figure 3-6.  Oxygen and carbon dioxide concentrations before and after irrigation at Twentynine Palms, California.
                                                     17

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Total water removal in 3 years:
           Moles H2O removed
                                 water
                       V
                                  RT
    day

17.5 mm Hgx 12,300m3
      m3-mm Hg'
       mole-°K
             0.0623

       Moles H2O removed
x298°K
               day
                          = 11,600=210
                           J<£L
                           day
     210 -fa- x 1,095 days = 230,000 kg removed
         day
This water loss represents a fairly small percentage, or:

    230,000 kg evaporated = QQQ6 _ QQ%      ^
     2.7 x 106 initial mass

This is equivalent to a soil moisture drop from approxi-
mately 15 percent to 13.7 percent. Assuming a contami-
nated  thickness  of 10 ft (3 m), an infiltration rate of
approximately 2.4 inches (6.1 cm) in 3 years, or less
than 1  inch (2.5 cm) per year, would  replace the lost
moisture. In practice, some drying very close to the vent
well may be observed but usually is not.

Water loss also will be replaced through biodegradation
of hydrocarbons. Calculating the total mass of hydrocar-
bons degraded over 3 years:

               x 1,095 days x (1.8 x 107 kg soil) x


             = 59,000 kg hydrocarbon  degraded
       10 mg

Based on the stoichiometry  in Equation 2-1, if 1.5 kg of
water  are generated  for every kg of hydrocarbon de-
graded, the amount of water generated would be:
      59,000 kg hydrocarbon x
                               1.5 kg water
                              kg hydrocarbon
                  88,500 kg water
Therefore, total water removal  in 3  years must also
account for the water generation, where:

  230,000 kg - 88,500 kg H2O = 141,500 kg H2O loss

This is equivalent to a water loss of 5.3 percent over 3
years.
survive. Most bacteria function best in a pH range be-
tween 5 and 9 with the optimum being slightly above 7
(Dragun, 1988). A shift in pH may result in a shift in the
makeup  of the microbial population  because each
species  exhibits  optimal  growth  at  a specific pH.
Throughout the Bioventing Initiative, pH has not been
found to limit in situ bioremediation and  is probably
only of concern  where contamination has radically
altered the existing pH.
Figure 3-7 illustrates the range of soil  pH found at the
Bioventing Initiative sites to date. In general, the majority
of sites have fallen  within the "optimal" pH range for
microbial activity of 5 to 9. Microbial respiration based
on oxygen utilization has been observed  at all sites,
however, even  in  soils where the pH  was below 5 or
above 9.  Figure 3-8 illustrates the observed relationship
between  pH and oxygen utilization rates. These obser-
vations suggest that pH is not  a concern when biovent-
ing at most sites.7
                                              <5.0  5.0-6.0  6.0-6.5  6.5-7.0  7.0-7.5 7.5-8.0  8.0-8.5  8.5-9.0   >9.0

                                                                   PH



                                         Figure 3-7.  Soil pH measurements at Bioventing Initiative sites.
                                            50 :—

                                            45 r

                                            40

                                            35 -

                                            30 -

                                            25 -

                                            20-'

                                            15 -

                                            10 -

                                            5 -
                                                     •   *
                                                       .    :•
                                            O1—
                                             4.5
                                                 5.0   5.5   6.0  6.5  7.0  7.5  8.0   8.5   9.0   9.5   10.0

                                                                   PH
3.2.2.3   Soil pH

Soil pH also may affect the bioremediation process be-
cause microorganisms require a specific pH range to
                                         Figure 3-8.  Correlation between oxygen utilization rate and soil
                                                   pH at Bioventing Initiative sites.

                                         7 See Section 5.2 for a discussion of the statistical relationship be-
                                          tween pH and oxygen utilization rates.
                                                    18

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3.2.2.4   Soil Temperature

Soil temperature may significantly affect the bio-remedia-
tion process. Microbial activity has been reported at tem-
peratures varying from -12°C to  100°C (10°F to 212°F)
(Brock et al., 1984); however, the optimal range for biode-
gradation of most contaminants  is generally much nar-
rower.  An   individual  microorganism may  tolerate a
temperature peak of up to approximately 40°C (104°F). A
microorganism's optimal  growth  temperature, however,
varies depending on climate. For example, microorgan-
isms  in a  subarctic  environment may  exhibit  optimal
growth at 10°C (50°F), whereas microorganisms in a sub-
tropical environment  may exhibit  optimal growth at 30°C
(86°F).

Generally biodegradation rates  double for every 10°C
(50°F) temperature increase, up  to some inhibitory tem-
perature. The van't Hoff-Arrhenius equation expresses
this relationship quantitatively as:
                0.6
                             -Ea
                    kT = k0 e
(Eq. 3-9)
where:
  kT = temperature-corrected biodegradation rate
      (percentage of O2/day)
  ko = baseline biodegradation rate (percentage of
      O2/day)
  Ea = activation energy (cal/mole)
  R = gas constant (1.987 cal/°K-mol)
Tabs = absolute temperature (°K)
Miller (1990) found Ea equal to 8 to 13 kcal/mole for in situ
biodegradation of jet fuel. In the 17°C to 27°C (63°F to
81 °F) range, the van't Hoff-Arrhenius relationship accu-
rately predicted biodegradation  rates. A similar analysis
was conducted at Site 20, Eielson AFB, Alaska, where the
activation energy was found to be equal to 13.4 kcal/mole
(Example 3-2). Figure 3-9 illustrates the relationship be-
tween oxygen utilization rate and temperature and be-
tween biodegradation and temperature observed at Site
20, Eielson AFB, a JP-4 jet fuel-contaminated site.
Example  3-2. Calculation of the  van't Hoff-Arrhenius
Constant From Site Data: Various forms of soil warming
were tested at Site 20, Eielson AFB, Alaska. This re-
sulted in a wide range of temperatures and biodegrada-
tion rates measured at the same site.
To calculate the van't Hoff-Arrhenius constant, the log of
the biodegradation rate must be calculated  versus the
inverse of the temperature to provide the relationship:

                  I  fM  ~Ea   1
                  ln            x

                0.4


                0.3


                0.2 -


                0.1 -
                0.0
•  •
                                    10     15     20
                                  Temperature (°C)
                                                      25
                                                            30
                 3.35    3.40    3.45    3.50    3.55   3.60   3.65   3.70
                                  1/T (°K) ' 1000

            Figure 3-9.  Soil temperature versus oxygen utilization and
                      biodegradation rate at Site 20, Eielson AFB, Alaska.

            The slope of the linear regression of inverse tempera-
            ture versus oxygen utilization rate is -6,740 °K (Figure
            3-9). Therefore,

                                -^ = -6,740


                                Ea
                           1.987
                                   cal
                                         = -6,740
                                °K-mole
                        Ea = 1.9870      ,
                         a        °K-mole
                  x -6,740 =
                                  cal         kcal
                          13,390 ——— ~ 13.4
                                 mole
                     mole
            Heat addition may improve bioventing processes. Solar
            warming, warm water infiltration,  and buried heat tape
            have been used to increase soil temperature. Their use
            has increased microbial activity and contaminant degra-
            dation (Leeson et al., 1995). Selection of a soil warming
            technique depends on a comparison of cost considera-
            tions versus remediation time requirements.8 Although
                                                        1 See Section 4.4 for a discussion of the cost benefit of soil warming.
                                                    19

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warm water infiltration or heat tape can significantly
increase biodegradation rates, the cost is significantly
higher than simply using surface insulation or no heat-
ing method. The use of warm water infiltration, although
effective, is limited to very permeable soils to ensure that
adequate drainage of the applied water occurs. The use
of soil heating to increase biodegradation rates may only
prove cost-effective in cold regions, such as Alaska.

3.2.2.5   Nutrient Supply
To sustain  microbial growth, certain nutrients must be
available at minimum levels. The following hutrients/co-
factors are known to be required in order to support
microbial growth: calcium, cobalt, copper, iron, magne-
sium, manganese, molybdenum, nitrogen, phosphorus,
potassium, sodium,  sulfur, and zinc. Nitrogen and phos-
phorus are required in the greatest concentrations and
are the nutrients most likely to  limit microbial growth.
The remaining chemicals are considered micronutrients
because they are required in  only small quantities and
generally are available in excess in nature.
Nutrients are required as components  of the microbial
biomass. The need for these  nutrients  is very different
from the need for oxygen (or other electron donors) and
the carbon source. Nutrients are not destroyed but are
recycled by the  ecosystem.  Thus, unlike oxygen, a
steady input of  nutrient is not  required.
An approach to estimation of nutrient requirements, sug-
gested by John  T. Wilson of the EPA Ada Laboratory, can
be made based on microbial kinetics. Starting with:
                  U  _ If V  if  V
                  — - l\b Y - l\d A
                                         (Eq. 3-10)
where:
 X
      =   biomass (mg biomass/kg soil)
 kB    =   biodegradation rate (mg hydrocarbon/kg
          soil-day)
 Y    =   cell yield (mg biomass/mg  hydrocarbon)
 kd    =   endogenous respiration rate (day"1)

Assuming that the biomass concentration achieves
steady state during bioventing,

                dX_n_K  Y-K v      (Eq-3-11)
                dt - u  r\b
                                 X
Solving:
                     X =
                         KbY
                          Kd
                                         (Eq. 3-12)
Little is known about the in situ cell yields or endogenous
respiration rates of hydrocarbon-degrading organisms,
but these parameters can be estimated based on ranges
reported in the wastewater treatment literature (Metcalf
                                                      and Eddy,  1979). An example for calculating  required
                                                      nutrients is shown in Example 3-3.
                                                      Example 3-3. Estimation  of Nutrient Requirements  in
                                                      Situ: For a given site, the following is assumed:
                                                        kB   -

                                                         Y   =
                                                         kd   =
                                                      Solving:
          10 mg/kg-day (typical rate found at
          bioventing sites)
          0.5 mg/mg
          0.05/day
                 kg-day
                                                                                   mg       mg
                                                                                       "
                                                                  -        0.05
                                                                           day

                                                      To sustain 100 mg/kg of bioniass, the nutrient require-
                                                      ments may be estimated from  biomass to nutrient
                                                      ratios. A variety of ratios is found in the literature. For
                                                      this  example,  a 100:10:1  ratio  of biomass:nitro-
                                                      gen:phosphorus is assumed. This ratio yields a nutri-
                                                      ent requirement of 10 mg/kg of nitrogen and 1 mg/kg
                                                      of phosphorus. Thus,  if the above  assumptions hold,
                                                      a site with at least these  levels of nitrogen and phos-
                                                      phorus initially should not be rate-limited by nitrogen
                                                      and  phosphorus.
Most soils  naturally contain nutrients in excess of the
concentrations  calculated in  Example 3-3. Therefore,
although the addition of nutrients may be desirable in
hopes of increasing biodegradation rates, field research
to date  does not indicate the need for these  additions
(Dupont et  al., 1991;  Miller  et al.,  1991). Therefore,
although nutrients are often  added  to bioremediation
projects in  anticipation  of  increased biodegradation
rates, field data to date do not show a clear relationship
between increased rates and supplied nutrients.

Concentrations of total Kjeldahl  hjtrogen (TKN) and
total phosphorus at the Bioventing Initiative sites and
                                                               <50 50-100  100-200 200-300 300-400 400-500 500-600 600-700  >700
                                                                              TK\ (mg,kg)


                                                      Figure 3-10. TKN measurements at Bioventing Initiative sites.
                                                   20

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    50 —

    45 -
"^
5   40 -

§"  35
25 -

20
   I
15 -

10 -A

 5

 0
  0
 a,
 I
                         400        600

                            TKN (me/kg)
                                            800   15002000
Figure 3-11.  Correlation  between  oxygen utilization rate  and
            TKN at Bioventing Initiative sites.
  "S  14-
  5.  10

  fr  8
        700
                      Total Phosphorus (mg/kg)

Figure 3-12.  Total phosphorus measurements at Bioventing In-
            itiative sites.
 &
 o
    50 -

    45 -

    40

    35

    30

    25

    20

    IS
                    600   800   I.OOO   1.200

                       Toial Phosphorus (mg/kg)
                                        1.400   1.600
                                                   3JDOO
Figure 3-13.  Correlation between oxygen utilization rate and to-
            tal phosphorus at Bioventing Initiative sites.
biological respiration at all sites when the most limiting
element, oxygen, was provided.

In controlled nutrient additions at Tyndall and Hill AFBs,9
no apparent increase in microbial activity was observed.
Therefore, there appeared to be  no benefit of nutrient
addition. The  relationship between oxygen utilization
rates and TKN and total phosphorus are shown in Fig-
ures 3-11 and 3-13, respectively. As illustrated  in these
figures, no  correlation  exists between phosphorus and
oxygen utilization  rates and only a weak relationship
exists between TKN concentrations and oxygen utiliza-
tion rates, again emphasizing that natural ambient  nutri-
ent levels seem sufficient for microbial activity.10

Figure 3-14 illustrates the range of iron concentrations
measured at Bioventing Initiative  sites. Iron concentra-
tions  varied greatly, with concentrations from less than
100 mg/kg to greater than 75,000 mg/kg. Soils in Hawaii
and Alaska  exhibited the highest iron contents. Although
iron is a nutrient  required for microbial growth, iron also
may react with oxygen to form iron oxides. Theoretically,
if a significant amount of iron oxidation occurs, the ob-
served oxygen utilization rate11 would not reflect micro-
bial activity  only.  Calculated biodegradation rates would
therefore be an  overestimate of actual  biodegradation
rates. Thus, background wells in uncontaminated areas
are recommended in bioventing applications in areas of
high iron concentrations. To date,  this study has shown
no correlation between  iron content and oxygen utiliza-
tion rates (Figure 3-15).

3.2.2.6  Contaminant Concentration

Contaminant concentration also may affect biodegrada-
tion of the contaminant itself. Excessive quantities of a
      <2,000
                                                                     2,000-4,000
                 4,000-8,000
                            12,000-16.000
                                                                                 8,000-12.000
                                                                                   Iron (mg/kg)
                                                                                             16,000-20,000
                                         20,000-25,000
                                                                                                           > 25,000
Figure 3-14.  Iron concentration measurements at Bioventing
            Initiative sites.
the corresponding relationship between oxygen utiliza-
tion rates are shown in Figures 3-10 through 3-13. Al-
though  optimal   ratios  of  carbon,  nitrogen,   and
phosphorus were not available at all sites, the natural
nutrient levels were sufficient to sustain some level of
 9 See Sections 4.1 and 4.2 for a detailed discussion of these sites.

10 See Section 5.2 for a discussion of the statistical relationship be-
  tween nutrients and oxygen utilization rates.

11 As measured by in situ soil gas oxygen concentrations.
                                                       21

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 -x,
 O
 ts
     0.   5000  10000 15000  20000 25000  30000  35000 40000    100000
                      Total Iron (mg/kg)

Figure 3-15. Correlation between oxygen  utilization rates and
           iron content at Bioventing Initiative sites.
contaminant can result in a reduction in biodegradation
rate because of a toxicity effect. Conversely, very low
concentrations of a contaminant also may reduce over1
all degradation rates because contact between the con-
taminant  and the microorganism  is  limited and the
substrate concentration is .likely below Smin.

In practice, petroleum hydrocarbons in fuel mixtures
do  not generally appear to be toxic to the  bioventing
process. Other more soluble compounds (i.e., pheno-
lics) or  less biodegradable compounds (i.e., TCE)
may exhibit a toxicity effect,  and reports indicate that
pure benzene may be toxic.  Although a general rela-
tionship  between bioventing rates and concentration
no  doubt exists,  the relationship is complex and not
fully understood. At sites where NAPLs are present
(soil concentrations above the  100  to 1,000  mg/kg
range), the bioavailable hydrocarbon is most probably
limited by solubilization, which  is linked to Raoult's
Law and, to an extent, is independent of total  hydro-
carbon concentration. Certainly,  the NAPL distribution
can affect the proportion of the soil in a site in which
biodegradation is occurring,  and at lower concentra-
tions, less soil may be in direct contact with NAPLs.
The reduction in biodegradation rates observed over
time on many sites is likely caused, at least in part, by
changes in the hydrocarbon makeup as more degrad-
able and more mobile compounds (i.e., benzene, tolu-
ene, ethylbenzene,  and xylenes)  are  removed.  At
lower hydrocarbon .concentrations where NAPLs are
not present, a decline in  rate would be expected with
time as the available substrate is removed.

3.2.2.7   Bioavailability and  Relative
         Biodegradability

Another important parameter  affecting the extent of in
situ bipremediation  is  bioavailability of  the contami-
nant^) of concern. Bioavailability  is. a term that de-
scribes  the  accessibility  of contaminants to  the
degrading populations.  Bioavailability consists of (1) a
 physical aspect related to phase distribution and mass
 transfer and (2) a physiological aspect related to the
 suitability of the contaminant as a substrate (U.S.  EPA,
 1993).  Compounds  with  greater aqueous solubilities
 and lower affinities to partition into NAPL or to sorb onto
 the soil  generally are  bioavailable to soil microorgan-
 isms  and  are  more readily degraded. For example,
 BTEX compounds are preferentially degraded relative
 to the larger alkanes  found in fuels. The most likely
 explanation for this is that BTEX compounds are more
 mobile and more soluble in pore water and therefore are
 more bioavailable.

 3.3   Compounds Targeted for Removal

 Any aerobically biodegradable compound, such as petro-
 leum  hydrocarbons, potentially can be degraded though
 bioventing. To date, bioventing has been applied primarily
 to petroleum hydrocarbons (Table 2-2); however, biovent-
 ing of PAHs (Lund et al., 1991; Hinchee and Ong, 1992;
 EPA,  1994a; Alleman et al., 1995) and bioventing applied
 to an acetone, toluene, and naphthalene mixture (Leeson
 et al., 1994) have been  implemented successfully.
 The key to bioventing feasibility in most  applications
 is biodegradability versus volatility of the compound.
 If the rate of volatilization greatly exceeds the rate of
 biodegradation, bioventing is unlikely to be successful
 because  removal  occurs primarily though  volatiliza-
 tion. This will occur most often in  cases where the
 contaminant is a fresh, highly volatile fuel. An unsuc-
 cessful bioventing application is unlikely to occur due
 to a lack of microbial activity. If bioventing is operated
 in an injection mode,  as this  manual  recommends,
 volatilized contaminants  may be biodegraded before
 reaching the surface, unlike during an extraction opera-
 tion.12 Figure 3-16 illustrates the  relationship between
 a compound's physicochemical properties and its po-
 tential for bioventing.

 In general, compounds with a  low  vapor pressure13
 cannot be successfully  removed by volatilization but can
 be biodegraded in a bioventing application if they are
 aerobically biodegradable. High vapor pressure  com-
 pounds are gases at ambient temperatures. These com-
 pounds volatilize too rapidly to be easily biodegraded in
 a bioventing system but are typically a small component
 of fuels and, because  of their high volatility, they will
 attenuate rapidly. Compounds with vapor pressures be-
tween  1  and 760 mm  Hg may be amenable to either
volatilization or  biodegradation. Within this  intermediate
12 See Section 2.1 of Volume II for a discussion of air injection versfts
  extraction considerations.

13 For the purposes of this discussion, compounds with vapor pres-
  sures below approximately 1 mm Hg are considered low, and
  compounds with vapor pressures above approximately 760 mm Hg
  are considered high.
                                                   22

-------
         a
         8
         3
         (0
         <0
         I
         o
         a,
                    Vapor Pressure
                    Too High to Easily Blovent
                                                                      /• cyclohexan»k   ,
                   Amendable to
                   Bioventing or
                   Vo.at.Son
                                                             mrthy1h«ane.    yknanel*    /\
                                                                                  '
                                   /£hiethyloctane»«   /    ethylbw
                                  Ar      / -.-r^'-' —/**••
                                  fj-J~—    S,~"   /    nmnutharmt
                                                                    Too Low to Volatlze
                                                                           10    100    1000
                10     10-°    10"6    10-*   10"3    10'2    10'1      1

                                   Aqueous  Solubility  (mmoles/litre)

                H - Henrys Law Coefficient (atm • mVmole)

Figure 3-16.  Relationship between contaminant physicochemical properties and potential for bioventing.
range  lie many of the petroleum  hydrocarbon  com-
pounds of greatest regulatory interest, such as benzene,
toluene, ethylbenzene, and xylenes. As can be seen in
Figure 3-16, various petroleum fuels are more or less
amenable to bioventing. Some components of gasoline
are too volatile to biodegrade easily but, as stated pre-
viously, are typically present  in low overall concentra-
tions  and are attenuated rapidly.  Most of  the diesel
constituents are sufficiently nonvolatile to preclude vola-
tilization, whereas the constituents of JP-4 jet fuel are
intermediate in volatility.
To be amenable to bioventing, a compound  must (1)
biodegrade aerobically at a rate resulting in an oxygen
                                                      demand greater than the rate of oxygen diffusion from
                                                      the atmosphere and (2) biodegrade at a sufficiently high
                                                      rate to allow in situ biodegradation before volatilization.
                                                      Practically, this means that low vapor pressure com-
                                                      pounds need not biodegrade as rapidly as high vapor
                                                      pressure compounds for bioventing to be successful.
                                                      Figure 3-17 illustrates this relationship. The actual fea-
                                                      sibility  of bioventing  is very site-specific, so Figures
                                                      3-16 and 3-17 should be used as general  guidelines
                                                      rather than absolutes.

                                                      Bioventing generally  is not considered appropriate for
                                                      treating compounds such as polychlorinated biphenyls
                                                      (PCBs)  and  chlorinated  hydrocarbons.  Through  a
                                                   23

-------
    -1,000,000,000

      -100,000,000

       -10,000,000

       -1,000,000

         -100,000

    a    -10,000

    •!•     -1,000

    I      -100

    I       "10

    !

               0

               1

              10

             100

            1,000
    1 3-ChlorofXOpena
    2 KchtoronielhanB
    3 Isoprena
    4 Melhyl chloride
    5 2,6-Dlnllrotoruene
    6 N-Nltrosodlmethylamlne
    7 2,3,4,6-TBlrachlorophenol
    8 Chlorolomi
    9 cls-1,2-Dlchloroethylane
   10 1,1-Olmelhyt hydrazlne
   11 trans-1,2-DlchlOK>ethylene
   12 Vinyl chloride
                                                              hlinuoranthene	..

                                                              i.hlanlhracerw	0fe
      Benzofghllfl

      Dibenz[a,h)anlhracenB	«*    J*

             Benzo[k]fluoranthenB

Benzo[a)anthracene

   Benzo[a]pyrene
        Chiysene
         o-Xylena
         m-Xylene
         p-Xylene
                          gamma-HexacNorocyctohexana (Llndane).
                                  Pentachlorophanol N
                               Heptachk>rN
                            Dlalhyl phlhalate
                           2-Nltrophenol^
                    1,2,4-Trlmelhylbenzenex
                    • DiBldrtn
        Benzo|b)fluoranlhane 9
     Fluoranthena .
             \
                      Chkmtane
\
                   |
                                m
1-Butanol   -
Melhyl Isobulyl ketone

        Formic ackJ
     Methyl elhyt ketone

             Ethanol
                  Penlachlorobenzane
              f
  • Aeenaphthlane"
       1 ,2,4,5-TelrachlofOoenzaiw

        rwxachloroetharw
            2,4-Dlnllrophenol
         1,2-Dlchlorobenzene % Pyrene
         2,6-Dlnltratoluene
                                                            TrlchtorofluoromelhanB
                                                            	•	L.
                          TelraclHoroothylene
                          1,2-DlcWoropropana
                        Trtchloroethylene
                        Cartoon tetrachlortde
                        1,1,1-Trtchloroethane
                        	I	
                                         1 Day
                                               1 Month
                                     Aerobic Half Life
                                                                                        1 Year
                                                                                                   5 Years
Figure 3-17.  Relationship between contaminant pressure and aerobic biodegradability.
cometabolic process,  however,  enhancement  of  the
degradation of  compounds  such as TCE through
bioventing  may be possible.  Laboratory studies have
shown that if toluene is present to provide the primary
source of carbon, organisms that grow on toluene may
be able to cometabolize TCE  (Wackett  and Gibson,
1992). More recently, Hopkins et al. (1993) demon-
strated TCE degradation in situ through the injection of
oxygen and phenol into an aquifer. TCE removal of 88
percent was observed in the field, indicating the poten-
tial for  cometabolic degradation  of  chlorinated com-
pounds in situ.

3.4  BTEX Versus TPH Removal in
      Petroleum-Contaminated Sites

In many areas, treatment of petroleum hydrocarbons is
based on   BTEX  compounds.  Typically,  these com-
pounds degrade rapidly during bioventing and, at most
sites, degrade to below detection limits within 1 year of
operation of a bioventing system. This trend was illus-
trated in a study at Tyndall AFB14 and has been con-
firmed at 81 sites  completing the 1-year testing under
the Bioventing Initiative.  At Tyndall AFB, two test plots
were studied with initial hydrocarbon concentrations of
5,100 and  7,700 mg/kg. After 9 months of bioventing,
                                       TPH decreased by 40 percent from the initial concentra-
                                       tion. Low-molecular-weight compounds such as BTEX,
                                       however, decreased  by more than 90  percent (Figure
                                       3-18). Low-molecular-weight compounds  were  prefer-
                                       entially degraded  over  heavier fuel components, which
                                       is consistent with  previous research (Atlas, 1986).

                                       If a  risk-based approach to remediation  is used that
                                       focuses on removing the soluble, mobile, and more toxic
                                       BTEX components of the fuel, remediation times can be
                                       significantly  reduced, making bioventing  an  attractive
                                       technology  for  risk-based  remediations.  In  addition,
                                       Bioventing Initiative  results illustrate that  BTEX com-
                                       pounds often initially are relatively low at many fuel-con-
                                       taminated sites. Data collected from the majority of the
                                       Bioventing Initiative sites demonstrate that more than 85
                                       percent of initial  soil samples contained  less  than 1
                                       mg/kg  of  benzene (Figure 3-19). An exception to  this
                                       may be  gasoline-contaminated  sites;  the majority of
                                       sites included in the Bioventing Initiative were contami-
                                       nated with heavier weight contaminants. Only 19 of 125
                                       Bioventing Initiative sites were contaminated  by gaso*-
                                       line or aviation gas (AVGAS).
                                       14 See Section 4.2 for a case history of the bioventing study at Tyndall
                                         AFB, Florida.
                                                       24

-------
                       300
                       200
                       1OO
Figure 3-18.  Results of soil analysis before and after venting from Plot V2 at Tyndall AFB, Florida.
75
70
65
£H
,— -. Ov
en
22 «c
.ta 33
C/3
•8 50
fe 45
| 40
Sz •«
O J->
^ -jrt
y

a 25
CT1
2 20
UH iU
15
10
5

























--
--







-












<








\
\
\
\
\
\

\

\
\
\
\
\
\

1












— .,
X

/^
^
X
X
X
X.
X
X
V


•H Benzene
- • 	 - - 1 - - - 1 -Toluene - - - -
	 	 	 jvVXJ ^Ethylbenzene
KXX Total Xylenes





— - - - - - - — - - 	 - --
	 . 	 _ 	 ^ 	





	 - - 	 „-----. . ... .- _ ,

^^T\
	 ;l~_ ^ _ ;; "^ 	 	 	 	 KL 	 	 	 ^ |
"T^x'-J^x j-^l J^x rf^"'r;"S"

1-5 5-10 10-20 20-50 50-200 >200
                                                          BTEX (mg/kg)




Figure 3-19.  Contaminant distribution at Bioventing Initiative sites.
                                                            25

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                                              Chapter 4
                                   Bioventing Case Histories
Four of the first well-documented bioventing studies
are presented in this chapter to illustrate significant
results that have contributed to the development of
bioventing,  the  Bioventing Initiative,  and this  docu-
ment. The development of the Bioventing Initiative
was largely based  upon the results from these four
early studies. Site 914, Hill AFB, Utah, was one of the
first bioventing systems studied. This study was de-
signed to examine the feasibility of biodegradation
through air injection and also to investigate the effect
of nutrient and moisture- addition on  biodegradation.
The second site was a bioventing system at Tyndall
AFB, Florida, initiated in  1990. This study was  short-
term (9 months)  but was designed to examine process
variables in more detail than was possible at Site 914,
Hill AFB. The third site discussed in this chapter was
conducted at Site 280, Hill AFB, Utah. This study was
initiated in 1991  as a bioventing site and was operated
for approximately 3 years. Research on air flow rates
and injection depth was conducted  at  this  site. The
fourth study presented in this chapter was conducted
at Eielson AFB, Alaska. This study was initiated in 1991
as a bioventing system and was operated for 3  years.
This study was conducted to examine the feasibility of
bioventing  in a subarctic climate and to evaluate the
effects of soil warming on biodegradation rates.

A case history of  the Fire Training Area, Battle Creek Air
National Guard  Base  (ANGB),  Michigan, also  is pre-
sented in  this chapter. This site was included  in the
Bioventing  Initiative, but additional 'Samples were col-
lected at the end of the 1 -year study as part of a sepa-
rate project. The  results from this study illustrate typical
installations and  results from a Bioventing Initiative site
and provide additional data  on BTEX  contamination
after 1 year of bioventing.

These case histories are not presented as design  exam-
ples because these studies were designed as research
efforts. In  fact, these studies  have been the basis for
development of current design practice as presented in
Volume  II  of this document. Details of each study are
presented in the  following sections.
4.1   Site 914, Hill AFB, Utah

A spill of approximately 27,000 gal of JP-4 jet fuel oc-
curred at Site 914 when an automatic overflow device
failed. Contamination was limited to the upper 65 ft (20 m)
of  a delta outwash  of the Weber River. This surficial
formation extends from the surface to a depth of ap-
proximately 65 ft (20 m) and comprises mixed sand and
gravel with occasional clay stringers. Depth to regional
ground water is approximately 600 ft (180 m);  however,
water occasionally  may be found  in  discontinuous
perched zones. Soil  moisture averaged less than 6 per-
cent by weight in the contaminated soils.

The collected soil samples had  JP-4 jet fuel concentra-
tions of up to 20,000 mg/kg, with an average concentra-
tion of  approximately 400 mg/kg  (Oak Ridge National
Laboratory,  1989). Contaminants were unevenly distrib-
uted to depths  of 65 ft (20 m). Vent wells were drilled to
approximately 65 ft (20 m) below the ground surface and
were screened  from 10 to 60 ft (3 to  20 m) below the
surface. A  background vent well was  installed in an
uncontaminated location in the  same geological forma-
tion approximately 700 ft (210 m)  north of the  site.

This system  originally  was designed  for SVE,  not
bioventing.  During the initial 9  months of operation,  it
was operated to optimize volatilization, while biodegra-
dation was  merely observed. After this period, air flow
rates were greatly reduced, and an effort was made to
optimize biodegradation and limit volatilization.

Soil vapor extraction was initiated in December 1988 at
a rate of approximately 25 cubic ft per minute (cfm) (710
L/min). The off-gas was treated  by catalytic incineration,
and initially the highly concentrated gas needed to be
diluted  to keep it below explosive limits and within the
incinerator's hydrocarbon operating limits. The venting
rate was gradually  increased  to approximately 1,500
cfm (4.2  x  104 L/min) as hydrocarbon  concentrations
dropped. During the period between December  1988
and November 1989, more than 3.5 x 108 ft3 (9.9 x 1010
L)  of soil gas were extracted from the site.
                                                  27

-------
In  November 1989, ventilation rates  were reduced to
between approximately 300 cfm and 600 cfm (8,500 to
17,000 LAnin) to provide  aeration for  bioremediation
while reducing off-gas generation. This change allowed
removal of the catalytic incinerators, saving approxi-
mately $13,000 per month  in rental and  propane costs.

Hinchee  and  Arthur  (1991)  conducted  bench-scale
studies using soils from this site and found that, in the
laboratory, both moisture  and  nutrients  appeared to
become  limiting  after aerobic conditions  had been
achieved. These findings led to  the addition  of first
moisture and then nutrients in the field. Moisture ad-
dition clearly stimulated biodegradation; nutrient addi-
tion  did not (Figure 4-1). The failure  to observe an
effect of nutrient addition could be explained by many
factors, including that the nutrients failed to move in
the soils, which is a problem  particularly for ammonia
and  phosphorus (Aggarwal et al., 1991); remediation
of the site was entering its final phase  and nutrient
addition  may  have been too late to result in  an ob-
served change; and/or nutrients simply may have not
been limiting.

During extraction, oxygen and hydrocarbon concentra-
tions in the off-gas  were  measured. To quantify the
extent of  biodegradation  at the site, the oxygen was
converted to an equivalent basis. This was based on the
stoichiometric  oxygen requirement for hexane minerali-
zation.1 Hydrocarbon  concentrations were determined
based on direct readings of a total hydrocarbon analyzer
calibrated to hexane.  Based on these calculations, the
mass of the JP-4 jet fuel as carbon removed (measured
as amount of carbon removed) was approximately 1,500
Ib  volatilized and 93,000  Ib biodegraded  (Figure 4-1).
           120
                                  After a 2-year period, cleanup and  regulatory closure
                                  were achieved (Figure 4-2).

                                  The results of this study indicated that aerobic biodegra-
                                  dation of JP-4 jet fuel did occur in the vadose zone at
                                  Site 914. Soil venting increased biodegradation at this
                                  site because, before venting, biodegradation appeared
                                  to  have been oxygen limited. The  SVE system, de-
                                  signed to volatilize the fuel, stimulated in situ biode-
                                  gradation with no added nutrients or moisture. In this
                                  study, approximately 15  percent of the  documented
                                  field removal observed at the site resulted from micro-
                                  bial-mediated mineralization to carbon dioxide. Addi-
                                  tional  biological  fuel  removal  .by  conversion  to
                                  biomass and degradation products no doubt occurred
                                  but was not  quantified.

                                  This study showed  that further studies of field biodegra-
                                  dation in unsaturated soils were needed to better under-.
                                  stand the effects of such variables as oxygen content,
                                  nutrient requirements, soil moisture, contaminant levels,
                                  and  soil  type on  the limitation and  optimization of
                                  bioventing of contaminated field sites. Also, further stud-
                                  ies of gas transport in the vadose zone were needed to
                                  ensure adequate design of air delivery systems.

                                  Further details of this study may be found in the following
                                  references: Dupont  et al., 1991; Hinchee et al., 1991b.

                                  4.2   Tyndall AFB, Florida

                                  A more controlled study than was possible at Site 914,
                                  Hill AFB, was designed at Tyndall AFB as a follow-up to
                                  the  Hill AFB research. The experimental area in the
                                  Tyndall AFB study was located at a site where past JP-4
                                  jet fuel storage had resulted in contaminated soils. The
                 o
                88
JFMAMJJASOND
                                   1989
                                                                                        - 0
JFMAMJ  JASON
               199O
                                                 Date
Figure 4-1.  Cumulative hydrocarbon removal and the effect of moisture and nutrient addition at Site 914, Hill AFB, Utah.
1 See Section 3.3 of Volume II for a discussion of this calculation.
                                                  28

-------
                     20
                  t
                  u
                  Q
                     40

xxxj
XXX.I
x/xx

XXXJ
-'XXJ
XXX ,1
/ / / /
XXX;
XXXJ
XXXJ

<5

-------
Operational data and biodegradation rates indicated that
soil moisture and nutrients were not limiting  factors in
hydrocarbon biodegradation for this site (Figure 4-3). The
lack of moisture effect contrasts with the Hill AFB findings
but most likely results from the contrasting climatic and
hydrogeologic conditions. Hill AFB is located in a high-ele-
vation desert with  a deep  water table. Tyndall AFB is
located  in a moist, subtropical environment, and at the
study sites, the water table was maintained at a depth of
approximately 5.25 ft (1.6 m). The nutrient findings support
field observations made at  Hill AFB that the addition of
nutrients does not stimulate biodegradation.  Based on
acetylene reduction studies, Miller (1990) speculated that
adequate nitrogen was present because of nitrogen fixa-
tion. The Hill and Tyndall AFB sites had been contaminated
for several years before the bioventing studies began, and
both sites were anaerobic. Nitrogen fixation, which is maxi-
mized under these conditions,  may have provided  the
required nutrients. In any case,  these findings  show that
nutrient addition is not always required.

The Tyndall AFB study included a careful evaluation of the
relationship between airflow rates and biodegradation and
volatilization. Researchers found that extracting air at the
optimal rate for biodegradation resulted in  90 percent re-
moval by biodegradation and 10 percent removal by vola-
tilization. They also found that passing the contaminants
volatilized in the off-gas  through clean soil resulted in
complete biodegradation of the volatilized vapors.

In situ respiration tests documented that oxygen con-
sumption rates  followed zero-order kinetics and that
rates were linear down to 2 percent to 4 percent oxygen.
Therefore, air flow rates  can  be minimized to maintain
oxygen levels between 2 percent and 4 percent without
fuel biodegradation, with the added benefit that lower air
       flow rates increase the,percentage of removal by biode-
       gradation and decrease the percentage of removal by
       volatilization.

       The study was terminated because the process moni-
       toring objectives had been met; biodegradation was still
       vigorous. Although the TPH had been reduced by only
       40 percent by the time of study termination, the low-mo-
       lecular-weight aromatics (the BTEX components) were
       reduced by more than 90 percent (Figure 3-18). Appar-
       ently, the  bioventing  process more rapidly removed
       BTEX compounds that other JP-4 fuel constituents.

       Results from this study demonstrated the effectiveness
       of bioventing for remediating fuel-contaminated soils,
       the ineffectiveness of moisture or  nutrient addition for
       increasing in situ biodegradation rates, and the impor-
       tance of air flow rates for optimizing  biodegradation over
       volatilization. This study demonstrated,  however, that a
       long-term bioventing  study was necessary to examine
       process variables. This led to the  initiation of the Site
       280, Hill AFB,  and the Site 20, Eielson AFB,  projects
       described in the following sections.

       Further details  of the Tyndall AFB study may be found
       in the following references: Hinchee et al., 1989; Miller,
       1990; Miller et al., 1991.

       4.3  Site 280, Hill AFB, Utah

       A key objective of the study at Site 280 was to optimize
       the injection air flow rates. These efforts were intended
       to maximize  biodegradation rates in JP-4 jet fuel-con-
       taminated  soils while minimizing  or eliminating volatili-
       zation.  The  site  studied  was a  JP-4 jet fuel spill at
       Hill AFB that had existed since the 1940s (Figure 4-4).
       The geology was similar to Site 914,  while average
                   100
                    80-
                    20
                                30
  90       120       150

Venting Time (days)
                                                                              180
210
Figure 4-3.  Cumulative percentage of hydrocarbon removal and the effect of moisture and nutrient addition at Tyndall AFB, Florida.
                                                    30

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                     F-16 Engine
                      Test Calls      V*
                               CW14
                       • SMP = Surface Monitoring Point
                       O  CW = Soil Vapor Cluster Well
                          A-A'= Cross Section Trace
                      <•• Projection of Cluster Well onto Cross Section Trace
Figure 4-4.  Schematic showing locations of soil gas monitoring points, surface monitoring points, and injection wells at Site 20,
           Hill AFB, Utah.
contaminant levels were slightly higher (Figure 4-5).
Vent wells were installed to a depth of approximately 110
ft, and ground water was at a depth of approximately
100ft.

From November 1992 through  January  1995, many
studies were conducted to evaluate low-intensity biore-
mediation at Site 280. These efforts included (1) varying
the air injection flow rates  in  conjunction  with  in situ
respiration tests and (2) testing surface emissions to
obtain information for system optimization.

Five airflow rate evaluations were conducted at Site 280
from 1991  through 1994 (28,  67, 67, 40, and 117 cfm
[790, 1,900, 1,900, 1,100,  and 3,300  L/min]).  In situ
respiration testing followed each evaluation. The 67-cfm
(1,900-L/min) study was repeated to include additional
soil gas monitoring points added to the site. Monthly soil
                                                     31

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    4790
           A (West)
           WWO CW9  WW7 CW7
WW8 CW8
                              Injection       A' (East)
                      CW4     Wall    CW1  CW5
    4770-
    4750-
    4730-
    4710
    4690-
    4670 -   Q
                                                                                                   4790
                                                                            ^            	-5	
                                                                                                 - 4770
                                                                                                 - 4750
                                                                                                   4730
                                                                                                   4710
                                                      - 4690
                                                      - 4670
              > Sand with Gravel and Clay
              'SlltySand
               Sand
D - Screened Interval
_  » Perched Water
    (Approx. Surface)
CW - Soil Gas Cluster Well
142 -  TPH In Soil dug/kg)
1.5 mg/L - TPH Cctn. In Ground Water
Figure 4-5.  Geologic cross-section showing known geologic features and soil TPH concentrations (mg/kg) at Site 280, Hill AFB,
          Utah.
gas monitoring was conducted at Site 280 to measure
the concentrations of oxygen, carbon dioxide, and TPH
at each sampling  point following system operation at
each of the different air flow rates.

Surface emissions tests were conducted during each air
injection  test and  while the air  injection system  was
turned off. In each surface emissions test, no significant
differences were found between the periods of air injec-
tion and no air injection. TPH soil gas levels measured
during the air injection periods averaged approximately
70 ppmv, while TPH soil gas levels during  resting peri-
ods averaged 42 ppmv. These averages were not found
to be statistically different. Likewise, surface emission
rates were not significantly different at different flow rates.

Final soil sampling was conducted in December 1994.
Results of initial  and final BTEX and TPH samples are
shown in Figures 4-6 and 4-7,   respectively.  Results
shown represent soil samples within a 0-ft to 25-ft radius
of the injection well and a 25-ft to 75-ft radius. In general,
BTEX and TPH concentrations decreased at all depths
within the 25-ft radius from the vent well, with the excep-
tion of the samples collected at a depth  of 90 ft to  100
ft. Samples  taken from this depth are  located at the
capillary fringe, and adequate aeration probably was not
possible. Samples collected outside of the 25-ft radius
           were less conclusive, indicating the lack of aeration in
           this area. Further details of the Site 280, Hill AFB, study
           may be found in the following reference: EPA, 1994b.

           4.4   Site 20, Eielson AFB, Alaska

           The objective of the Eielson AFB study was to install and
           operate an in situ soil bioremediation system to investi-
           gate the feasibility of using bioventing to remediate JP-4
           jet fuel contamination in a subarctic environment and to
           actively increase soil temperature to determine the de-
           gree to which increased soil temperature  can enhance
           the biodegradation rates  of JP-4 contaminants  in soil.
           This study comprised  four test  plots: (1)  a test plot in
           which heated ground water was circulated through the
           test plot (active warming test plot), (2) a test plot in which
           plastic sheeting was placed over the ground surface of
           the test plot during the spring and summer months to
           capture solar heat and  passively warm the soil (passive
           warming test plot), (3) a test plot in which heat tape was
           installed in the test plot to heat the soil directly (surface*
           warming  test plot),  and  (4) a control test plot,  which
           received  air injection but no soil warming (control  test
           plot).  In addition, an uncontaminated background loca-
           tion also received air  injection but no soil  warming to
           monitor natural background respiration rates. The site
                                                   32

-------
                    9
                    "So
                    \—'
                    §
                    o
                    u
                        1000
100
 10
          Initial Concentration
          Final Concentration
                                            1
                             0-10  10-20 20-30  30-40  40-50 50-60  60-70  70-80 80-90 90-100

                                                   Depth (ft)
                           a.   BTEX Concentration Within a 25 to 75 ft Radius of the Injection Well
                    •w
                     §

                    1
                        1000
 100 -
                              20-30    30-40    40-50   50-60    60-70    80-90    90-100
                                                   Depth (ft)
                           b.    BTEX Concentration Within a 0 to 25 ft Radius of the Injection Well


Figure 4-6.  Site average initial and final BTEX soil sample results at Site 280, Hill AFB, Utah.
soils were a sandy silt, with increasing amounts of sand
and  gravel with depth. Ground water was typically at
approximately 7 ft. Figure 4-8 illustrates site geologic
features  and typical construction details of the  active
warming test pilot, which is typical of other site installa-
tions as well.

Differences in soil temperatures have been significant
among the four test plots (Figure 4-9). When in opera-
tion, the active warming test plot consistently maintained
higher temperatures than the other test plots during the
winter months. In the passive warming test plot, plastic
sheeting increased soil temperature, with average soil
temperatures as high as 18°C (64.4°F) during the sum-
mer months, compared  with average temperatures of
approximately  10°C (50°F) in the control test  plot. A
significant  feature of this soil warming technique was
that the addition of plastic sheeting in the spring caused
a rapid increase in soil temperature, nearly 6 weeks to
8 weeks  sooner than in unheated test plots. This signifi-
                               cantly increased the period of rapid microbial degrada-
                               tion. During the winter months, the passive warming test
                               plot remained warmer than the control test plot.

                               Respiration rates were measured quarterly in each test
                               plot. Of particular interest were rates measured  in the
                               control test plot.  No substantial microbial activity was
                               expected to occur during the winter months in unheated
                               test plots because of the extreme temperatures. Signifi-
                               cant microbial activity was consistently measured in the
                               control  test  plot,  however, even in  winter when soil
                               temperatures are just below freezing (Figure 4-10). Res-
                               piration rates in  the passive warming test  plot  were
                               observed to increase nearly one order of magnitude as
                               soil temperature increased during the summer months,
                               indicating the success of  using  of plastic sheeting to
                               promote soil warming (Figure  4-10). Respiration rates
                               measured  in the active warming test plot were  higher
                               than those measured in the passive warming or control
                               test plot when warm water circulation was  operating.
                                                     33

-------
                        1000
                    t
                    u
                    I
                             0-10  10-20 20-30 30-40  40-50  50-60  60-70 70-80  80-90 90-100
                                                  Depth (ft)
                          a.     TPH Concentration Within a 25 to 75 ft Radius of the Injection Well
                     e
                     o
                     U

                     o.
                        10000
                         1000 -
                          100 -
10 -
                              20-30   30-40  40-50   50-60  60-70   70-80   80-90   90-100
                                                   Depth (ft)
                           b.     TPH Concentration Within a 0 to 25 ft Radius of the Injection Well

Figure 4-7.  Site average initial and final TPH soil sample results at Site 280, Hill AFB, Utah.
Warm water circulation was discontinued in fall 1993,
and as the soil temperature dropped, no significant mi-
crobial activity could be measured in the test plot during
the winter months. This phenomenon  is interesting  in
that it suggests that during the 2 years of soil heating,
microorganisms adapted to growth at  higher tempera-
tures  yet lost the ability to remain active in colder soils.
To  determine whether the microbial population could
adapt to cold temperatures given  time, a  final in situ
respiration test was conducted in January 1995. Signifi-
cant microbial activity was measured, comparable to the
control test plot, indicating either readaptation or recolo-
nization by the microbial population.
The surface warming test plot has shown promise as a
form of soil warming. Soil temperatures and respiration
rates were higher than temperatures or rates in either
the passive warming or control test plot and were similar
to those measured in the active warming test plot during
warm water circulation. These results indicate that the
use of heat tape may prove to be a more efficient means
                            of soil warming than hot water circulation because  it
                            avoids the problem of high soil moisture content.

                            An evaluation of cost versus remediation time was con-
                            ducted to evaluate the feasibility of soil warming. Costs
                            for the basic bioventing system in Table 4-1 were based
                            on costs calculated by Downey et al. (1994). Given that
                            average biodegradation rates were higher in the actively
                            warmed plots, overall remediation time would be more
                            rapid than in  the unheated test plots (Table 4-1). Al-
                            though  capital costs were higher in the active and sur-
                            face warming  test plots, the  rapid  remediation  time
                            results in lower total cost for power and monitoring. Final
                            costs based on dollars per cubic yard illustrate that costs
                            are comparable among the four treatment cells. These
                            results  indicate that implementation of a soil warming
                            technology over basic bioventing is not necessarily
                            based on  cost but  on  desired remediation time and
                            funds available for  operation and  maintenance versus
                            capital costs.

                            Final soil sampling at this site was conducted in August
                            1994. Results of initial and final BTEX and TPH samples
                                                    34

-------
            • Plastic Sheeting
Styroloam Insulation

      - Plywood

         r- Vinyl Cover
                                                  Three-Level
                                                Thermocouples
                                                                  Air Injection/Withdrawal Well


                                                                                   Three-level
                                                                                 Soil gas probe
                                                                            Ball
                                                                            Valve
    2-
     4-
     6-
    10
    12
    14
                                     Brown Sand
                                     and Gravel
        Soaker Hose
                                    Gray
                                   Sandy
                                    Silt
Water Table j
        '////////////////////, Gray Sand and Gravel '//,\
                                                                    4-'4-' 4- 4- <•' 4 •' 4-" •«•" 4-* 4-" *•'*•"•!•" 4-" 4-" 4-" 4-' *-'4'
                                                                                                 ,.- (-•«.•«.• 4.- <.-«.-i-'V-'V-"V-'V-'V
                                                                     fffff/fffftffttttf/tfrttf/tftttt
                                                                                                                    '
Figure 4-8.  Cross-section showing geologic features and typical construction details of the active warming test plot, Site 20, Eielson
            AFB, Alaska.
                       25
                       20
                       15
                    3
                    n
                    I
       10
                       -5
                            Active Wanning
                                                                                \  Surface Wanning
                                      •' \jj   Contaminated Control
                                                                     Uncontaminated Background
                          SEP NOV. JAN MAR MAY JUL  SEP  NOV. .JAN MAR MAY JUL SEP NOV  IAN MAR MAY JULY.
                           1991
                            1992
                                                    1993
1994
Figure 4-9.  Soil temperature in four test plots and the background area at Site 20, Eielson AFB, Alaska.
                                                           35

-------
                    10
                I
                "So
                 E
                 g

                1
                 00
                I
                3
                                           •  Active Warming
                                           T  Passive Warming
                                           •  Contaminated Control
                                           »  Surface Wanning
                        OCT'nJAN  APR   AUG  NOV., JAN  MAY  JULY  NOV ,, JAN  APR  JULY,
                        1991          1992                   1993

Figure 4-10.  Biodegradation rates in four test plots at Site 20, Eielson AFB, Alaska.
                          1994
Table 4-1 . Cost Analysis
Task
Site visit/planning
Work plan preparation
Pilot testing
Regulatory approval
Full-scale construction
Design
Drilling/Sampling
Installation/Startup
Remediation time required0
Monitoring
Power
Final soil sampling
Cost per yd0
of Soil Warming Techniques at Site
Basic Bioventing
(No Warming) ($)
5,000
6,000
27,000
3,000

7,500
15,000
4,000
9.4 years
30,550
13,160
13,500
25.50
20, Eielson AFB,
Active Warming
5,000
6,000
27,000
6,000

7,500
20,000b
26,000
2.8 years
9,800
9,800
13,500
26.12
Alaska3
($) Passive Warming ($)
5,000
6,000
27,000
3,000

7,500
15,000
10,500
6.9 years
24,150
9,660
13,500
24.86
Surface Warming ($)
5,000
6,000
27,000
3,000

7,500
15,000
13,000
3.4 years
11,050
17,000
13,500
24.21
" Costs are estimated bas.ed on a 5,000-yd3 contaminated area with an initial contamination level of 4,000 mg/kg.
b Requires installation and development of one well.
0 Estimated based on average biodegradation rates in four test plots.
are shown in Figures 4-11 and  4-12,  respectively. A
dramatic reduction in BTEX compounds was observed
at all sample locations, while TPH was reduced by an
average of approximately 60 percent.

Spatial variability in contaminant distribution and biode-
gradation rates makes quantitative comparison between
the test plots difficult;  however,  the results from the
active, surface, and  passive warming test plots clearly
demonstrate that these forms of soil warming have in-
creased biological  activity in these areas. In the active
and surface warming test plot, despite problems caused
by high oil moisture content, biodegradation rates con-
sistently have been higher than those measured  in
either the passive warming or the control test plot, even
though the control test plot appears to be more heavily
contaminated than  the active warming test plot. These
results have demonstrated the feasibility of bioventing
in a subarctic climate and the potential  advantages of
soil warming to decrease remediation times.

Further details of the Site 20, Eielson AFB study riiay be
found in the following references: Leeson et al., 1995;
EPA, 1994c.
                                                     36

-------
                    120
                    100 -
                     80 -

                     40 -
                     20
                      0
                         NS
ND
                              BND B NpjND BND| NE>B
                                    ND
                                                                              Initial BTEX
                                                                              Final BTEX
                                                  ND        NS   NS
                                          ND_  ND  ND    ND   ND  ND
                        4.5-5.0     5.5-6.0    6.5-7.0     7.5-8.0     8.5-9.0     9.5-10     10.5-11
                                                    Depth (ft)


Figure 4-11.  Site average initial and final BTEX soil sample results at Site 20, Eielson AFB, Alaska.
                  I
                  OB

                  a.
                  H
                     300 -
                     250 -
                     200 r
150
                      100
                      50
-


H Initial TPH
Final TPH
                         4.5-5.0
             5.5-6.0
                                             6.5-7.0
                                 7.5-8.0
                                                      Depth (ft)
                                      8.5-9.0
                                                                                     10.5-11
Figure 4-12.  Site average initial and final TPH soil sample results at Site 20, Eielson AFB, Alaska.
4.5   Fire Training Area, Battle Creek
       ANGB, Michigan

The Fire  Training Area,  Battle Creek ANGB,  was  in-
cluded as part of the Bioventing Initiative. An estimated
54,000 gal to 74,000 gal of mixed waste fuels, oils, and
solvents were burned  at this site  during  fire  training
exercises. Soils at the site consist of fine-to-coarse, silty
sand interbedded with gravel and cobbles (Figure 4-13).
Ground water is at a depth of approximately 30 ft.

As  dictated by  the  Bioventing Initiative  Protocol, one
vent well  and three  monitoring points were installed at
this site. The vent well  was installed to a depth of 30 ft
                                   with 20 ft of  0.04-in.  slotted screen. Each monitoring
                                   point consisted of three levels, with screens located at
                                   depths of 8 ft, 17 ft, and 27 ft.  Monitoring points were
                                   located at distances of 15 ft, 30 ft, and 50 ft away from
                                   the vent well.

                                   Initial treatability tests (an in situ  respiration test and a
                                   soil gas permeability test) were conducted to determine
                                   the feasibility of bioventing. Oxygen utilization rates ranged
                                   from  2.9 to 22  percent/day (2.0 to 15  mg/kg-day), with
                                   higher rates associated with more contaminated locations.
                                   Soil  gas permeability  testing demonstrated an  average
                                   permeability of approximately 230 darcy and a radius of
                                                      37

-------
               BC-MPC
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             LEGEND
              BC'MPA«   MONITORING POINT

               BC-VW
                     A   INJECTION WELL


                     92   FIELD SCREENING RESULTS FOR

                         TOTAL VOLATILE HYDROCARBONS (ppmv)


                         LABORATORY RESULTS FOR SOIL TOTAL
Tio]
                         PETROLEUM HYDROCARBONS (mg/kg)
J2	GROUNDWATER ELEVATION

	GEOLOGIC CONTACT,
            DASHED WHERE INFERRED

       ifa    MONITORING POINT
       T    SCREENED INTERVAL

            INJECTION WELL
            SCREENED INTERVAL
                    VC   VISUAL CONTAMINATION
Figure 4-13  Hydrogeologic cross-section of the Fire Training Area, Battle Creek, ANGB, Michigan.


influence of greater than 50 ft. These results indicated    and soil  gas samples were  collected.2  Although the

that both the microbial activity and the permeability were    number of soil3 and soil gas samples collected was not

conducive to an effective bioventing operation.            sufficient to allow for statistically significant comparis©n
Initial soil and soil gas samples were collected, and a    2 Blower operation was discontinued for 1 month before collecting soil
1-hp regenerative blower was installed at the Site  for     gas samples to allow time for soil gas equilibration.

continuous air injection in September 1992. The blower    3 Three initia| soN sampies were collected, but 29 final soil samples

was operated for 1 year, and in October 1993, final soil     were collected as part of an intrinsic remediation study.
                                                    38

-------
of the data, certain trends were observed. Final BTEX
and TPH soil gas concentrations were significantly lower
than initial measurements (Figure 4-14). Soil BTEX con-
centrations were  significantly lower after 1  year of
bioventing, while soil TPH concentrations changed little,
as expected (Figure 4-15). In addition, in situ respiration
rates declined  from the  initial  treatability test, which
indicates decreased contaminant levels.4 These results
illustrated the effectiveness  of  bioventing  at this site.
Because Michigan uses a risk-based standard for site
closure, this site is  likely to be  closed based on these
results.
                      30000 -
                                        Initial Concentration
                                                                       Final Concentration
Figure 4-14.  Initial and final soil gas concentrations at the Fire Training Area, Battle Creek, Michigan.
                                                          4 See  Chapter 4 of Volume II for a detailed  discussion of in situ
                                                           respiration rates and site closure.
                                                       39

-------
              60

              50

              40

              30

              20

              10
                                                               • Initial
                                                               0 Final
                                                      NS = Not sampled
                                                      NO = Not detected
                   NS NO NS ND  NS ND NS NO
             I
                                                      ND NS ND  NS NO  NS ND  NS ND  NS ND NS |
                                                                                                NS ND  NS
                    2-2.5
4-4.5
10-10.5        18-19
 Depth (ft)
21.5-22.5
27-27.5
               50000
               45000

               40000

               35000

f               30000
           _  25000

           £  20000

               15000 i

               10000

                5000 i
                            NS
                                                                  • Initial
                                                                  El Final
                                                        NS = Not sampled
                                                        ND = Not detected
                                         NSND
                                                           NS ND  NS
                                                                        NSND  NSND   NS    NSND  NS
                                                                                                       NSND
                       2-2.5
   44.5
  10-10.5        18-19

    Depth (ft)
                                                                                   21.5-22.5
                                                                27-27.5
Figure 4-15.  Initial and final soil concentrations at the Fire Training Area, Battle Creek, Michigan.
                                                          40

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                                              Chapter 5
                          Analyses of Bioventing Initiative Results
In May 1992, the U.S. Air Force began the Bioventing
Initiative to examine bioventing at 55 contaminated sites
throughout the country. In December 1992, the program
was increased to  more than 130 sites  because of in-
creased demand by Air Force managers. To date, data
have been collected from 125 contaminated sites at a
total of 50 Air Force bases, one Army base, one Naval
installation, and one  Department of Transportation in-
stallation. Sites are located in 35 states and in all 10 EPA
regions. Figure 2-2 illustrates the locations of Bioventing
Initiative sites to date. The selected sites represent a
wide range of contaminant types  and concentrations,
soil types, contaminant depths, climatic conditions, and
regulatory frameworks.  Sites were selected based on
contamination  level  (preferably  greater than  1,000
mg/kg TPH). Selection was not biased regarding factors
such as soil type or climatic conditions so that bioventing
potential  could be properly evaluated under favorable
and unfavorable conditions.

A Bioventing Test Protocol was developed  to provide
strict guidelines for treatability testing and  bioventing
system design. The Bioventing Test Protocol was peer
reviewed and was also reviewed by EPA Headquarters
and  the  EPA  National  Risk Management Research
Laboratory. Using the Bioventing  Test Protocol, initial
testing was  conducted  at each site to determine the
feasibility of bioventing.  Based on the initial testing, a
decision was made about whether to install a bioventing
system for 1 year of operation. At the majority of sites
(95 percent), a bioventing system was installed for the
1 -year operational period. At the end of this period, each
Air Force base could either elect to keep the bioventing
system in operation or remove it if the site was deemed
to be sufficiently remediated.

At each site in which a bioventing system was installed, a
series of data was collected as described in Section 2.3:

• Initial site characterization data consisting of soil and
  soil gas sampling,  in situ respiration rate testing re-
  sults, and soil gas permeability testing results.

• Six-month in situ respiration testing results.

• One-year soil and soil gas sampling and in situ res-
  piration testing  results. Data from the initial  testing
  are summarized in Appendix B and have been used
  in the statistical analyses as described in Section 5.2.
  A summary of the results to date and potential impli-
  cations are presented in the following sections.

5.1   Estimate of Contaminant Removal at
      Bioventing Initiative Sites

At all Bioventing Initiative sites in which a blower was
installed and operated for 1 year, initial and final soil and
soil  gas  BTEX and TPH concentrations have been
measured. The approach was to compile a limited num-
ber of samples from each site and statistically analyze
for trends to avoid known spatial variability. Distribution
of soil and soil gas BTEX and TPH concentrations from
the initial  and 1-year sampling events are shown in
Figures 5-1 through 5-4, respectively. The average soil
and  soil gas BTEX and TPH concentrations across all
sites are shown in Figure 5-5. In  general, the most
dramatic reductions were observed in BTEX removal in
both  soil and soil gas  samples. As an example,  soil
results from Site 3,  Battle Creek ANGB, are shown in
Figure 5-6. BTEX concentrations after 1 year of biovent-
ing operation are very low and are no longer a source
of ground water contamination; therefore, site closure is
now  a viable option for this site.

The  objective of the 1-year sampling event was not to
collect the large number of samples  required for statis-
tical  significance for a single  site. Rather, the sampling
event was conducted to give a qualitative indication of
changes  in contaminant mass.  Soil gas samples are
somewhat similar to composite samples in that they are
collected over a wide area. Thus, they indicate changes
in soil gas profiles  (Downey and Hall, 1994). Blower
operation was discontinued 30 days before sample col-
lection to allow for soil gas equilibration. In contrast, soil
samples  are discrete point  samples subject  to large
variabilities over small distances/soil types.  Given this
variability, coupled with known sampling and analytical
variabilities, many samples at a single site would have
to be collected to conclusively determine real  changes
in soil contamination. Because of the limited number of
samples, these results should not be viewed as conclu-
sive  indicators of bioventing progress or evidence of the
success or failure of this technology.
                                                   41

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                                                                                      Initial Concentration

                                                                                      Final Concentration
                                     <0.1    0.1-1
1-5    5-10     10-25  25-100  100-250 250-500  >500
      Concentration (ppmv)
Figure 5-1.  Soil gas BTEX concentrations at Bioventing Initiative sites: initial and 1-year data.
                                                                                     Initial Concentration
                                                                                     Final Concentration
                                     <10        so-ioo      500-1000    2500-5000  10,000-20,000   >50,000
                                            10-50       100-500      1000-2500  5000-10,000  20,000-50,000

                                                          TPH Concentration (ppmv)


Figure 5-2.  Soil gas TPH concentrations at Bioventing Initiative sites: initial and 1-year data.
                                70



                                60



                            I  50



                             °  40



                            t  30



                             I  20


                                10





-
7




^






pn

^

xi


ff Initial Concentration
Y///\ Final Concentration



1 1 II I . 1 1 ill
                                      <0.1        1-5        10-20      30-40      50-75     100-200       >500
                                           0.1-1.0      5-10       20-30      40-50     75-100    200-500

                                                              Concentration (rug/kg)


Figure 5-3.  Soil BTEX concentrations at Bioventing Initiative sites: initial  and 1-year data.
                                                                  42

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z
Sx
                               50

                               45

                               *°
                               35

                               30

                               25

                               20
                               15

                               10

                                 5

                                 0
                                              Initial TPH Concentration (mg/kg)
                                              Final TPH Concentration (mg/kg)
                                                50-250     500-1000    2000-5000   7500-10,000   15,000-20,000 25,000-30.000
                                                     250-500    1000-2000   5000-7500  10.000-15.000  20.000-25,000  > 30.000
                                                              Concentration (mg/kg)
Figure 5-4.  Soil TPH concentrations at Bioventing Initiative sites: initial and 1-year data.
                                              TPH      BTEX
                                             ^| Initial Concentration
                                                  TPH      BTEX
                                                     1 -Year Concentration
Figure 5-5.  Average soil and soil gas BTEX and TPH concentrations at Bioventing Initiative sites: initial and 1-year data.

                                                                                                               50
                        15000
                        12000
                    .3   9000
                         6000
                    £   3000
                                     u.ooo
                                                                                      BTEX
                                                                                                               40
                                                                                                               30
                                                                                                               20
                                                                                                               10
                                 H Initial Concentration (mg/kg)        YZ/2\ Final Concentration (rag/kg)

Figure 5-6.  Initial and final soil sampling results at Site 3, Battle Creek ANGB, Michigan.
                                                                   43

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If a risk-based approach to remediation is  used that
focuses on removing the soluble, mobile, and more toxic
BTEX component of the fuel, remediation times can be
significantly  reduced. As discussed in the Tyndall AFB
case history,1 the BTEX fraction was removed preferen-
tially over TPH. The potential for bioventing to preferen-
tially remove BTEX makes this technology suitable for
risk-based remediations.  In addition, the low levels of
BTEX that have been  encountered at the majority of
Bioventing Initiative sites further supports an  emphasis
on risk-based remediation (Figure 5-7). Over 85 percent
of the initial soil samples contained less than 1 mg/kg of
benzene.
                       10-20   20-50  50-100
                      Tool BTEX (mg/kg)
                                       100-200  >200
Figure 5-7.
          Average BTEX concentrations at Bioventing Initia-
          tive sites.
5.2  Statistical Analysis of Bioventing
      Initiative Data

One primary objective of the Bioventing Initiative was to
develop a  large database  of bioventing systems that
could be used to determine which parameters are most
important in evaluating the feasibility of bioventing. This
is the largest  field  effort  to  date  where  data  have
been collected in a consistent manner, allowing for di-
rect comparison of results across sites. Results of the
statistical analyses can be  used to evaluate which soil
measurements should be taken and, if bioventing per-
formance is poor, which parameters  can be  adjusted to
improve performance.

Data generated from the Bioventing  Initiative were sub-
jected to  thorough statistical analyses  to determine
which parameters most influenced observed  oxygen
utilization  rates. Procedures  used for conducting the
statistical analyses and the results of these analyses are
presented in the following sections.

5.2.1  Procedures for Statistical Analysis

Data collected from 125  Bioventing Initiative sites have
been analyzed for this study. The study involved in situ
respiration test data, soil gas permeability test data, and
soil chemistry and nutrient data from each site. Several
parameters  were measured in the soil samples. The
statistical analyses had five specific objectives:

• To develop a consistent statistical approach for cal-
  culating the oxygen utilization and  carbon dioxide
  production rates from the  in situ respiration data.

• To characterize the oxygen utilization rate as a func-
  tion of parameters measured during  initial testing.

• To determine the relationship between carbon dioxide
  production rate and pH or alkalinity by characterizing
  the ratio of oxygen utilization rate to carbon dioxide
  production rate as a function  primarily  of pH and
  alkalinity.

• To characterize soil gas permeability as a function of
  particle size and moisture content.

• To compare primarily TKN concentrations at contami-
  nated sites with those at uncontaminated background
  areas.

Averages for oxygen utilization and carbon dioxide pro-
duction  rates and soil parameters were computed for
each site. All subsequent analyses were performed on
the site averages. Table 5-1 displays  the  parameters
included in the statistical analyses, their units, and trans-
formations performed on these parameters wherever
necessary.

Data were stored in Statistical Analysis System (SAS)
databases, and all statistical manipulations and analy-
ses were conducted  using the SAS software. Methods
used for characterizing the data and the final regression
model are presented in the following sections for each
of the listed  objectives..

5.2.2   Calculation of Oxygen Utilization and
        Carbon Dioxide Production Rates

A statistical analysis was conducted to consistently cal-
culate oxygen utilization and carbon dioxide production
rates. A linear time-related change in oxygen and carbon
dioxide  levels that is characterized by a constant (or
zero-order) rate is typical of most sites. In some sites,
however, a two-piecewise linear change is observed. An
initial rapid rate is observed followed by a  leveling off.
This change in  rates generally occurs once oxygen
becomes limiting, typically below 5 percent to 10 percent
oxygen.

The two-piecewise regression model, with a slope change
at time t0, was fitted to the oxygen (and carbon dioxide)
versus time data obtained at every monitoring point. The
piecewise regression  model  is presented below:
1 See Section 4.2 for a presentation of this case history.
                                                                    RI = a + p t|
                                           (Eq. 5-1)
                                                   44

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Table 5-1.  Data Parameters Included in the Statistical Analyses
Category
In Situ Respiration Rates


Soil Parameters






'








Other
Parameter
Oxygen utilization rate
Carbon dioxide production rate
Ratio of the carbon dioxide
production rate to oxygen
utilization rate
Soil gas TPH
Soil gas BTEX
Soil TPH
Soil BTEX
PH
Alkalinity
Iron content
Nitrogen content
Phosphorus content
Moisture content
Gravel
Sand
Silt
Clayc
Soil gas permeability
Soil temperature
Season (time of year)
Units
%/hr
%/hr
No units
ppmv
ppmv
mg/kg
mg/kg
No units
mg/kg as CaCOs
mg/kg
mg/kg
mg/kg
% weight
% weight
% weight
% weight
% weight
Darcy
Celsius
Day
Transformation3
Log
None
Square root
Log
Log
Log
Log
Log
Log
Log
Log
Log
None
None
None
None
None and log
Log
None
None
Acronymb
02
CO2
Ratio
tphsg
btexsg
tphs
btexs
PH
ALK
IRN
NIT
PHO
MOI
GRA
SAN
SIL
CLA
PRM
TMP
Season
 a Transformation was applied to the parameter for purposes of statistical analysis.
 b Acronym is used for the parameter in this report.
 0 The correlations presented in Figures 5-9 through 5-14 and Figure 5-17 are based on untransformed clay.
       R, = (a + pto, + (P + 8) (tj - t0)   tj > t0
                                           (Eq. 5-2)
 where i =  number of observations at each monitoring
 point (1, 2,...), and where:
 RJ = measured ith oxygen or carbon dioxide level at
      time t| (%)
  a = oxygen or carbon dioxide level at initial time
  p = rate of change of oxygen or carbon dioxide
      level with time (%/hr)
  5 = increase or decrease in the rate  of change at
      time t0 (%/hr)
  t0 = time at which the slope change occurs (hr)
 The piecewise regression model was implemented us-
 ing the nonlinear regression  procedure (NLIN  proce-
 dure) in the SAS software package.

 The parameter 5 in  the  above  model measures  the
 increase or decrease in the slope at time t0. Therefore,
 the statistical significance of confirmed the suitability of
 a two-piecewise model fitted  to  the data. The  rate of
 oxygen utilization (or carbon  dioxide production) was
 estimated  from the slope of  the first linear piece, p,
 wherever 8 was statistically significant at  the 0.05 sig-
 nificance  level.  For example,  Figure 5-8  presents  the
 piecewise  linear model fitted to oxygen data at a moni-
toring point at Site FSA-1, AFP 4,  where p was esti-
mated to be -1.1 percent/hr.

In cases where 8 was not significant at the 0.05 level, a
linear regression model of the following form was fitted
to the data:
             RI = a + pt|
for all
(Eq. 5-3)
where:
the rate of oxygen utilization (or carbon dioxide produc-
tion) was determined from the slope of the straight line,
P.
For cases in which six or fewer observations were avail-
able at a monitoring point, or where the oxygen levels
exhibited virtually no change over a short initial period
followed by a linear change, the piecewise analysis was
not attempted. In such cases, a linear regression model,
as  described  above, was fitted.  In these cases,  the
suitability of the linear model was confirmed by inspec-
tion of the model fit  to observed data.

5.2.3   Correlation of Oxygen Utilization Rates
        and Environmental Parameters

A preliminary  analysis of  the untransformed data was
performed in which a regression model was fitted to the
oxygen utilization rate using forward stepwise regression.
                                                    45

-------
                   20.0 r
                   15.0
                   10.0
                 g
                 o
                 c
                 a
                 g
                    5.0
                    0.0
                                                                 Observed Oxygen Level
                                                                 Predicted Oxygen Level
                                                                Base   AFP 4
                                                                Site    Site FSA-1
                              \ Oxygen Rate = 1.1%/hour
                                                          I
       I +   I
                               10   15   20  25   30   35  40   45   50   55   60  65   70  75
                                                   Time (hours)
Figure 5-8. Use of piecewise analysis of oxygen utilization data from Site FSA-1, AFP 4, Texas.
This model accounted for the effects of the soil parame-
ters and their interactions. To reduce the effect of multi-
collinearity among the parameters on the fitted model,
soil gas BTEX levels and gravel were excluded from the
modeling. In other words, soil gas BTEX was highly
correlated with soil gas TPH, and therefore, it was con-
cluded that the effect  of soil gas BTEX levels on  the
oxygen utilization rate can almost completely be  ex-
plained by soil gas TPH concentrations. Also, because
the particle size levels added up to a constant value (100
percent), the effect of gravel was assumed to be redun-
dant in the modeling.
Fitting the regression model to the oxygen utilization rate
revealed that soil particle sizes and permeability had a
dominating influence on the oxygen utilization rate; that
is, low levels of permeability and  sand,  and high levels
of silt and clay appeared to correlate strongly with high
oxygen utilization rates.
To determine  whether a handful of sites  was unduly
influencing the statistical modeling, sites with high oxy-
gen  utilization  rates were  examined in detail.  Seven
sites in the analyses had extremely high oxygen utiliza-
tion rates, well above average rates from other sites. A
two-sample t-test was performed on each parameter
(e.g., sand, nitrogen) to determine whether the average
value of the parameter over the seven sites was different
from the corresponding average for the remaining sites.
This  analysis  revealed  statistically significant differ-
ences in particle size, soil gas permeability, and soilTPH
concentrations between the two groups of sites (Table
5-2). The results of this analysis led to the determination
that the seven sites with  extremely high oxygen utiliza-
tion rates were atypical with respect to their levels of
particle size, soil gas permeability, and soil TPH concen-
trations.
Table 5-2.  Parameters That Distinguish the Seven Sites
          With High Oxygen Utilization Rates From the
          Remaining Sites
Parameter
                         Level of Parameter in Seven
                         Sites Relative to Other Sites
Sand

Silt

Clay

Soil gas permeability

Soil TPH
Lower

Higher

Higher

Lower

Lower
To reduce the influence of these  seven sites  on the
model for oxygen utilization rate, the log transformation
of the oxygen utilization rate was taken. Additionally, the
log transform resulted in more normally distributed data
for the oxygen utilization rate. Sites with oxygen utiliza-
tion rates near zero, however, are artificially inflated in
importance as a result of the transformation. To elimi-
nate this artificial effect, all the  log transformed values
of the oxygen rate below -2.5 were censored (i.e., set to
a constant value of -2.5). Censoring was based on visual
inspection of the log transformed data.
Subsequently, the log transform of some soil parameters
was  taken if the data  for the parameter were not well
represented by  a normal distribution. Normality in the
data was checked using the Shapiro-Wilk test for nor-
mality and by observing histograms  and normal prob-
ability plots.
As a preliminary step to determine the influence of soil
parameters on oxygen utilization rate, correlations be-
tween each soil parameter and the  oxygen  utilization
rate  were examined. This was  conducted  to examine
strong relationships between oxygen  utilization  rates
                                                    46

-------
              02
                        rol io
                                    IRN
                                               NIT
                                                          PRO
                                                                    UOI
                                                                                PH
                                                                                          ALK
                02 m log 02 Rate   Ratio - (C02 Ratt/O2 Rat*)1*  IRN  =- log Iron   NIT - log Nitrogen
                  PHO * log Phosphorus   MOI = Moisture   PH » log pH   ALK - log Alkalinity
                              Z1
                                         90%
60%
30%
0%
                                         Key to Correlation Scattarplots.
Figure 5-9.  Oxygen  utilization  rates, oxygen to  carbon dioxide rate ratios, element concentrations, moisture content, pH,  and
          alkalinity site average correlation scatterplot.
                                                     47

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                    02
                            ratio
                                      btexsg
                                                 Iphsg
                                                           btexs
                                                                      tphs
                                                                                 TUP
                                                                                           UOI
          02 - log 02 Rate   Ratio = (C02 Rate/O2 Rate)54   btexag - log BTEX in Soil Gas   tphsg = log TPH in Soil Qa*
                 btexs » log BTEX in Soil   tphs = log TPH in Soil  TMP = Soil Temperature   MOI =  Moisture
                                  Z1
                                            90%
60%
30%
0%
                                            Key to Correlation Scatterplots.
Figure 5-10.  Oxygen utilization rates, oxygen to carbon dioxide rate ratios, contaminant concentrations, temperature and moisture
            content site average correlation scatterplot.
                                                        48

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              02
                       rat io
                                   GRA
                                              SAN
                                             ++
                                                         SIL
                                                                    CLA
                                                                              UOI
                                                                                         PRM
           02 = log 02 Rate  Ratio =• (C02 Rate/02 Rate)54    GRA = Gravel   SAN - Sand    SIL - Silt
                       CLA - Clay   MOI - Moisture   PRM - log Soil Gas Permeability
                             Z1
                                        90%
60%
30%
0%
                                       Key to Correlation Scatterplots.
Figure 5-11.  Oxygen utilization rates, oxygen to carbon dioxide rate ratios, particle size, moisture content, and soil gas permeability
           site average correlation scatterplot.
                                                     49

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             IRN
                          NIT
                                      PHO
                                        +
                                                  GRA
                                                              SAN
                                                                           SIL
                                                                                       CIA
                 IRN - log Iron    NIT - log Nitrogen   PHO - log Phosphorus   GRA =» Gravel
                                  SAN - Sand   SIL = Silt   CLA - Clay
                            Z1
                                       90%
60%
30%
0%
                                      Key to Correlation Scatterplots.
Figure 5-12.  Element concentrations and particle size site average correlation scatterplot.
                                                    50

-------
           btexsg
                      tphsg
                                btexs
                                           tphs
                                                      GRA
                                                                SAN
                                                                          SIL
                                                                                        i+
                                                                                        +.1
                                                                                    CLA
               btexsg - log BTEX in Soil Gas   tphsg = log TPH in Soil Gas   btexs » log BTEX Soil
                tphs - log TPH in Soil   GRA = Gravel   SAN » Sand   SIL = Silt   CLA - Clay
                           Z1
                                      90%
60%
30%
0%
                                     Key to Correlation Scatterplots.
Figure 5-13.  Contaminant concentrations and particle size site average correlation scatterplot.
                                                  51

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                PH
                              ALK
                                            GRA
                                                          SAN
                                                                         SIL
                                                                                       CLA
          PH  = log pH   ALK • log Alkalinity   GRA - Gravel   SAN = Sand   SIL =• Silt   CLA - Clay
                             Z1
                                        90%
60%
30%
0%
                                        Kay to Correlation Scattarplots.
Figure 5-14.  pH, alkalinity, and particle size site average correlation scatterplot.
                                                    52

-------
and  measured environmental parameters to assist in
developing a statistical  model describing performance
at the Bioventing Initiative sites. First, the log transfor-
mation of the oxygen utilization rate and some of the soil
parameters was taken to obtain more normally distrib-
uted data on each parameter (Table 5-1).  After these
transformations, the data for each parameter were plot-
ted against the corresponding data for each of the other
parameters.

Figures 5-9 through 5-14 display the magnitude of the
correlations  among data parameters. Specifically, Fig-
ures 5-9 through 5-11 display the correlations between
the oxygen utilization rate and the soil parameters, and
Figures 5-12 through 5-14 present the  correlations be-
tween soil parameters. In each figure, ellipses are drawn
on each plot  containing 95 percent of the estimated
bivariate distribution. The plots with narrow ellipses rep-
resent pairs of elements that have a strong observed
correlation. Pairs of elements that are  positively corre-
lated have the ellipse with the major axis running from
the lower  left to  the upper right, while negative correla-
tions are indicated by the major axis running from the
lower right to the upper left. The  magnitude of the cor-
relation can be inferred from the shape of the ellipse by
comparing it with the key figure. In the  key figure, com-
parable ellipses are displayed  for distributions with
known correlations of 90 percent, 60 percent, 30 per-
cent, and  0 percent.
For  example,  Figures 5-9 through 5-11 show that the
oxygen rate is most positively correlated with  nitrogen
(Figure 5-9, correlation  coefficient r = 0.40), moisture
(Figure 5-9, r = 0.30), and soil gas TPH concentrations
(Figure 5-10,  r = 0.20)  and negatively correlated with
temperature (Figure 5-10, r = 0.25) and sand (Figure
5-11, r = 0.25). This indicates that high levels of nitrogen,
moisture, and  soil gas TPH concentrations, but low lev-
els of sand  and temperature, appear to correlate with
high oxygen utilization rates.
The correlation  between soil temperature and oxygen
utilization  rate is of little practical significance  in this
analysis, however. At a given site, temperature has been
shown to  correlate well with microbial activity, having
peak activity in summer months and low activity in winter
months. This relationship is also very site-specific, how-
ever. In other words, microorganisms  in Alaska show
peak activity in summer months with comparable oxy-
gen  utilization rates to those of organisms from more
temperate climates; however, soil temperatures are sig-
nificantly different. Therefore, correlating rates with tem-
perature under such different climatic conditions as was
seen at Bioventing Initiative sites  is impossible.

Among the soil  parameters, the  correlation coefficient
between soil gas BTEX and TPH concentrations is 0.92
(Figure 5-9) and that between pH and alkalinity is 0.75
(Figure 5-8). The correlations between the particle sizes
(sand, silt, and clay), moisture, and soil gas permeability
are also pronounced.

After taking the log transformation, a second regression
model was fitted to the oxygen utilization rate  using
stepwise regression. Finally, the effect of a cyclic sea-
sonal component on residuals obtained  from the fitted
regression model was investigated by including the date
of the initial in situ  respiration test.

The final regression model for oxygen utilization rate is:

    log(O2) = -2.7 + 0.39 log(NIT) - 0.108 (MOI) +

             0.017log(TPHsg)*MOI-

              0.004 log (TPHsg) * TMP      (Eq. 5-4)

Each  effect in the above model is statistically significant
at the 0.05 significance level. Note that the effects ap-
pearing in the model  are consistent with relationships
observed in the bivariate setting. The model explains 41
percent of the variability in the log-transformed oxygen
utilization rate (i.e., a 64-percent correlation between the
observed and model-predicted log transformed oxygen
rates). Figure 5-15 illustrates actual versus predicted
oxygen utilization rates based on model predictions. As
shown, the model appears to explain mid-range oxygen
utilization  rates fairly well but does not predict low oxy-
gen utilization rates as accurately. This may be due to
an  effect on  microbial activity that was  not measured
during the Bioventing  Initiative and,  therefore, was un-
explained in the model.

5.2.4   Correlation  of Oxygen Utilization and
        Carbon Dioxide Production  Rate Ratios
        With Environmental Parameters

Because in situ  biodegradation rates are measured in-
directly through  measurements of soil gas oxygen and
carbon dioxide concentrations,  abiotic processes that
affect oxygen and  carbon dioxide concentration will af-
fect measured biodegradation rates. The factors that may
most  influence soil gas oxygen and carbon dioxide con-
centrations are soil pH, soil alkalinity, and iron content.

At nearly  all  sites  included in the Bioventing Initiative,
oxygen utilization  has  proven  to be a more useful
measure of  biodegradation rates than carbon dioxide
production. The biodegradation rate in mg of hexane-
equivalent/kg of soil per day  based on carbon dioxide
production usually is less than can be accounted for by
the oxygen disappearance. A study conducted at the
Tyndall AFB site was an exception. That site had low-al-
kalinity soils and low-pH quartz sands, and carbon diox-
ide production  actually resulted in a  slightly  higher
estimate of biodegradation (Miller, 1990).

In the case  of higher pH and higher alkalinity soils at
such  sites as Fallon NAS and Eielson AFB, little or no
                                                    53

-------
                      £
                      ^
                      5
                      1
                      •I
                      a
                      a.

                      I
                        o.oi
                                                      ••
                            -(•-•
                           0.01
  0.1                    1
Actual Oxygen Utilization Rate (%/hr)
 Figure 5-15.  Actual versus model-predicted oxygen utilization rates.
 gaseous carbon  dioxide production1  was  measured
 (Hinchee et al., 1989;  Leeson et al.,  1995). This may
 result from the formation of carbonates from the gase-
 ous evolution of carbon dioxide produced by biodegra-
 dation  at  these sites,  van  Eyk and Vreeken (1988)
 encountered a similar phenomenon iii their attempt to
 use carbon dioxide evolution to qua'ntify bbdegradation
 "associated with soil venting.

 To determine whether pH'-and alkalinity influenced carb-
 on .dioxide production.rates at Bioventing Initiative sites,
 an 'analysis- ofr the ratio .of oxygen  utilization to carbon
 dioxide; production  versus soil  parameters was per-
 formed; Because-of stoichiometry,2 the ratio of the oxy-
 gen utilization to carbon dioxide productionTate-will not
 be 1 because for every. 9.5 moles of oxygen consumed,
 ,6 moies: of'carbon dioxide are produced;  A square root
 transformation of  the oxygen utilization and carbon di-
 oxide production rate ratio (ratio) and log transformation
 of some of the soil parameters were .taken wherever the
 data were not well represented  by the normal  distribu-
 tion: Figures 5^9 through 5-11: display the  bivariate rela-
 tionships'between the ratio and the soilparameters after
•the transformation. These figures, as expected, show a
 negative cprrejatipn between the ratip and the oxygen
 utilization .rate (Fig,yre!5.-9, r = -0.45). The.correlation of
 the ratio with,clay.is;th,e most pronounced (Figure 5-11,
 r.= -0.40), The ratio is also negatively correlated with pH
,(Figure 5.^!vr = -.0.25),:and  alkalinity (Figure,  5-9, r  =
 --P.3Q)-  As,J.hpted  previously, pH  .and  alkalinity  are
 strongly positively related (Figure  5-9, r  = 0.75). The
 correlations of the  ratio with iron, moisture, permeability,
 arid particle sizes  are between -0.20 airid 0.30  (Figures
 5*9'and 5-11).

 The statistical methods used to model the ratio of the
 oxygen utilization rate to carbon didkide production rate
 as a function ©f the'soil  parameters are similar  to those
           used for the oxygen utilization rate analysis. As a pre-
           liminary step, a square root transformation of the ratio
           and log transformation of some soil  parameters were
           taken to obtain more ndrmaliy distributed data. AN'trans-
           formations for the  soil parameters except dlay were
           consistent with those taken previously to model  the
           oxygen utilization rate. A log transformation of clay was
           considered as it was more correlated  with the ratio.

           After applying the transformation,,,a.  regression .model
           was fitted to the ratio using forward stepwise regression.
           The model accounted for the effects of all soil parame-
           ters '(except season) and1 their interactions. Finally, the
           effect of a cyclic seasonal component on the residuals
           obtained from the fitted model was determined by incor-
           porating the date  of the initial in situ respiration test.

           The final model for the,ratio of the carbon  dioxide pro-
           duction rate to the oxygen utilization rate is as follows:

            (CO2 rate ""I |
              02 rate   = 1.28 - 0.38log(pH) - 0.095log(clay) +.
                          0.0007log(tphs) * TMP
                                                      (Eq, 5-5)
 ! See Section 3.2.1 for the stoichiometry of hydrocarbon degradation.
           Each effect in the above model is statistically significant
           at the =0:05 significance .level-., The model  explains 40
           percent of .the variability in the transformed ratio. This,
           amounts  to a  63 percent correlation between the ob-
           servedand model-predicted transformed ratios. The ef-
           fects of pH:on the ratio as predicted by the model are
           presented in Figure 5-16,

           The. complicated nature of the.fitted, regression model
           for the ratio makes the quantification pf the effects in fhe
           model difficult. Figure 5-16, however, shows that as pH
           increases/the ra'tip of the carbon dioxide production rate
           to the oxygen  utilization rate decreases,  as would be
           expected given the.formation-of carbonates.
                                                    54

-------
                    I
                    c
   0.8


   0.7


   0.6


   0.5
2
X



I  0.3


lo.2
S
   0.1


   0.0
                                                                       Obaenwd Ratio
                                                                       Predicted Ratio
                                                       7
                                                      PH
                                                                                    10
Figure 5-16.  Variation of pH and the effect on oxygen utilization to carbon dioxide rate ratio based on model predictions with average
           levels of other parameters.
5.2.5   Correlation of Soil Gas Permeability
        With Environmental Parameters

The bivariate relationships between log-transformed soil
gas permeability and each of the independent variables
of interest are shown in Figure 5-17.  In  this figure,
permeability correlates most  strongly with clay (r  =
-0.50). The magnitude of the correlations with both mois-
ture and sand  are less  pronounced and similar.

The statistical  methods used here are similar to those
described previously for the oxygen utilization rate and
the ratio.  Forward  stepwise  regression  was used to
determine a regression model for the log-transformed
soil gas permeability. The independent variables of in-
terest in the modeling were moisture content and parti-
cle size (sand, silt, and clay).

The final model describing soil gas permeability is given
below:

            log(PRM) = 3.2 - 0.064 clay     (Eq. 5-6)

Based on this  model, clay alone explains 21 percent of
the variability in the log-transformed soil gas permeabil-
ity. The effect  of clay on soil gas permeability as pre-
dicted by the model is presented in Figure 5-18. In this
figure, the soil gas permeability levels greater than 100
have been censored (i.e., they were set  to a constant
value of 100). Based  on the  regression  model it  is
determined that an increase in clay of 5 units decreases
soil gas permeability by 25 percent on average.

5.2.6   Analyses of Data From Contaminated
        and Background Areas

As the preliminary step to comparing the data at back-
ground and contaminated sites, transformations of the
data parameters were considered. These transforma-
                                  tions were consistent with those  taken  previously to
                                  address the other objectives of the statistical analysis.
                                  After taking the transformation, statistical analyses were
                                  performed separately on each parameter (e.g., nitrogen,
                                  oxygen rate). The goal of this analysis was to determine
                                  significant differences in the levels of each parameter at
                                  background and contaminated sites, with particular in-
                                  terest in TKN concentrations. Measurement of TKN ac-
                                  counts  for nitrogen sources within  cellular material;
                                  therefore, it is possible that TKN concentrations may be
                                  higher in contaminated areas, where microbial popula-
                                  tions may be higher, than in uncontaminated areaS. To
                                  date, no significant difference exists between TKN con-
                                  centrations at contaminated sites (average of 232 mg/kg)
                                  and those at background areas (average of 226 mg/kg).

                                  5.2.7  Summary

                                  Based on the statistical analyses presented  in the previous
                                  sections, the following overall conclusions are drawn:

                                  • The relationships between  biodegradation rates and
                                    soil parameters are not very strong. Some significant
                                    relative effects of the soil parameters stand out from
                                    the statistical evaluation conducted in the  study, how-
                                    ever. Namely, nitrogen, moisture, and  soil gas TPH
                                    concentration  appear to be the most important char-
                                    acteristics  influencing observed field oxygen utiliza-
                                    tion rates.

                                  • The ratio of the carbon dioxide production rate to the
                                    oxygen utilization rate correlates strongly with pH and
                                    clay levels in the soil.

                                  • Soil gas permeability correlates with each  particle size
                                    (sand, silt, and clay) and moisture content; however,
                                    the relative effect  of clay on permeability is most
                                    important.
                                                    55

-------
                    PRM
                                  GRA
                                               SAN
                                                             SIL
                                                                         CLA
                                                                                       MOI
         PRM > log Son Gat Permeability   GRA - Gravel   SAN - Sand   SIL - Silt  CLA - Clay   MOI - Moisture
                                  Z1
                                            90%
60%
30%
0%
                                            Key to Correlation Scatterplota.
Figure 5-17.  Soil gas permeability, moisture content, and particle size site average correlation scatterplot.
                                                      56

-------
                      100

                       90

                       80


                    I™
                    I 60
                    £
                    •g 50


                    I «

                       30

                       20

                       10

                        0
             Observed Permeability
             Predicted Permeability
                                                      Clay(%)
Figure 5-18.  Variation of clay and the effect on soil gas permeability based on model predictions.
The Bioventing Initiative has provided a large database
of information useful in the design and implementation
of bioventing systems. The statistical analyses provide
guidelines for determining which parameters are most
important to bioventing technology. These data must be
balanced,  however,  by  experience and site-specific
data. For example, sites with relatively low soil nitrogen
concentrations should not be discarded  as bioventing
sites for this reason alone, nor should an assumption be
made that nitrogen addition at these sites will increase
oxygen utilization rates. Data collected from the U.S. Air
Force Bioventing Initiative have shown that even sites
with low  soil nutrient concentrations can exhibit signifi-
cant microbial activity and would therefore respond well
to bioventing.
                                                     57

-------
                                                        Chapter 6
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                                             Appendix A
                                               Glossary
abiotic  not relating to living things, not alive

acidity  measure of the hydrogen ion concentration of
a solution

adsorption  process  by which molecules  collect on
and adhere to the surface of an adsorbent solid because
of chemical and/or physical forces

aeration   process of supplying or introducing air into a
medium such as soil or water

aerobic   living, active, or occurring only in the pres-
ence of oxygen

air sparging  technology of introducing gases, usually
air, beneath the water table to promote site remediation;
air sparging can be divided into two distinct processes:
in-well aeration and air injection

alkalinity  measure of the hydroxide ion concentration
of a solution
alluvial
river
relating to flowing water, as in a stream or
anaerobic   living, active, or occurring only in the ab-
sence of oxygen

aquifer   water-bearing layer of permeable rock, sand,
or gravel

bentonite  clay composed of  volcanic ash decompo-
sition, which is used to seal wells

bioavailability  accessibility of  contaminants to the
degrading populations; consists of (1) a physical aspect
related to phase distribution and mass transfer and (2)
a physiological aspect related  to the suitability of the
contaminant as a substrate

biodegradable   material or compound that can be
broken down by natural processes of living things such
as metabolization by microorganisms

biodegradation   act of  breaking down material (usu-
ally into more innocuous forms)  by natural processes of
living things such as metabolization by microorganisms

biofilm   structure in  which bacteria fixed to a surface
produce a protective extracellular polysaccharide layer
biofiltration   process using microorganisms immobi-
lized as a biofilm on a porous filter substrate, such as
peat or compost, to separate contaminants; as air and
vapor  contaminants  pass through the filter, contami-
nants transfer from the gas phase to the biolayer, where
they are metabolized

biomass   amount of living matter (in a specified area)

bioreactor   container or area in which a  biological
reaction or biological activity takes place

bioreclamation   process of making  a contaminated
site usable again through biological processes

bioremediation   technology of using biological proc-
esses such as microbial metabolism to degrade soil and
water contaminants and decontaminate sites

bioslurping   technology application that teams vac-
uum-assisted free-product recovery with bioventing to
simultaneously recover free product and remediate the
vadose zone

bioventing   process of aerating subsurface soils by
means of installed vents to stimulate in situ  biological
activity and optimize  bioremediation, with some volatili-
zation  occurring

capillarity  action by which  a liquid is held  to a solid
by surface tension

capillary fringe   first layer of rock above a layer  in
which water is held by capillarity

catalyst   substance that initiates a chemical reaction,
allows a reaction to proceed under different conditions
than otherwise possible, or accelerates a chemical re-
action; catalysts  are  not consumed in the reaction; en-
zymes are catalysts

catalytic oxidation   incineration  process  that uses
catalysts to increase the oxidation  rate of organic con-
taminants, allowing equivalent destruction efficiency at
a lower temperature than flame incineration

clay   fine-grained soil that can exhibit putty-like prop-
erties within a range of water content and is very strong
when air-dried
                                                    63

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cometabolic process   metabolism of a less-favored
substrate occurring  during the metabolism of the pri-
mary substrate

cone of depression  area  of  lowered  water table
around a well site because of active pumping

contaminant   something that makes material in con-
tact with it impure, unfit, or unsafe; a pollutant

diffusion  process of passive transport through a me-
dium motivated by a concentration gradient

diffusivity   diffusion coefficient; the amount of mate-
rial, in grams, that diffuses across an area of 1  cm2 in 1
second because of a unit concentration gradient (articu-
lar to compound and medium pair)

electron acceptor  relatively oxidized, compound that
takes electrons from electron donors during cellular res-
piration, resulting  in  the release of energy to the cell

electron donor   organic carbon, or reduced inorganic
compound, that gives electrons to electron acceptors
during  cellular respiration, resulting in the  release of
energy to the cell

enzyme   biologically produced, protein-based catalyst

ex situ   refers to a technology or  process for which
contaminated material must be removed from the site of
contamination for treatment

facultative   microbiai trait enabling  aerobic or anaero-
bic respiration, depending on environment

head  pressure difference between  two places; an en-
ergy term expressed in length units

immiscible  refers to liquids that do not  form a single
phase when mixed (e.g., oil and water)

in situ   refers to a technology  or treatment  process
that can be carried out within the site of contamination

in situ respiration test   test  used  to provide  rapid
field measurement  of in situ biodegradation  rates to
determine the potential applicability  of bioventing at a
contaminated site and to provide information for a full-
scale bioventing system design

in-well aeration  process of injecting gas into a well to
produce an in-well airlift pump effect

miscible   refers to liquids  that form a  single phase
when mixed (e.g., ethanol and water)

nitrogen fixation   metabolic  assimilation  of atmos-
pheric nitrogen by soil  microorganisms and release of
the nitrogen for plant use upon the death of the micro-
organisms

nutrients   constituents  required to support  life and
growth
off-gas  gas that leaves a site, typically from a point
source during extraction operations

oxidation   chemical process that results in a net loss
of electrons in an element or compound

oxygen utilization rate  rate of reduction of the in situ
oxygen content of soil gas because of biological and
chemical action

ozonation   injection of ozone into a contaminated site

packed-bed thermal treatment   process that oxidizes
organic contaminants by passing the off-gas  stream
through a heated  bed of ceramic beads, resulting  in
destruction of the organic compounds

perched aquifer   unconfined ground water separated
from an underlying main body of ground water by a
low-permeability rock  layer that  blocks vertical move-
ment of water

permeability   measure of the ability of liquid or gas to
move through pores and openings in a material

pH   measure of the alkalinity or acidity of a solution;
the  negative log of the hydrogen  ion  concentration

photocatalytic oxidation   process by which  volatile
organic compounds are converted to carbon dioxide and
water by exposure to ultraviolet light

pore space  open space in a material through which
liquid and gas can move

porosity   measure of the amount of available space in
a material through which liquid and gas can move

primary substrate  substrate that  provides  most  of
the  growth  and  energy requirements for cells

pump and treat technology   treatment   method  in
which  the  contaminated water is pumped out of the
contaminated site, then treated  off site  before  being
returned

radius of influence   maximum  distance from the air
extraction or injection well where vacuum or pressure
(soil gas movement) occurs

radius of oxygen influence   radius to which  oxygen
has to be supplied to sustain maximal biodegradation; a
function of air flow rates and  oxygen utilization  rates
and, therefore,  depends on site geology, well  design,
and microbiai activity

Raoult's law   physical chemical law that states that
the vapor pressure of a solution is  equal to the  mole
fraction of the solvent multiplied  by the vapor pressure
of the  pure solvent

reduction   chemical process that results in a net gain
of electrons to an element or compound
                                                   64

-------
remediation  activity involved with reducing the haz-
ard from a contaminated site

sand   unconsolidated rock and mineral particles with
diameters ranging from 1/16 mm to 2 mm

silt   unconsolidated rock  and mineral  particles with
diameters ranging from 0.0002 mm to 0.05 mm

soil gas permeability   soil's  capacity for fluid flow;
varies according to grain size, soil uniformity, porosity,
and moisture content

soil vacuum extraction (SVE)  process designed and
operated to maximize the volatilization of low-molecular-
weight compounds, with some biodegradation occurring

sorb  to  take up or hold  by  means of adsorption or
absorption
substrate   base on which an organism lives; reactant in
microbial respiration reaction (electron donor, nutrient)

surfactant  substance that lowers the surface tension
of a liquid

treatability   ability of a site to be remediated

vacuum-enhanced pumping   use of a vacuum pump
to lift ground water, or other liquids or gases, from a well
while producing a reduced pressure in the well

vadose zone   zone of  soil  below the  surface and
above the permanent water table

volatile   easily vaporized at  relatively low tempera-
tures

volatilization   process of vaporizing a liquid into a gas
                                                   65

-------
                                  Appendix B
                   Data From Bioventing Initiatives Sites
Table B-1.  Bioventing Initiative Results: Soil Chemical Characterization
Air Force Base
AFP 4

AFP PJKS
Battle Creek
Beale


Boiling

Camp Pendleton
Cannon
Cape Canaveral



Charleston


Davis Monthan

Dover

Dyess
Edwards


Eglin
Eielson


Site
FSB-1
FSA-3
ST-35
Fire Training Area
Site 3
Site 18
Site 11
Building 18
Former Storage Tank Farm
Site 1
SWMU 70
FTA-2
Facility 1748
Facility 44625D
Facility 44625E
FT-03
Site ST-27
Site SS-41
Site 35.
Site 36
ST-04
North Storage Tank Farm
Site FT40
Site FT41
Site 21
Site 16
Site 43
FTA Hurleburt Field
Old Eglin FTA
ST-10
Site 48-E2
Site 48-E3
PH
8.8
7.7
7.5
8.2
7.7
7.4
8.2
4.9
8.1
7.7
8.4
7.7
8.5
9.2
8.8
7.1
6.7
4.7
8.3
8.1
5.3
5.5
8.7
8.8
9.3
9.6
8.9
8.2
7.5
6.3
7.8
7.5
Alkalinity
(mg/kg)
210
365
NS
170
87
67
240
<50
910
120
1,150
165
400
265
350
280
130
<50
360
220
36
<50
3,130
2,790
730
640
500
300
170
<50
240
230
TKN
(mg/kg)
33
190
490
73
105
42
15
48
100
73
190
18
110
74
54
350
62
61
32
57
48
410
180
240
26
22
150
74
<43
390
320
690
Total
Phosphorus
(mg/kg)
270
340
46
165
400
250
820
85
170
46
76
280
310
190
270
350
75
37
760
450
270
100
200
280
650
630
360
33
24
7.4
650
790
Iron
Content
(mg/kg)
7,450
9,800
NS
5,050
27,500
26,400
17,500
15,300
9,610
3,360
6,570
860
900
1,380
970
2,940
8,400
530
15,700
12,700
4,700
8,740
16,900
19,500
9,960
12,500
13,400
670
1,600
10,400
17,400
16,700
                                       67

-------
Table B-1.  Bioventing Initiative Results: Soil Chemical Characterization (Continued)
Air Force Base
Ellsworth

Elmendorf



FE Warren

Galena


• ;
Hanscom

Hickam


Hill







Johnston Island


Keesler

Kelly



Kirtland

Kl Sawyer
Kodiak Island
Little Rock

Los Angeles


March
Site
Area D Bulk Fuel Storage
Building 102 Base Fuel
Station
43/45 Valve Pit
ST-61
ST-71
43/55 Pumphouse
Fire Training Pit
Spill Site
Saddle Tank Farm
Power Plant
Million Gallon Hill'
Campion POL Leak Site
Building 1639
Building 1812
Area H
Area K
Site 2 FSA
Site 204.1
Site 214.1
Site 228
Site 924
Site 1705
Site 388
Site 40002
Site 510.8
Old Fire Training Area
Former POL Tank Farm
Storage Tanks 260 and 261
SWMU 66
AOC A
Site S-4
Site FC-2
Site B-2093
Site D-10
Fire Training Area 13
Fire Training Area 14
POL Area
Tank 191
Fire Training Site 1
Spill Site 18
Building 125
Building 241
Gate 3
IRP Site 35c
PH
8.5
8.6
7.2
7.7
7.8
7.5
7.8
8.2
7.5
7.8
NS
8.1
6.0
6.6
9.0
8.3
4.7
7.8
NS
NS
8.0
NS
6.8
NS
8.7
8.9
9.0
9.0
7.5
7.0
7.5
8.2
8.2
7.7
8.4
7.0
7.9
7.0
6.1
6.1
8.7
7.5
8.4
8.2
Alkalinity
(mg/kg)
1,150
640
100
160
200
87
1,300
340
520
490
NS
300
<50
58
1,500
860
35
740
NS
NS
74
NS
52
NS
340
540
405
355
260
250
500
750
1,100
1,100
340
380
98
260
86
<50
440
830
310
21
TKN
(mg/kg)
320
24
64
78
110
66
1,300
55
800
620
NS
710
630
60
30
1,700
38
140
NS
NS
120
NS
350
NS
100
440
185
140
102
43
690
590
310
640
58
200
22
590
710
390
87
120
65
130
Total
Phosphorus
(mg/kg)
500
1,000
3.5
1,200
3.1
1,200
440
320
730
710
NS
570
320
530
3,400
2,300
470
NS
NS
NS
710
NS
NS
390
2,200
370
520
340
190
35
620
790
880
310
300
1,000
140
930
130
140
1,200
1,600
1,400
280
Iron
Content
(mg/kg)
15,000
36,800
24,800
23,700
28,000
25,300
20,200
11,200
21,400
24,200
NS
15,200
7,620
6,810
75,100
34,100
99,000
5,270
NS
NS
6,500
NS
9,380
NS
4,700
270
115
84
4,300
2,100
16,000
13,400
14,000
13,300
11,200
26,200
2,190
24,900
53,000
36,300
8,900
33,800
18,700
32,200
                                                   68

-------
Table B-1. Bioventing Initiative Results: Soil Chemical Characterization
Alkalinity
Air Force Base Site pH (mg/kg)
McClellan






McGuire
Mt. Home
Nellis


Newark


Offutt



Patrick

Pease

Plattsburgh


Pope
Randolph
Robins

Shaw

Tinker
Travis

Vandenburg

Westover

Wright Patterson

Building 720
Davis Site
Capehart Gas Station
PRL T-46
Study Area 6
Tank Farm #2
Tank Farm #4
Bulk Fuel Storage
POL Yard
Site 27
Site 28
Site 44
Facility 27
Facility 89
Facility 14
Low Point Drain
Building 30
Building 406
POL Storage Area
FTA-2
BX Service Station
Bulk Fuel Storage Area
Site 2
Fire Training Area 1
Fire Training Pit 4
Fire Training Areas 2 and 3
IRP Site ST-08
Tank 20 Site
UST 173
SS10
Site FT-01
Site SS-15
POL Storage Area C
Fuel Storage Area G
South Gas Station
Service Station
JP-4 Site
Building 7701
Building 7705
Fire Training Area
Spill Sites 2 and 3
7.5
8.0
5.8
7.4
8.0
7.8
7.4
6.1
8.4
8.8
8.6
8.5
7.8
7.8
7.9
8.0
8.7
7.8
7.9
8.8
8.4
6.6
5.7
6.6
6.4
7.6
6.7
8.1
5.2
5.3
5.6
5.2
7.3
7.4
7.9
6.9
6.1
6.1
6.8
7.2
8.1
22.5
350
95
46
71
120
100
37
2,100
1,600
410
800
370
460
320
330
1,600
360
470
220
160
140
22.5
84
22
120
200
340
<50
<50
22
22
<50
120
120
20
180
<50
22
730
340
(Continued)
TKN
(mg/kg)
44
260
54
50
10
47
74
480
76
260
100
53
35
360
200
190
250
220
750
32
60
190
59
75
36
49
<40
230
90
46
190
20
30
79
210
103
57
61.5
200
680
<20
Total
Phosphorus
(mg/kg)
260
400
180
5.9
590
1,100
150
217
5.0
170
290
210
515
540
260
480
680
720
600
260
290
730
630
<1.0
330
160
110
920
84
78
38
260
55
220
300
100
100
580
190
570
310
Iron
Content
(mg/kg)
11,400
40,200
26,700
21 ,300
28,400
26,700
25,200
5,830
21,100
6,950
5,800
6,800
15,400
16,100
16,400
7,500
13,700
18,500
9,800
440
360
21,000
39,100
4,500
4,500
4,200
3,000
12,400
6,000
3,600
4,100
13,900
3,210
28,400
22,100
2,920
9,700
6,835
4,900
16,200
6,900
NS = not sampled.
69

-------
Table B-2.  Preliminary Bioventing Initiative Results: Average BTEX and TPH Soil Concentrations
                                                                             Soil Analysis
Air Force Base
AFP 4



AFP PJKS

Battle Creek

Beale





Boiling



Camp Pendleton
Cannon
Cape Canaveral




Charleston



Davis Monthan

Dover



Dyess



Edwards





.Eglin

.Eielson





Ellsworth



Site
FSA-1

FSA-3

ST-35

Fire Training Area

Site3

Site 18

Site 11

Building 18 ,

Former Storage
Tank Farm
Site 1
SWMU 70
FTA-2

Facility 1748
Facility 44625D
Facility 44625E
FT-03

ST-27
Site SS-41
Site 35
Site 36
ST-04

North STF

Site FT40

Site FT41

Site 21

Site 16

Site 43

FTA Hurleburt Field
Old Eglin FTA
ST-10

Site 48-E2

Site 48-E3

Area D Bulk Fuel
Storage
Building 102 Base
Fuel Station
Time
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Initial
Final
Initial
Initial
Initial
Initial
Final
Initial
Initial
Initial
Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
initial
Final
Initial
Final
Initial
Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Benzene
(mg/kg)
0.36
BDL
2.7
BDL
BDL
BDL
0.43
BDL
1.5
BDL
BDL
BDL
. 1.4
0.6
BDL
BDL
0.27
0.064
0.028
1.5
BDL
BDL
0.58
0.35
0.40
BDL
BDL
BDL
0.70
3.3
20
0.90
BDL
BDL
BDL
BDL
BDL
0.05
BDL
BDL
BDL
0.24
BDL
BDL
BDL
0.97
3.8
BDL
BDL
1.4
BDL
BDL
BDL
8.2
0.842
0.18
BDL
Toluene
(mg/kg)
1.3
BDL
9.1
BDL
BDL
BDL
3.0
BDL
4.8 '
BDL
1.1
BDL
50
0.61
BDL
BDL
8.4
BDL
0.072
14
4.2
BDL
0.58
0.35
0.51
2.0
BDL
0:0056
28
16
100
1.1
BDL
0.33
0.25
BDL
BDL
0.05
BDL
0.13
BDL
0.29
BDL
BDL
BDL
14
7.5
230
0.015
4.4
.BDL
> 4.3
BDL
8.9
BDL
0.60
BDL
Ethyl-
benzene
(mg/kg)
12
BDL
7.1
BDL
0.73
BDL
2.6
BDL
3,5 .
0.41
2.5
BDL
24
4.4
2~0
BDL
1.5
0.12
0.45
14
2.6
BDL
2,0
0.35
0.61
0.82
BDL
0.0033
2.2
14
63
1.7
BDL
13
0.080
BDL
BDL
0.05
BDL
1.6
BDL.
2.3
BDL
0.12
BDL
7.3
11
41
0.0071
11
0.34
BDL
,BDL
37
1.8
0.78
11
Total
Xylenes
(mg/kg)
31
BDL
60 ,
BDL
1.5
BDL
12
0.016
17
1.4
6.0
BDL
175
240
1.8
BDL
3.7
0.22
0.50
53
6.6
BDL
5.7
1.3
7.1
2.3
BDL
0.015
17
23
140
8.7
BDL
37
0.19
0.93
BDL
0.07
BDL
6.5
BDL
12
BDL
0.68
BDL
48
32
340
0.0050
45
1.4
4.6
BDL
190
10
4.3
44
Total
BTEX
(mg/kg)
45
BDL
79
BDL
2.2
BDL
23
0.016
26.20
1.81
9.6
BDL
253.
246
3.80
BDL
13.87
0.40
1.05
83
13.40
BDL
8.86
2.4
8.62
5.12
BDL
0.02
47.90
56
323.00
12.40
BDL
50.33
0.52
0.93
BDL
0.22
BDL
6.20
BDL
14.59
BDL
0.95
BDL
70.27
54.30
611.00
0.027
62
1.7
8.90
BDL
244.10
12
5.86
55
TPH
(mg/kg)
29
680
140
84
1,100
130
7,200
1,800
14,000
10,100
17,000
5,600
400
1,600
1,800
4,100
72
160
3,400
2,700
300
1,100
17,200
10,500
9,200
1,100
790
15
730
530
2,700
8.7
BDL
1,200
650
450
160
930
200
110
23
24
5.1
540
74
9,600
4,100
4,100
52
5,400
1,200
2,600
21
2,800
2,800
11
651
Moisture
Content
(%)
13.7
14.7
16.2
15.4
8.9
11.9
4.8
5.0
23^8
20.9
22.8
19.8
16.8
12.5
16.0
6.1
15.7
15.5
11.0
12.4
14.3
NR
9.2
6.4
6.4
15.8
8.1
13.9
14.6
9.4
7.2
11.7
14.2
24.9
22.0
17.2
17.0
16.6
15.4
11.1
10.
13.7
13.3
9.4
1.65
6.6
6.9
12.3
2.7
14.9
6.2
27?8
36.9
17.7
16
7.2
9.8
                                                          70

-------
Table B-2.  Preliminary Bioventing Initiative Results: Average BTEX and TPH Soil Concentrations (Continued)
                                                                              Soil Analysis
Air Force Base
Elmendorf







FE Warren


Fort Drum
Galena





Hanscom



Hickam





Hill















Johnston Atoll





Keesler



Kelly
/


Site
43/45 Valve Pit

ST-61

•ST-71

43/55 Pumphouse

Fire Training Pit
Spill Site

Area 1 595
Saddle Tank Farm
Power Plant

Million Gallon Hill
Campion POL
Leak Site
Building 1639

Building 1812

Area H

AreaK

Site 2 FSA

Site 204.1 ••

Site 214.1

Site 228

Site 924

Site 1705

Site 388

Site 40002

Site 510.8

Old Fire Training
Area
Former POL Tank
Farm
Storage Tanks 260
and 261
SWMU 66

AOCA

Site S-4

Site FC-2

Time
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Final
Initial
Initial
Initial
Final
Initial
Initial

Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial '
Final
Initial

Initial

Initial

Initial
Final
Initial
Final
Initial
Final
Initial
Final
Benzene
(mg/kg)
BDL
BDL
BDL
BDL
BDL
BDL
1.7
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
NS
0.028

0.57
0.032
BDL
BDL
2.8
0.078
1.1
BDL
0.6
0.93
0.021
BDL
3.3
BDL
0.64
BDL
BDL
BDL
'BDL
BDL
1.9
0.045
50
32
BDL
BDL
BDL

BDL

BDL

4.7
BDL
0.10
BDL
BDL
BDL
BDL
0.014
Toluene
(mg/kg)
BDL
32
0.019
0.098
BDL
0.001
41
BDL
0.46
BDL
4.1
BDL
0.85
BDL
BDL
NS
0,25

1.5
0.57
0.026
0.016
5.3
0.013
12
BDL
11
3.5
0.16
0.01
3.7
BDL
9.2
BDL
BDL
BDL
BDL
BDL
43
0.046
470
410
BDL
BDL
0.65

BDL

BDL

35
0.018
0.039
0.0017
9.1
0.94
8.0
0.13
Ethyl-
benzene
(mg/kg)
BDL
32
0.30
0.22
•BDL
BDL
52
BDL
0.66
4.8
BDL
3.4
BDL
BDL
BDL
NS
BDL

0.58
0.073
BDL
BDL
5.5
0.0049
10
BDL
7.4
11
0.54
BDL
5.3
BDL
7.1
BDL
BDL
0.0068
BDL
BDL
25
0.54
160
78
BDL
BDL
BDL

3.5

15

16
BDL
0.22
BDL
BDL
BDL
BDL
0.014
Total
Xylenes
(mg/kg)
BDL
140
0.34
0.75
BDL
0.00053
241
BDL
1.4
31
10
25
3.7
BDL
BDL
NS
0.19

4.2
0.3
0.047
0.023
7.5
0.0046
19
BDL
38
12
5.1
0.089
9.1
BDL
240
BDL
BDL
0.029
0.12
BDL
250
4
1,300
1,200
BDL
0.1
BDL

2.5

14

116
0.0050
0.080
0.0020
13
1.5
22
0.022
Total
BTEX
(mg/kg)
BDL
200
0.66
1.1
BDL
0.0015
330
BDL
2.5
36
14
28
4.6
BDL
BDL
NS
0.47

6.85
0.98
0.03
0.039
21.10
0.10
34.04
BDL
71.74
27
5.82
0.099
21
BDL
256.94
BDL
BDL
0.036
0.12
BDL
320
4.6
1 ,977.00
1,700
0.06
0.10
0.45

6.0

29.00

171.70
0.023
0.44
0.0037
20.20
2.4
30.00
0.18
TPH
(mg/kg)
4.9
6,000
790
2,400
32
26
3,900
4.9
3,000
400
700
15,000
270
97
BDL
NS
760

13
130
6,500
1,800
12
4.8
20
47
1,100
1,400
960
4,500
12,100
550
5,800
BDL
BDL
BDL
4,400
600
7,500
1,100
28,100
12,300
5,200
2,600
7,700

13,000

265

3,300
2,500
87
19
920
590
1,600
64
Moisture
Content
(%)
5.6
9.8
8.4
11.6
4.6
5.1
8.1
4.6
20.7
20.8
19
10.6
21.9
22.3
5.8
NS
12.3

16.6
15.3
4.7
3.1
24.6
24.1
15.5
13.7
33.7
31.8
6.2
7.7
19
NS
11.7
8
6.7
16.7
8.3
6.3
8.7
6.9
23.5
27
8.1
6.9
11.0 '

10.7

12.5

11.5
34.1
8.4
9.0
21.1
22.9
20
20.5
                                                           71

-------
Table B-2. Preliminary Bioventlng Initiative Results: Average BTEX and TPH Soil Concentrations (Continued)
Soil Analysis


Air Force Base



Kirtland



Kl Sawyer





Kodiak UCSG
Little Rock


Los Angeles


Malmstrom


March

McClellan












McGuire

Mt. Home
Nellis





Newark



Offutt






Site
Site B-2093
Site D-10

Fire Training
Area 13
Fire Training
Area 14
POL Area

FTA-06

FTA-07

Tank 191
Fire Training Site 1
Spill Site 18

Building 125
Building 241
Gate 3
Pumphouse 2

Bulk POL
IRP Site 35c

Building 720
Capehart Gas
Station
Davis Site

PRL T-46

Study Area 6

Tank Farm #2

Tank Farm #4

Bulk Fuel Storage

POL Yard
Site 27

Site 28

Site 44

Facility 27

Facility 89

Low Point Drain
Building 406

Building 30



Time
Initial
initial
Final
Initial
Final
Initial

Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Initial
Final
Initial
Initial
Initial
Initial
Final
Initial
Initial
Final
Initial
Initial

Initial
Final
Initial
Final
Initial
Final
initial
Final
Initial
Final
Initial
Final
Initial
initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Final
Initial
Final

Benzene
(mg/kg)
13
BDL
BDL
BDL
BDL
BDL

BDL
BDL
0.72
0.84
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.0054
0.031
BDL
BDL
4.7
0.011
BDL
0.10
1.0

0.13
BDL
0.0022
BDL
4.2
0.098
0.0065
BDL
0.017
BDL
5.6
BDL
84
0.39
8.1
-14
2.2-
1.2
0.40
BDL
0.0028
BDL
BDL
0,11
2:2
0.048
BDL
BDL

Toluene
(mg/kg)
130
0.0096
BDL
9.1
2.2
BDL

40
BDL
7.5
2.2
0.48
0.047
0.027
BDL
BDL
BDL
BDL
0.018
0.23
0.71
0.067
130
0.011
BDL
0.10
1.6

0.13
BDL
0.0022
BDL
18
0,11
1.6
BDL
0.029
BDL
110
0.92
440
1.9
33
65
11
53
2.6
BDL
0.0079
BDL
0;014
1.8
1.4
0.88
0.0029
0.0041
Ethyl-
benzene
(mg/kg)
39
BDL
BDL
.9.5
7.2
0.79

9.7
0.35
7.8
3.6
1.7
0.75
BDL
BDL
0.53
BDL
BDL
0.35
1.4 '
1.6
0.21
22
0.050
BDL
0.10
0.12

0.13
0.077
0.94
BDL
14
0.51
0.12
0.11
0.017
BDL
120
3.1
82
1.0
18
30
8.1
28
1.1
BDL
BDL
BDL
BDL
1,0
21
0.034
BDL
BDL
Total
Xylenes
(mg/kg)
200
BDL
BDL
57
38
3.7

27
7.8
36
11
19
2.6
BDL
0.43
0.74
BDL
BDL
0.36
2.3
3.7
0.13
120
0.16
BDL
8.2
0.84

0.25
0.15
1.2
BDL
27
1.1
0.57
BDL
1.1
BDL
200
12
930
4.7
67
130
25
110
5.5
BDL
0.0019
BDL
0.0011
6.3
35
1.8
0.014
0.00053
Total
BTEX
(mg/kg)
382.00
0.01
BDL
76
. 47
4.49

77.70
8.2
52
18
21
3.4
0.027
0.43
1.27
BDL
BDL
0.73
3.96
6.0
0.41
280
0.23
BDL
8.50
3.56

0.64
0.23
2.14
BDL ,
63.20
1.8
2.30
0.11
1.16
BDL
435.30
16
1 ,536.00
7.99
130
239.00
46
192.20
9.6
BDL
0.013
BDL
0.015
9.2
60
2.8
0.02
0.0046

TPH
(mg/kg)
53
86
250
1,800
4,800
7,900

1,300
2,600
6,700
8,200
250
4,000
6.3
990
8.2
BDL
560
3,700
4,000
240
84.6
2,700
1,000
8.6
3,800
5.4

6,000
1,200
3,100
61
1,200
BDL
37
98
41
BDL
2,100
1 ,600
5,800
50
7,800
2,200
1,500
300
140
43
92
12
6
15
730
1.6CO
6.6
BDL
Moisture
Content
(%)
18.7
22.5
9.3
10.3
11.4
11.3

13.3
10.6
5.8
4.9
5.7
6.6
5.9
19.0
16.3
16.1
9.6
17.1
15.4
22
ND
NS
3.5
3.2
12
17.1

18.3
17.6
21.3
14.2
17.0
20.1
15.3
13.5
20.7
22.5
15.7
14.9
15.7
14.0
19.4
24.1
21.2
24.9
18.9
16.1
NR
18.9
NR
1§.7
23.0
20.0
24.3
22.4
72

-------
Table B-2.  Preliminary Bioventing Initiative Results: Average BTEX and TPH Soil Concentrations (Continued)

                                                                              Soil Analysis
Air Force Base


Patrick



Pease


Pittsburgh



Pope
Randolph

Robins



Shaw

Tinker

Travis


Vandenburg

Westover
1


Wright Patterson



Site
POL Storage Area

FTA-2

BX Service Station

Bulk Fuel Storage
Area
Site 2
Fire Training Areas
2 and 3
Fire Training Pit 4
Fire Training Area 1
Site ST-08
Tank 20 Site

UST 173

SS10

Site FT-01
SiteSS-15
POL Storage
Area C
Fuel Storage
Area G
South Gas Station
Service Station
JP-4 Site
Building 7701

Building 7705

Fire Training Area

Spill Sites 2 and 3

Time
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Final
Initial
Initial
Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Initial
Filial
Initial
Final
Initial
Initial
Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Benzene
(mg/kg)
0.0042
BDL
3.4
BDL
4.5
0.60
0.33
BDL
0.024
BDL
BDL
0.85
1.8
BDL
BDL
NS
BDL
BDL
0.018
7.3
0.31
1.7
1.9
0.0012
0.26
BDL
4.6
BDL
0.44
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Toluene
(mg/kg)
0.00082
BDL
26
BDL
0.72
0.067
1.1
BDL
3.2
0.026
BDL
0.85
30
BDL
4.7
NS
0.00067
BDL
20
21
1.7
3.8
45
0.0015
0.69
BDL
22
5.4
2.0
BDL
BDL
0.47
0.20
0.026
BDL
0.016
BDL
Ethyl-
benzene
(mg/kg)
0.019
0.004
190
0.034
3.0
0.07
5.2
BDL
0.057
0.0042
0.94
16
20
BDL
3.3
NS
0.11
0.82
14
21
3.6
7.1
53
0.0049
9.1
13
13
4.9
1.8
BDL
BDL
BDL
0.087
0.0028
BDL
BDL
BDL
Total
Xylenes
(mg/kg)
0.028
0.0073
920
BDL
18
0.2
15
BDL
0.68
0,14
1.5
80
135
BDL
33
NS
1.0
0.73
76
100
3.2
36
83
0.037
13
88
71
46
6.4
BDL
BDL
0.73
0.35
0.015
BDL
0.0054
BDL
Total
BTEX
(mg/kg)
0.05
0.011
1,100
0.034
26
0.94
21.63
BDL
3.96
0.17
2.4
97.70
186.80
BDL
41.00
NS
1.11
1.6
110.02
150
8.81
48.60
138.59
0.045
22.72
100
110.60
56.30
11
BDL
BDL
1.22
0.64
0.04
BDL
0.02
BDL
TPH
(mg/kg)
4.3
5.5
930
6,500
10,500
63
310
210
17
5,200
5,200
4,500
2,500
3,200
230
NS
1,900
340
3,100
3,600
4,500
2,400
2,300
BDL
64
5,400
20
230
6.2
BDL
BDL
22
BDL
19.5
BDL
BDL
BDL
Moisture
Content
(%)
19
21
6.6
8.3
4.1
7.6
12.3
12.5
11.0
3.8
10.5
8.3
8.2
12.9
10.5
NS
14.3
11.2
9.9
12.0
10.2
11.0
9.4
11
15.2
14.6
17.3
16.6
13.1
4.7
NR
9.8
8.9
19.0
17.0
6.6
4.2
 BDL = below detection limit.
 NR = not reported
 NS = not sampled.
                                                            73

-------
Table B-3.  Preliminary Bioventing Initiative Results: BTEX and TPH Soil Gas Concentrations
                                                                             Soil Gas Analysis
Air Force
Base
AFP 4



AFP PJKS

Battle Creek

Beale





Boiling



Camp
Pendleton
Cannon
Cape
Canaveral



Charleston



Davis Monthan

Dover

Dyess



Edwards





Eglin

Eielson





Ellsworth


Elmendorf
Site
FSA-1

FSA-3

ST-35

Fire Training Area

Site3

Site 18

Site 11

Building 18

Former Storage Tank
Farm
Site 13115

SWMU 70
FTA-2

Facility 1748
Facility 44625D
Facility 44625E
FT-03

ST-27
Site SS-41
Site 35
Site 36
ST-04
North STF
Site FT40

Site FT41

Site 21

Site 16

Site 43

FTA Hurleburt Field
Old Eglin FTA
ST-10

Site 48-E2

Site 48-E3

Area D Bulk Fuel
Storage
Building 102 Base Fuel
Station
43/45 Valve Pit
Time
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial

Initial
Initial
Final
Initial
Initial
Initial
Initial
Final
Initial
Initial
Initial
Initial
Initial
Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Benzene
(ppmv)
BDL
0.24
BDL
0.28
8.2
BDL
50
BDL
2.3
0.27
11
4.7
350
1.3
0.056
BDL
0.21
BDL
0.34

30
1.5
0.016
1.5
0.36
0.059
BDL
BDL
126
0.30
693
583
65
5.4
0.015
BDL
0.016
BDL
190
0.26
230
0.8
BDL
BDL
36
146
567
BDL
66
0.32
4.6
BDL
140
0.0091
320
BDL
13
Toluene
(ppmv)
BDL
0.094
BDL
0.21
8.8
0.004
18
0.0027
1.9
0.60
1.fi
BDL
530
13
0.18
0.0033
7.9
BDL
1.2

18
0.11
0.011
0.021
0.20
0.53
BDL
BDL
557
0.30
681
665
44
4.8
0.08
0.002
0.19
0.018
16
0.24
26
0.83
0.0088
0.006
46
179
150
1.6
51
2.1
0.25
BDL
13
0.017
48
0.074
80
Ethylbenzene
(ppmv)
21
0.23
6.4
0.65
6.5
0.026
2.8
BDL
0.71
0.87
2.0
0.80
37
7.3
0.30
0.016
4.0
BDL
1.2

7.4
3.6
0.026
3.4
0.015
0.33
0.061
0.0013
81
4.87
93
118
13.4
2.5
0.011
BDL
0.14
BDL
12
0.72
20
2
0.091
0.012
12
29
4.0
BDL
3.4
2.5
0.45
1.8
12.9
2
6.7
6.7
7.5
Total
Xylenes
(ppmv)
19
0.67
12.5
0.93
14
0.070
11
BDL
2.3
2.0
1.8
1.7
300
180
0.74
0.058
5.2
BDL
3.4

23
4.8
0.071
3.3
1.6
2.2
0.11
BDL
253
9.8
153
254
47
5.4
0.042
0.012
0.26
0.013
38
1.7
89
5.3
0.48
0.11
78
120
43
4.4
12
26
1.1
4.2
30
8.4
39
32
28
Total
BTEX
(ppmv)
40.96
1.2
19.03
2.1
37.50
0.10
81.40
0.0027
3.74
3.7
16.40
7.2
1,215.00
200
1.28
0.077
17.31
BDL
6.1

78
10.01
0.12
8.22
2.18.
3.12
0.17
0.0013
1,017.00
15.27
1 ,620.00
1 ,620.00
169.40
61.30
0.15
0.014
0.61
0.031
253.00
2.9
365.00
8.9
0.59
0.13
172.00
474.00
764.00
6.0
132.40
31
6.40
6.0
128.50
10
416.70
39
128.50
TPH
(ppmv)
25,000
290
12,800
480
2,300
1.1
10,900
7.9
3,000
270
3,600
1,600
59,300
2,800
317
15
11,900
12,700
460

9,000
3,900
210
750
397
303
410
6.7
118,333
19,667
46,098
39,667
33,500
6,150
49
1.5
320
1.6
49,000
220
63,000
575
380
0.95
17,667
16,000
48,000
2,100
6,000
1,200
1,866
610
35,000
780
79,000
840
13,550
                                                          74

-------
Table B-3. Preliminary Bioventing Initiative Results

Air Force
Base






FE Warren


Fort Drum
Galena




_
Hanscom


Hickam





Hill















Johnston Atoll



Keesler


Kelly








Site
ST-61

ST-71

43/55 Pumphouse

Fire Training Pit
Spill Site

Area 1595
Saddle Tank Farm
Power Plant

Million Gallon Hill

Campion POL 'Leak Site
Building 1639

Building 1812
Area H

AreaK

Site 2 FSA

Site 204.1

Site 214.1

Site 228

Site 924

Site 1705

Site 388

Site 40002

Site 510.8

Old Fire Training Area
Former POL Tank Farm
Storage Tanks 260 and
261
SWMU 66
AOCA

Site S-4

Site FC-2

Site B-2093
Site D-10



Time
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Final
Initial
Initial
Initial
Final
Initial
Final
Initial
Initial
Final
Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Initial

Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Final
: BTEX and TPH Soil Gas Concentrations (Continued)
Soil Gas Analysis

Benzene
(ppmv)
0.053
BDL
BDL
BDL
19
0.87
0.92
180
BDL
BDL
40
0.059
0.060
6.4
BDL
0.022
8.1
8.3
NS
BDL
BDL
85
BDL
16
BDL
0.026
0.0025
0.010
BDL
0.81
0.021
34
0.0025
0.012
BDL
175
2.3
BDL
1.2
BDL
BDL
0.016
0.1
0.059

23
1,100
42
200
0.041
38
BDL
175
0.003
BDL

Toluene
(ppmv)
0.32
0:22
BDL
0.004
64
0.86
2.5
28
0.012
7.2
8.3
1.1
BDL
5.7
BDL
0.040
10
9
NS
BDL
BDL
BDL
BDL
29
BDL
0.11
0.0047
0.039
BDL
2,2
0.029
80
0.0045
0.019
0.0025
180
97
280
140
0.18
BDL
0.47
0.11
0.066

44
550
220
22
0.88
15"
0.6
323
0.051
0.016

Ethylbenzene
{ppmv)
0.4
0.95
0.22
0.032
15
5.1
1.9
24
0.049
2.7
2.7
3.8
1.4
0.64
3.5
0.054
3.6
0.47
NS
28
0.0067
22
2
12
7.4
0.085
BDL
0.26
0.036
0.85
0.016
3.6
BDL
0.011
0.0017
8.9
25
12
9.7
0.06
0.065
0.95
3.03
1.5

4.5
51
53
22
0.3
18
0.15
25
0.18
0.003
Total
Xylenes
(ppmv)
1.1
1.3
1.12
0.033
50
33
5.1
110
0.27
16
6.4
3.5
3.2
2.5
10
0.22
17
5.5
NS
22
0.0053
48
5.3
40
18
0.39
0.0023
0.26
0.18
4.7
0.13
34
BDL
0.053
0.035
80
260
110
150
0.43
0.20
2.8
2.3
2.0

20
120
230
19
0.63
15
0.34
87
0.34
0.015
Total
BTEX
(ppmv)
1.87
2.5
1.35
0.069
150
40
10.42
348.00
0.33
26
57.40
8.5
4.7
15
14
0.34
38.70
23
NS
56.80
0.012
155.70
7.3
97.00
25
0.61
0.0095
0.57
0.22
8.48
0.20
150
0.0070
0.10
0.039
440.90
380
303.59
300
0.69
0.27
4.24
5.54
3.63

91.50
1,800
550
265.00
1.9
86.00
1.1
610.00
0.57
0.034

TPH
(ppmv)
1,000
200:
390
3.2
19,700
2,700
1,059
15,400
33
2,300
2,745
897
390
2,000
1,000
254
7,000
1,900
NS
240,000
73
26,300
15,900
13,800
6,400
220
3.2
480
620
1,300
20
2,900
1.5
44
1.2
26,000
9,000
11,100
7,800
660
340
450
3,833
1,588

8,183
130,000
22,300
36,500
430
12,400
100
9,467
54
1.1 .
75

-------
Table B-3.  Preliminary Bioventing Initiative Results: BTEX and TPH Soil Gas Concentrations (Continued)
                                                                             Soil Gas Analysis
Air Force
Base
Kirtland

K.I. Sawyer




Little Rock

Los Angeles


Malmstrom

March
McClellan







McGuire
Mt. Home
Nellis


Newark


Offutt



Patrick

Pease
Plattsburgh

Site
Fire Training Area 13
Fire Training Area 14
POL Area
FTA-06

FTA-07

Fire Training Site 1
Spill Site 18
Building 125
Building 241
Qate 3
Pumphouse 2
Bulk POL
IRP Site 35c
Building 720
Davis Site

PRL T-46

Study Area 6
Tank Farm #2
Tank Farm #4
Bulk Fuel Storage
POL Yard
Site 27
Site 28
Site 44
Facility 27
Facility 89
Facility 14
Low Point Drain
Building 30
Building 406
POL Storage Area
FTA-2
BX Service Station
Bulk Fuel Storage Area
Fire Training Pits 2 and 3
Fire Training Pit 4
Fire Training Area 1
Time
Initial
Final
Initial
Initial
Initial
Final
Initial
Final
Initial
Initial
Initial
Initial
Initial
Initial
Final
Initial
Final
Initial
Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Final
Initial
• Initial
Initial
Initial
Initial
Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Final
Initial
Initial
Benzene
(ppmv)
19
0.011
MS
393
8.6
0.16
3.1
1.2
NS
BDL
0.026
0.065
0.026
6.6
BDL
BDL
BDL
0.035
NS
0.0053
BDL
0.18
0.34
165
3.8
0.68
BDL
0.11
BDL
73
10
550
543
6.0
520
203
0.019
0.0072
NS
88
BDL
BDL
290
BDL
67
BDL
BDL
0.048
BDL
0.027
117
4.4
BDL
11
6.01
•
Toluene
(ppmv)
56
BDL
NS
178
7.2
0.13
6.2
10
NS
BDL
0.026
0.31
0.026
BDL
BDL
12
BDL
0.035
NS
0.004
0.0045
0.18
3.0
124
7.2
28
0.38
0.11
BDL
190
22
25
372
14
547
753
0.023
0.015
NS
153
BDL
BDL
BDL
BDL
11
BDL
BDL
0.003
44
0.002
9.7
10
0.016
18
20
Ethylbenzene
(ppmv)
8.3
0.1
NS
9.1
0.53
0.23
0.40
4.0
NS
8.7
0.089
0.59
0.57
9.1
0.15
12
2
0.41
NS
0^39
0.0050
3.3
2.8
13
4.8
7.9
7.0
5.3
0.046
17
5.1
560
37
5.1
55
68
0.0097
0.0045 .
NS
29
BDL
BDL
44
6.5
4
BDL
1.5
0.024
24
0.0045
18
2.1
0.0045
24
4.2
Total
Xylenes
(ppmv)
34
0.56
NS
15
2.6
0.68
2.2
22
NS
16
0.2
0.91
1.17
12
0.28
38
4.2
0.67
NS
0.67
0.10
1.84
6.0
81
36
30
13
5.7
0.15
58
45
270
100
16
185
377
0.11
0.0088
NS
77
1.4
BDL
51
28
9.5
0.36
5.2
0.058
200
0.23
22
14
0.013
82
15
Total
BTEX
(ppmv)
117.30
0.67
NS
595.10
19
1.2
12
37
NS
25
0.34
1.88
1.79
28
0.43
62
6.2
1.15
NS
1.07
0.11
5.50
12
383.00 '
52
66.58
20
11.22
0.20
340
82
1 ,400
1 ,052.00
41
1 ,307:00
1,401.00
0.16
0.04
0.00
347.00
311.00
BDL
382.92
35
304.00
0.36
267.60
0.13
7.18
0.26
166.70 ,
30.50
0.034
140
45.21
TPH
(ppmv)
13,000
690
NS
41,067
1,300
20
820
710
NS
23,700
2,200
340
857
8,800
65
46,000
580
136
NS
245
230
7,167
930
39,264
900
29,333
11,900
2,370
27
54,000
4,900
67,000
81,667
1,400
72,000
29,333
1,043
28
NS
29,750
8,200
170
18,300
2,300
13,500
860
10,400
.68
62,000
4.3
48,060
4,312
9,9
7,200
8,348
                                                          76

-------
Table B-3. Preliminary Bioventing Initiative Results
: BTEX and TPH Soil Gas Concentrations (Continued)
Soil Gas Analysis
Air Force
Base
Pope
Randolph

Robins


Shaw
Tinker
Travis

Vandenburg

Westover

Wright Patterson

Site
Site ST-08
Tank 20 Site

UST173

SS10
Site SS-15
POL Storage Area C
Fuel Storage Area G
South Gas Station
Service Station
JP-4 Site
Building 7701
Building 7705
Fire Training Area
Spill Sites 2 and 3
Time
Initial
Initial
Final
Initial
Final
Initial
Final
Initial
Initial
Final
Initial
Final
Initial
Initial
Initial
Initial
Final
Initial
Final
Initial
Initial
Benzene
(ppmv)
BDL
16
BDL
0.0013
0.086
270
57
210
53
0.018
1,300
7.1
1,650
160
NS
NS
610
BDL
BDL
0.23
0.07
Toluene
(ppmv)
25
0.53
BDL
0.028
0.011
109
40
200
100
0.022
550
11
1,125
84
NS
NS
BDL
BDL
0.0093
0.42
2.59
Ethylbenzene
(Ppmv)
4.0
6.1
0.048
0.17
BDL
16
15
32
11
0.73
100
6.4
61
28
NS
NS
0.13
0.12
0.0063
0.21
1.92
Total
Xylenes
(ppmv)
10
18
0.21
1.04
0.016
84
67
120
36
1
97
31
240
139
NS
NS
0.031
0.087
0.023
0.29
6.76
Total
BTEX
(ppmv)
39
40.63
0.26
1.24
0.11
479.00
180
560
202.00
1.8
2,048.00
56
3,076.00
411.00
NS
NS
610
0.23
0.039
1.15
11.34
TPH
(ppmv)
3,800
19,667
50
206
1.1
55,000
13,000
69,700
11,500
190
110,000
2,300
145,000
19,467
NS
NS
0.57
92
0.34
1,147
2,398
NS = not sampled.
BDL = below detection limit.
                                                          77

-------
Table B-4.   In Situ Respiration Test Results at Bioventing Initiative Sites
                                                              Initial
6-Month
                            1-Year
Air Force Base
AFP 4

AFP PJKS
Battle Creek
Beale


Boiling

Camp Pendleton
Cannon
Cape Canaveral



Charleston

Davis Monthan

Dover

Dyess

Edwards


Eglin

Eielson


Ellsworth

Elmendorf



FE Warren

Galena



Hanscom

Site
FSA-1
FSA-3
ST-35
Fire Training Area
Site 3
Site 18
Site 11
Building 18
Former Storage Tank Farm
Site 1
SWMU 70
FTA-2
Facility 1748
Facility 44625D
Facility 44625E
FT-03
Site SS-41
Site 35
Site 36
ST-04
North STF
Site FT40
Site FT41
Site 21 •
Site 16
Site 43
FTA Hurleburt Field
Old Eglin FTA
ST-10
Site 48-E2
Site 48-E3
Area D Bulk Fuel Storage
Building 102 Base Fuel
Station
43/45 Pumphouse
ST-61
ST-71
43/55 Pumphouse
Fire Training Pit
Spill Site
Saddle Tank Farm
Power Plant
Million Gallon Hill
Campion POL Leak Site <
Building 1639
Building 1812
%/hr
0,32
0.91
0.52
0.39
0.14
0.74
0.12
0.11
1.4
0.021
0.53
0.18
0.16
0.39
0.17
0.54
0.38
0.009
0.078
0.18
0.30
0.010
NC
0.16
0.031
0.033
0.18
0.18
0.29
0.18
NC
1.1
0.034
0.51
0.38
0.056
0.34
0.62
1.4
1.05
1.4
0.44
0.99
0.78
NC
mg/kg-
day
5.22
14.85
8.49
6.36
2.-28
12.08
1.96
1.80
22.85
0.34
8.65
2.94
2.61
6.36
2.77
8.81
6.20
0.15
1.27
2.94
4.90
0:16
NC"
2.61
0.51
0.54
2.94
2.94
4.73
2.94
NC
17.95
0.55
8.32
6.20
0.91
5.55
10.12
22.85
17.14
22.85
7.18
16.16
12.73
NC
%/hr
0.058
0.36
0.17
0.12
0.043
0.078
0.031
0.011
1.5
NC
NC
NC
NC
NC
NC
0.0059
NC
NC
NC
NC
NC
NC
NC
0.016
0.0051
0.0060
NC
NC
6.22
0.046
0.067
0.068
0.0096
0.09
0.072
0.015
0.0066
NC
0.052
NC
NC
NC
NC
0.26
0.036
mg/kg-
. day
0.95
5.88 •
2.77
1.96
0.70
1.27
0.51
0.18
24.48
NC
NC
NC
NC
NC
NC
0.10
NC
NC
NC
NC
NC
NC
NC
0.26
0.08
0.10
NC
NC
3.59
0.75
1.09
1.11 ,
0.16
1.47
1.18
0.24
0.11
NC
0.85
NC
NC
NC
NC
4.24
' 0.59
%/hr
0.059
0.54
0.33
0.16
0.016
0.069
0.033
0.080
0.98
NC
NC
NC
NC
-NC
NC
0.084
NC
NC
NC
NC
NC
NC
NC
0.23
0.059
0.019
NC
NC
0.10
0.11
0.11
0.074
0.0056
0.32
0.44
0.06
0.16
NC
0.018
NC
0.059
0.11
NC
0.048
NC
mg/kg-
day
0.96
8.81
5.39
2.61
0.26
1.13
0.54
1.31
15.99
NC
NC
NC
NC
NC
NC
1.37
NC
NC
NC
NC
NC
NC
NC
3.75
0.96
0.31
NC
NC
1.63 •
1.80
1 .80
1.21
0.09
5.22
7.89
1.23
2.61
NC
0.29
NC
%63
1.80
NC
0.78
NC
                                                               78

-------
Table B-4. In Situ
Air Force Base
Hickam


Hill







Johnston Atoll


Keesler

Kelly


Kirtland

XI Sawyer


Little Rock
Los Angeles


Malmstrom

March
McClellan




McGuire
Mt. Home
Nellis


Newark
Offutt

Respiration Test Results at Bioventing Initiative Sites (Continued)
Initial 6-Month
Site
Area H
Area K
Site 2 FSA
Site 204.1
Site 214.1
Site 228
Site 924
Site 1705
Site 388
Site 40002
Site 510.8
Old Fire Training Area
Former POL Tank Farm
Storage Tanks 260 and 261
SWMU 66
AOCA
Site S-4
Site FC-2
Site D-10
Fire Training Area 1 3
Fire Training Area 14
POL Area
FTA-06
FTA-07
Spill Site 18
Building 125
Building 241
Gate 3
Pumphouse II
POLSA
IRP Site 35c
Davis Site
PRL T-46
Study Area 6
Tank Farm #2
Tank Farm #4
Bulk Fuel Storage
POL Yard
Site 27
Site 28
Site 44
Facility 27
Facility 89
Low Point Drain
Building 406
Building 30
POL Storage Area
%/hr
0.71
1.2
0.6
0.98
0.31
0.54
0.56
NC
0.42
0.22
0.022
0.42
0.24
0.64
0.65
0.081
2.4
1.9
1.1
0.061
0.0055
0.11
0.13
0.074
2.04
0.33
0.25
0.27
3.2
1.1
0.29
0.37
0.91
0.32
0.31
0.33
1.2
0.32
0.048
0.21
0.69
0.026
0.021
0.86
5.6
4.9
0.1
mg/kg-
day
11.59
19.58
9.79
15.99
5.06
8.81
9.14
NC
6.85
3.59
0.36
6.85
3.92
10.44
10.61
1.32
39.17
31.01
17.95
1.00
0.09
1.80
2.12
1.21
33.29
5.39
4.08
4.41
52.22
17.95
4.73
6.04
14.85
5.22
5.06
5.39
19.58
5.22
0.78
3.43
11.26
4.24
0.34
14.04
91.39
79.97
1.63
%/hr
0.093
0.45
0.27
0.057
0.015
0.031
0.043
NC
0.090
0.016
0.021
NC
NC
NC
0.41
0.097
0.28
0.72
0.057
0.012
0.0043
0.11
0.047
0.021
NC
NC
NC
NC
0.29 <•
0.34
NC
0.12
0.19
0.016
0.030
0.011
0.28
NC
0.0035
0.038
0.028
NC
0.0096
NC
0.33
0.051
NC
mg/kg-
day
1.52
7.34
4.41
0.93
0.24
0.51
0.70
NC
1.47
0.26
0.34
NC
NC
NC
6.69
1.58
4.57
11.75
0.93
0.20
0.07
1.80
0.77
0.34
NC
NC
NC
NC
4.73
5.55
NC
1.96
3.10
0.26
0.49
0.18
4.57
NC
0.06
0.62
0.46
NC
0.16
NC
5.39
0.83
NC
1-Year
%/hr
0.012
0.38
0.53
0.096
0.015
0.059
0.007
NC
0.39
0.083
0.091
0.44
0.22
0.23
0.60
0.083
0.11
0.58
0.070
0.0083
NC
0.16
0.029
0.012
NC
NC
NC
NC
NC
0.25
NC
0.50
0.37
0.11
0.064
0.099
0.72
NC
0.031
0.016
0.022
0.015
0.021
NC
0.26
0.039
0.46
mg/kg-
day
0.20
6.20
8.65
1.57
0.24
0.96
0.12
NC
6.36
1.35
1.49
7.2
3.5
3.7 ,
9.79
1.35
1.80
9.47
1.14
0.13
NC
2.61
0.47
0.20
NC
NC
NC
NC
NC
4.08
NC
8.16
6.04
1.80
1.04
1.62
11.75
NC
0.51
0.26
0.36
0.24
0.34
NC
4.24
0.64
7.51
79

-------
Table B-4.  In Situ Respiration Test Results at Bioventing Initiative Sites (Continued)
                                                            Initial
6-Month
                           1-Year
Air Force Base
Patrick

Pease
Pittsburgh

Randolph
Robins

Shaw

Tinker
Travis

Vandenburg
Westover

Wright Patterson

Site
FTA-2
BX Service Station
Bulk Fuel Storage Area
Fire Training Areas 2 and 3
•Fire Training Pit 4
Tank 20 Site
UST 173
SS10
Site FT-01
Site SS-15
POL Storage Area C
Fuel Storage Area G
South Gas Station
Service Station
Building 7701
Building 7705
Fire Training Area
Spill Sites 2 and 3
%/hr
0.34
0.16
3.57
0.84
0.20
0.41
0.029
0.18
0.43
0.16
0.18
3.6
2.47
0.24
0.33
0.12
0.19
0.26
mg/kg-
day
5.55
2.61
58.26
13.71
3.26
6.69
0.47
2.94
7.02
2.61
2.94
58.75
40.31
3.92
5.39
1.96
3.10
4.24
%/hr
0.41
0.21
NC
0.17
NC
0.15
0.0023
0.031
NC
NC
0.038
0.79
NC
NC
0.0098
NC
NC
NC
mg/kg-
day
6.69
3.43
NC
2.77
NC
2.45
0.04
0.51
NC
NC
0.62
12.89
NC
NC
0.16
NC
NC
NC
%/hr
0.33
0.028
NC
0.094
NC
0.28
0.013
0.020
NC
NC
0.056
0.86
NC
NC
0.052
0.05
NC
NC
mg/kg-
day
5.39
0.46
NC
1.53
NC
4.57
0.21
0.33
NC
NC
0.91
14.04
NC
NC
0.85
0.82
NC
. NC
 NC = not conducted.
                                  »U.S.  GOVERNMENT PRINTING OFFICE: 1997-549-001/60168
                                                             80

-------