Citation
An evaluation of the attenuation mechanisms for dissolved aromatic hydrocarbons from gasoline sources in a sandy surficial Florida aquifer

Material Information

Title:
An evaluation of the attenuation mechanisms for dissolved aromatic hydrocarbons from gasoline sources in a sandy surficial Florida aquifer
Creator:
Angley, Joseph Timothy, 1958-
Publisher:
[s.n.]
Publication Date:
Language:
English
Physical Description:
xv, 319 leaves : ill. ; 28 cm.

Subjects

Subjects / Keywords:
Aquifers ( jstor )
Biodegradation ( jstor )
Gasoline ( jstor )
Groundwater ( jstor )
Hydrocarbons ( jstor )
Hydrogen ( jstor )
Isotherms ( jstor )
Oxygen ( jstor )
Solutes ( jstor )
Sorption ( jstor )
Dissertations, Academic -- Environmental Engineering Sciences -- UF
Environmental Engineering Sciences thesis Ph. D
Gasoline -- Environmental aspects ( lcsh )
Groundwater -- Pollution ( lcsh )
Hydrocarbons -- Environmental aspects ( lcsh )
Oil pollution of water ( lcsh )
City of Lake Alfred ( local )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1987.
Bibliography:
Bibliography: leaves 306-318.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Joseph Timothy Angley.

Record Information

Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Resource Identifier:
021911603 ( ALEPH )
18277859 ( OCLC )

Downloads

This item has the following downloads:


Full Text












AN EVALUATION OF THE ATTENUATION MECHANISMS
FOR DISSOLVED AROMATIC HYDROCARBONS FROM GASOLINE
SOURCES IN A SANDY SURFICIAL FLORIDA AQUIFER







By

JOSEPH TIMOTHY ANGLEY





























A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY


UNIVERSITY OF FLORIDA


1987
































Copyright 1987

by

Joseph T. Angley















ACKNOWLEDGEMENTS


My sincere thanks are extended to my commitee chairman, Dr. Lamar Miller, for his insight and support during this research. Special thanks are also extended to my cochairman, Dr. Joseph J. Delfino, for his guidance and thoughtful criticism. I would also like to thank Dr. Paul Chadik, Dr. Peter Nkedi-Kizza and Dr. Daniel Spangler for their generous assistance in the design and interpretation of these experiments. My thanks also go to Dr. Suresh Rao for his probing questions and criticisms and for the kind use of his laboratory.

The work presented in this dissertation could not have been accomplished without the support and assistance of many of my colleagues. my sincere thanks are extended to Mr. Norman Cabrera for his valuable assistance with several laboratory experiments, and to Mr. Gene Killan, Ms. Vicki Card and Mr. Ben Horenstein for their help in the collection of field samples and maintenance of the field site. I would also like to thank Ms. Robin Mitchell for her work on the microbial analyses, Mr. Jimmy Yeh for his work on GC analyses, Ms. Linda Lee for her help in setting up the column studies, and Mr. Bill Davis for his expert assistance with gas chromatography and quality assurance procedures.



iii









Finally, this work would not have been possible without the love, support and friendship provided by my wife Beth. I also thank my family for their financial support during my many years of schooling.

This research was funded through a research grant from the Institute for Food and Agricultural Sciences.











































iv















TABLE OF CONTENTS

2age

ACKNOWLEDGEMENTS ................................... iii

LIST OF TABLES .................. o .................. vii

LIST OF FIGURES ............................... x

ABSTRACT ........................................... xii

CHAPTERS

I INTRODUCTION, ................................ 1

II OBJECTIVES ................................... 6

III LITERATURE REVIEW ............................ 7

3.1 Introduction ............................ 7
3.2 Environmental Effects of Gasoline
Contamination ....................... 7
3.3 Convective-Dispersive Models ............ 10
3.4 Sorption of Aromatic Compounds .......... 13
3.5 Biodegradation of Aromatic Compounds .... 24 3.6 Summary ................................. 33

IV MATERIALS AND METHODS ........................ 34

4.1 Introduction ......................... :*: 34
4.2 Site Description .................... 34
4 3 Aquifer Material ........................ 35
4 4 Choice of Solutes ....................... 38
4 5 Hydrocarbon Analyses .................... 40
4 6 Hydrolysis Studies ...................... 42
4.7 Batch Sorption Studies .................. 43
4.8 Column Sorption Studies ................. 45
4.9 Hydrogen Peroxide Evaluation ............ 47
4.10 Batch Biodegradation Studies ............ 48
4.11 Column Biodegradation Studies ........... 53
4.12 Field Studies ........................... 56

V RESULTS AND DISCUSSION ....................... 59

5.1 Introduction ............................ 59
5.2 Hydrolysis of Aromatic Compounds ........ 59 5.3 Characterization of Aquifer Materials ... 61 5.4 Batch Sorption Studies .................. 61

V










5.5 Breakthrough Curves for Aromatic Solutes 79
5.6 Evaluation of Sorption models ........... 93
5.7 Comparison of Mixed Solute and Single
Solute Retardation .................. 106
5.8 Evaluation of Hydrogen Peroxide
Reactivity .......................... 108
5.9 Batch Biodegradation Experiment #1 ...... ill 5.10 Batch Biodegradation Experiment #2 ...... 128 5.11 Column Biodegradation Experiments ....... 146 5.12 Comparison of Field and Laboratory data. 156

VI SUMMARY AND CONCLUSIONS ...................... 168

6.1 Summary ................................. 168
6.2 Conclusions ............................. 178

APPENDICES

A CHROMATOGRAPHIC CONDITIONS AND QUALITY
CONTROL PARAMETERS FOR THE ANALYSIS OF
AROMATIC HYDROCARBONS ........................ 179

B FIELD SAMPLING PROCEDURES .................... 182

C ISOTHERM DATA FOR THE SORPTION OF
STUDY COMPOUNDS TO AQUIFER MATERIALS ......... 186

D BREAKTHROUGH CURVE DATA FOR SORPTION OF
STUDY COMPOUNDS TO AQUIFER MATERIALS ......... 214

E BATCH BIODEGRADATION DATA .................... 229

F COLUMN BREAKTHROUGH DATA FOR
BIODEGRADATION COLUMNS ....................... 272

G HYDROCARBON CONCENTRATIONS IN MONITORING
WELLS AT THE LAKE ALFRED CITRUS RESEARCH
AND EDUCATION CENTER ......................... 291

REFERENCES ............ o ........ o ................... 306

BIOGRAPHICAL SKETCH ................................ 318













vi















LIST OF TABLES


Table Page


3-1 Selected physical properties of study compounds 9

3-2 Summary of adsorption data for aromatic
hydrocarbons ................................... 23

3-3 Sorption coefficients of selected aromatic
hydrocarbons on low organic soil ............... 25

4-1 Experimental design for batch biodegradation
experiment #1 .................................. 49

4-2 Experimental design for batch biodegradation
experiment #2 .................................. 51

5-1 Selected physical and chemical properties of the
Lake Alfred aquifer material ................... 62

5-2 Regression parameters for the analysis of
average values of equilibrium batch isotherm
sorption data with the linear model ............ 65

5-3 Regression parameters for the analysis of
average values of equilibrium batch isotherm
sorption data with the linear model suppressedd
intercept) ..................................... 67

5-4 Regression parameters for the analysis of
average values of equilibrium batch isotherm
data with the Freundlich model ................. 68

5-5 Ratios of sorbed concentrations calculated from
Freundlich and linear equilibrium models ....... 71

5-6 Regression parameters for the analysis of
average values of equilibrium batch
desorption data with the linear model .......... 76

5-7 Regression parameters for the analysis of
average values of equilibrium batch desorption data with the linear model
suppressedd intercept) .......................... 77



Vii











5-8 Regression parameters for the analysis of
average values of equilibrium batch
desorption data with the Freundlich model .........78

5-9 Values of Dispersion calculated from the
breakthrough curves of unretained solutes in
laboratory columns................................. 81

5-10 Calculated values of R, K and K from
analysis of solute breakthrough curves........... 87

5-11 Retardation factors calculated from leaching
column and equilibrium batch isotherm data ........88

5-12 An empirical index of sorption nonequilibrium
(ISNE) for 12 selected aromatic solutes leaching
through Lake Alfred aquifer material............. 90

5-13 Regression coefficients for plots of log Koc
VS. log Kow and log Koc vs log WS................ 98


5-14 Comparison of relationships to predict Koc
from Kow values.................................... 99

5-15 Regression coefficients for the relationship
between log Koc and X............................ 104

5-16 Total average hydrocarbon values (ug/L) in the
microcosms of batch biodegradation
experiment #1...................................... 113

5-17 Biodegradation rate constants, half lives and
correlation coefficients for the fit of
biodegradation experiment #1 data to a first
order rate equation................................ 116

5-18 Biodegradation rate constants, half lives
and correlation coefficients for the fit of
biodegradation experiment #1 data to the
Thomas-slope rate equation........................ 118

5-19 Total average hydrocarbon values (ug/L) in
the microcosms of batch biodegradation
experiment #2...................................... 129

5-20 Biodegradation rate constants, half lives and
correlation coefficients for the fit of
biodegradation experiment #2 data to a first
order rate equation................................ 133


viii











5-21 Biodegradation rate constants, half lives and
correlation coefficients for the fit of
biodegradation experiment #2 data to the
Thomas-slope rate equation........................ 135

5-22 First order biological rate constants and
half-lives of aromatic hydrocarbons for the
biodegradation column with flow at 0.90 mL/hr.. 149

5-23 First order biological rate constants and
half-lives of aromatic hydrocarbons for the
biodegradation column with flow at lmL/min........151

5-24 Microbial populations in a soil core taken
south of the paint shop (bldg 54), June, 1986.. 163

5-25 Microbial populations in a soil core taken
in the spray field June, 1986..................... 163

5-26 Microbial populations in a soil core taken
south of the pump house (bldg 12) july, 1986 ... 164

5-27 Microbial populations from samples collected
during instasllation of monitoring wells
RAP-5 amd RAP-6, September, 1986.................. 165

5-28 Water chemistry parameters from selected
monitoring wells at Lake Alfred CREC, 1986 ........166

























ix















LIST OF FIGURES

Figure

4-1 Site plan of the field research site at
the Citrus Research and Education Center,
Lake Alfred, Fl.................................... 36

4-2 Extent of the hydrocarbon pl1ume at the field
research site as of October, 1986................. 37

5-1 Approach to equilibrium for several aromatic
solutes on Lake Alfred aquifer material.......... 63

5-2 Freundlich sorption isotherm
for benzene at equilibrium........................ 73

5-3 Freundlich sorption isotherm for
toluene at equilibrium............................ 74

5-4 Breakthrough curve for chloride for a 5 cm
sorption column.................................... 80

5-5. Breakthrough curve for benzene from
Lake Alfred water (Co = 4700 ug/L)................ 83

5-6 Breakthrough curve for toluene from
Lake Alfred water (Co 2600 ug/L)................ 84

5-7 Breakthrough curve for n-propylbenzene from
Lake Alfred water (C. = 1000 ug/L)................ 85

5-8 Log K o vs. log K o for study compounds.......... 95

5-9 Log K H(from column data) vs. log WS
for s udy compounds................................ 97

5-10 Regression equations for several models
describing the relationship between K and K :(a) Curtis et al., 1985
(8 Schwaorzenbach and Westall, 1981 (c) this
study (d) Briggs, 1981 (e) Chiou et al., 1983.. 101

5-11 Log K ocVS. l X for aromatic solutes (a) in this
study and (b) from Sabljic (1987)................. 103

5-12 Breakthrough curve for benzene (single solute)
spiked into RAP-2 well water (Co = 4000 ug/L).. 107


X











5-13 Reaction of OHM-4 well water to the
addition of 50% hydrogen peroxide and aquifer
material............................................ 110

5-14 Relative concentration vs. time for five aromatic
compounds in biodegradation treatment 1A ..........121

* 5-15 Relative concentration vs. time for~ four C9H1
compounds in biodegradation treatment 1A ..........122

5-16 Concentration vs. time for dissolved oxygen
in biodegradation treatments 1A, 1B and 1C ........124

5-17 Concentration vs. time for dissolved oxygen
in biodegradation treatments 1D, 1E, 1F
and 1G.............................................. 126

5-18 Relative concentrations of C C aromatic
hydrocarbons vs. time in biogegradation
treatment 2B....................................... 137

5-19 Relative concentrations of C -Caromatic
hydrocarbons vs. time in biogegradation
treatment 2D....................................... 139

5-20 Concentration vs. time for dissolved oxygen
in biodegradation treatments 2D, 2E and 2F ........140

5-21 Electron transport activity in biodegradation
treatments 2D, 2E and 2F.......................... 141

5-22 Electron transport activity in biodegradation
treatments 2A, 2B and 2C.......................... 145

5-23 Breakthrough curves for aromatic compounds in
column biodegradation experiments performed
at a flow rate of 0.90 mL/hr..................... 148

5-24 Breakthrough curve for benzene in column
biodegradation experiment performed at a flow
rate ofl1mL/min.................................. 152

5-25 Breakthrough curve for toluene in column
biodegradation experiment performed at a flow
rate of 1 mL/min.................................. 153

5-26 Breakthrough curve for 1,2,4-trimethylbenzene
in column biodegradation experiment performed
at a flow rate of 1 mL/min....................... 154


Xi











5-27 Breakthrough curve for field tracer (NH4Cl)
experiment measured at RAP-10 ..................... 158

5-28 Distribution of benzene (ug/L) at the
Lake Alfred field site ........................ 160

5-29 Distribution of o-xylene (ug/L) at the
Lake Alfred field site ........................ 162













































xii















Abstract of Dissertation Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy




AN EVALUATION OF THE ATTENUATION MECHANISMS
FOR DISSOLVED AROMATIC HYDROCARBONS FROM GASOLINE
SOURCES IN A SANDY SURFICIAL FLORIDA AQUIFER


by

JOSEPH TIMOTHY ANGLEY


December 1987

Chairman: Wesley Lamar MIller Cochairman: Joseph J. Delfino Major Department: Environmental Engineering Sciences


Gasoline is a significant source of groundwater

contamination in Florida. This results from the large numbers of gasoline storage tanks, high rainfall, reliance on groundwater-based potable water supplies and the hydrogeology of Florida. Sorption, biodegradation and hydrolysis of dissolved aromatic hydrocarbons (all isomers of C 6H 6- C9 H12 ) were determined in multicomponent experiments with natural aquifer materials under saturated conditions. Hydrogen peroxide, air, oxygen gas and ammonium chloride treatments were evaluated as methods to enhance microbial degradation of aromatic hydrocarbons. The solutes and sorbents were from a gasoline contaminated aquifer in central Florida. This site was typical of sandy surficial Xiii










aquifers in Florida with a low organic carbon content (0.015%). The aquifer was composed primarily of fine to medium grained sands.

Hydrolysis was not a significant removal mechanism for the selected aromatic solutes. Equilibrium batch isotherms and column studies determined sorption coefficients for aromatic solutes ranging between 0.045 and 0.1 with retardation values between 1.36 and 2.40. Column breakthrough curves exhibited minimal effects of adsorption non-equilibrium. Sorption isotherms were linear through the concentration range tested and no significant hysteresis was noted. Partitioning and surface dependent adsorption were evaluated by regression of column K oc data with literature values of K ow water solubility and first order connectivity indices. No single model fully described the sorption process, and the sorption mechanism appeared to be a combination of several processes. Competitive solute interactions were not shown to be significant.

Column biodegradation experiments with acclimated

microorganisms were performed at flow velocities close to those from the contaminated aquifer. Half lives ranged from

0.940 hr for benzene to 0.086 hr for n-propylbenzene at

0.680 cm/min. Branched aromatic solutes were more easily degraded in column studies.

Batch studies demonstrated the ability of field

microbes to degrade aromatic hydrocarbons to less than 0.5 ug/L given sufficient oxygen. Microbes were not phosphorus Xiv









or nitrogen limited. Hydrogen peroxide increased dissolved oxygen, but did not lead to increased hydrocarbon removal in lab studies. Ammonium chloride produced nitrifying conditions. Oxygen augmentation with air and oxygen gas was shown to enhance biological removal of aromatic hydrocarbons.















































Xv















CHAPTER I
INTRODUCTION


Groundwater contamination is a topic of great

scientific interest and public concern. Groundwater provides approximately 100 million people with potable water in the United States (Hoag and Marley, 1986) and nearly every state contains some number of contaminated wells (Barbash and Roberts, 1986). The sources of groundwater contamination are numerous. These include seepage from lagoons and impoundments, landfills, agricultural and silvicultural practices, accidental spills and leaking storage tanks and transfer equipment.

Gasoline and petroleum products are some of the most common groundwater pollutants. The potential magnitude of this problem is evident from the volume of petroleum used in the United States. Approximately 110 billion gallons of motor fuels are stored underground each year, in an estimated 1.4 million underground storage tanks, 85% of which are unprotected steel tanks with finite lifetimes (Hoag and Marley, 1986). It is expected that 10 to 30% of these tanks may leak (Dowd, 1984).

Gasoline contamination of groundwater in Florida is a particularly serious problem. This results from the confluence of three factors: the large number of petroleum storage tanks in the state, the reliance on groundwater

1







2


based potable water supplies, and the hydrogeology of Florida.

The major sources of petroleum contamination in Florida are leaking storage tanks and pipes. The high water table in the'state leads to conditions favorable for corrosion. As of February 1986 there were 455 known storage tank incidents resulting in 368 cases of groundwater contamination. The total volume of spilled gasoline exceeds

4.2 million gallons (FLDER, 1986). The remaining 60,000 petroleum storage tanks in the state provide potential sources for future groundwater pollution.

These sources of contamination are particularly significant owing to the importance of groundwater in Florida. Groundwater withdrawal for potable water use is approximately 1400 Mgal/d, comprising 87% of public water and 94% of rural water supplies. It is noteworthy that nearly 2 million residents drink untreated water from shallow private wells which are particularly prone to contamination from underground storage tanks (Fernald and Patton, 1984).

Hydrogeology is the third factor which contributes to the sensitivity of Florida's water supplies to gasoline contamination. Most of the potable water aquifers are surficial or intermediate in depth, and are susceptible to contamination. In addition, the generally porous nature of top soil in the state enhances pollutant transport to the underlying aquifers. Most soils in Florida are sandy loam,







3

sandy clay and sandy clay loams, all of which are noted for their relatively high permeabilities (Fernald and Patton, 1984). The sandy deposits of the Pliocene and Pleistocene ages common to Florida are also marked by low organic carbon and clay content (Fetter, 1980), resulting in high permeability and low sorptive capacity.

Given the magnitude of this problem, the transport and environmental reactions of dissolved gasoline components in shallow sandy aquifers is an important area of study. This is particularly true of the aromatic constituents of gasoline, owing to their toxicity, concentrations in gasoline and their high aqueous solubility. Gasoline products which are released into the vadose zone travel downward under the influence of capillary and gravitational forces. When the sorptive capacity of the soil is exceeded, gasoline moves onto the groundwater table, where it spreads laterally across the top of the saturated zone. This is a result of the density of gasoline (0.7-0.75 g/cm 3 ). Gasoline components partition into the water to the extent of their water solubility, and move in the direction of the water table gradient.

Physical, chemical and biological factors must all be

considered in the determination of the fate and transport of dissolved gasoline hydrocarbons in groundwater. The interaction of these factors may be conveniently examined in the context of a generalized mass transport equation. A one-dimensional form of this equation is












@C3 D h ( C/9x2) V v( 3C/3x) -/ E/( @S/ 3t) Qi [1.1]


where C = solution phase concentration of solute (ug/L)
S = adsorbed phase concentration of 3solute (ng/g)
a = volumetric water content (mL/cm
t = time (min)
x = horizontal distance (cm)
p = bulk density (g/cm ) 2
D h= hydrodynamic dispersion coefficient (cm /min)
v = average pore water velocity (cm/min)
Q.i = degradation rate (minm



The components of this equation are convection,

dispersion, sorption and degradation terms. Convection describes the movement of a dissolved contaminant with the groundwater. Dispersion describes the spreading of the solutes during flow through the aquifer material. Sorption terms account for the retardation of the dissolved solutes by interaction with the aquifer matrix, and degradation terms evaluate the removal or transformation of the contaminants. Research has shown that sorption and biological degradation are the major attenuation mechanisms for organic solutes in soils and groundwater (Woodburn, 1985).

Mathematical models based on such equations are

important tools for the prediction of contaminant movement (Pinder, 1984). However, the adequacy of these predictions is directly related to a knowledgeable and accurate quantification of the processes involved (MacKay et al., 1985). The remediation of groundwater contamination also







5

requires detailed and usually site specific data for these processes.

This dissertation presents a detailed investigation of the attenuation of selected dissolved aromatic gasoline hydrocarbons in a typical sandy surficial aquifer in Florida, using a variety of batch and column techniques. Sorption coefficients and biological and abiotic degradation rates from laboratory studies are presented. These studies simulated conditions at a contaminated field site and included experiments to assess various treatment alternatives. Actual field data are summarized, and compared to the laboratory data.

The improved understanding obtained from the collection and analysis of these data should aid in the formation and improved use of predictive models describing the movement and reaction rates of water soluble components of gasoline. in shallow groundwater systems and aid in the selection of appropriate groundwater reclamation technologies.















CHAPTER II
OBJECTIVES

The main objectives of this study were:



(1) To evaluate the sorption coefficients for 12

selected aromatic hydrocarbons found in water at the Lake Alfred research site, employing batch isotherms and soil columns;

(2) To determine the rates of hydrolysis of the 12 selected aromatic hydrocarbons;

(3) To determine the rates of biodegradation of the 12 selected aromatic hydrocarbons under simulated field conditions, and after treatment with hydrogen peroxide, oxygen gas and ammonium chloride;

(4) To determine the most appropriate predictive model for sorption of the 12 selected aromatic hydrocarbons in a sandy surficial aquifer in Florida;

(5) To correlate molecular properties of the selected aromatic hydrocarbons with sorptive and biological parameters;

(6) To evaluate field data based on the laboratory measurements of sorption and biodegradation and

(7) To extrapolate the laboratory data for application of aquifer remediation practices.


6













CHAPTER III


LITERATURE REVIEW



3.1 Introduction



This chapter presents a review of the pertinent

literature for the reactions of gasoline derived aromatic hydrocarbons in groundwater. The major areas of discussion are the environmental effects of gasoline contamination, the use of advection-dispersion transport models, the sorption of aromatic compounds to aquifer materials, and the biodegradation of aromatic compounds in groundwater systems.



3.2 Environmental Effects of Gasoline Contamination



Gasoline is a complex mixture of many hydrocarbon compounds. A typical gasoline contains between 150-250 identifiable hydrocarbon components (Sanders and Maynard, 1968) consisting of alkane, alkene, aromatic and napthene hydrocarbons. Automobile gasolines are comprised of C 5- C12 hydrocarbons with boiling points in the range 32-210 C. Unleaded gasolines contain greater~ concentrations of aromatic hydrocarbons to provide for anti-knock protection and branched hydrocarbons to increase octane ratings (Moore and Moore, 1976).

7







8

Despite the large number of hydrocarbons comprising

gasoline, much of the environmental concern focuses on the water soluble components of gasoline, particularly the single ring aromatic compounds. These compounds are of concern based on their toxicity, aqueous solubility and concentration in gasoline (Barker and Patrick, 1985). Acute toxicity is associated with the water soluble fraction of oils (Blumer et al., 1973) and the major components of the water soluble fraction are aromatic (Coleman et al., 1984). Data from the work of Coleman et al. (1984) showed that although aromatic components made up only 50% of the unleaded gasoline product in their study, 87-95% of the components in the water soluble fraction were aromatic. Thus in a spill situation a significant amount of the contaminants in the water phase will be aromatic. Selected physical properties of the compounds used in this study are listed in Table 3-1.

The health effects from the use of gasoline

contaminated water may be significant. Benzene is a carcinogen in rats and mice and exposure is linked with leukemia (USPHS, 1981). The maximum contaminant level for benzene in community drinking water supplies is 1 ppb in Florida. Toluene, ethylbenzene and m-xylene affect the central nervous system (Windholtz, 1976). Unleaded gasoline induces renal and hepatocellular carcinomas in rats and the use of petroleum contaminated water can produce elevated levels of indoor air pollutants allowing chronic exposure to












Table 3-1. Selected physical properties of study compounds.



Moleculara Waterb Boilinga
a c
Weight, Solubility, Point, Density, log d
Compound AMU mg/L OC g/ml Kow X
ow


Benzene 78.11 1740-1791 80.1 0.8675 1.56-2.28 3.000
Toluene 92.13 515- 724 110.6 0.8669 2.11-2.73 3.394
Ethylbenzene 106.2 131- 208 136.2 0.8670 3.15 3.932
m,p-Xylene 106.7 134- 196 139.1 0.8642 3.18 3.788
138.4 0.8611
o-Xylene 106.7 142- 213 144.4 0.8802 2.77-3.13 3.805
3,4-Ethyltoluene 120.2 40 161.3 0.8645 4.326
162.5 0.8616
1,3,5-Trimethylbenzene 120.2 48- 92 164.7 0.8652 3.42-3.60 4.182
2-Ethyltoluene 120.2 40 165.2 0.8807 4.343
1,2,4-Trimethylbenzene 120.2 52- 59 169.3 0.8758 4.198
1,2,3-Trimethylbenzene 120.2 75 176.1 0.8944 3.60 4.215
Isopropylbenzene 120.2 48- 73 165.4 0.9106 3.60 4.305
n-Propylbenzene 120.2 55 159.2 0.8620 3.57-3.68 4.432


aCRC Handbook of Chemistry and Physics, 1980.

Brookman et al., 1985.

cLeo et al., 1971.

dSabljic, 1987.

Ik0







10

hydrocarbons (Shehata, 1985). Dermal absorption of volatile organic contaminants from gasoline may also be a significant exposure (Brown et al., 1984).

Fire and explosion hazards are also a risk factor in

the release of gasoline to the environment. Volatilization and subsequent gas phase transport of hydrocarbons in the unsaturated zone have destroyed buildings (Hoag and Marley, 1986).



3.3 Convective-Dispersive models



The cogent evaluation of contaminant plumes, remedial action alternatives, and risk assessment for organic compounds in groundwater requires a thorough understanding of the behavior of these contaminants in groundwater systems. This includes an assessment and quantification of the relevant processes which influence their fate and transport (Miller and Weber, 1984).

The interaction of these processes may be examined in the context of convective-dispersive models. These models have been reviewed (Anderson, 1979, Freeze and Cherry, 1979) and are marked by their computational simplicity, reasonable data requirements and sufficiently accurate output (Roberts et al., 1985). Although the adequacy of convective-dispersive models for describing solute transport has been questioned (Anderson, 1979, Smith and Schwartz, 1980), particularly with regard to dispersivity









approximations, these models provide a convenient framework for understanding the transport of dissolved solutes in groundwater.

The general form of the solute transport equation under saturated flow conditions is given by Bear (1979). A onedimensional form of this equation for conservative contaminants under steady flow conditions is



aC/at = D h (a 2C/ax2 )- v( ac/ax) [3.1]


where C = solution phase concentration of solute (ug/L)
S = sorbed phase concentration of solute (n2/g)
D h = hydrodymanic dispersion coefficient (cm /min)
t = time (min)
x = horizontal distance (cm)
V = average pore water velocity (cm/mmn)


The major components of this equation are convection (bulk flow) and dispersion (deviation from bulk flow). A brief discussion of dispersion follows, with reference to extrapolation of laboratory data to field scale applications.

The hydrodynamic dispersion coefficient describes the spreading of a solute as it moves through porous media. Hydrodynamic dispersion (D h) is the sum of mechanical dispersion, caused by differences in water velocity through sinuous and tortuous pores, and molecular diffusion (Biggar and Nielsen, 1962). Dispersion values reflect the heterogeneity of the aquifer material. Dispersion is usually determined by measuring the breakthrough of a conservative tracer such as chloride or tritiated water.






12



The physical and mathematical relationships of water and solute transport were reviewed by Davidson et al. (1983). Solute dispersion was noted to occur because of macroscale spatial changes in the direction and magnitude of water flow. The continuum approach to mathematically describe water and solute transport in laboratory soil columns was shown to be reasonably successful.

In practice, laboratory measurements and theory may be of little value in predicting dispersion in natural aquifers. Laboratory columns give dispersivity estimates on the order of centimeters, whereas field scale dispersion is usually in meters (Bedient et al., 1985). This is a result of the greater heterogeneity of a field site versus a small homogeneous laboratory column. A solution for equation [3.1] for a finite column using dimensionless variables was presented by Brenner (1962). The dimensionless Peclet number (P e) was used as a measure of dispersion: P= vL/4D h [3.2]
where v is pore water velocity (cm/mmn), L is the length

(cm) of the soil column and D h is the hydrodynamic dispersion coefficient (cm 2 min). For values of P e> 100 dispersion is assumed negligible. Values of P e< 10 generally indicate complete mixing. Boundary conditions for displacement experiments through short laboratory columns were reviewed by van Genuchten and Parker (1984). The solution of Brenner (1962) was shown to correctly conserve mass in finite laboratory soil columns, based on mass






13



balance considerations. For a flux type inlet boundary condition (flowing concentrations), Brenner's solution was applicable provided the column Peclet number was not much less than five. The solution of Lapidus and Amundson (1952) was recommended to evaluate flux averaged concentrations in finite laboratory columns or semi infinite field profiles.



3.4 Sorption of Aromatic Compounds



Sorption is a major mechanism in the attenuation of organic solutes in the saturated zone. Solutes differentially sorb onto aquifer materials and thus are retarded in their movement through the subsurface, resulting in a chromatographic like separation of the soluble constituents of a plume, with groundwater as the mobile phase.

Sorption describes the transfer of solutes from a

liquid phase to a solid phase (Miller and Weber, 1984). In this literature review the liquid phase is assumed to be water, containing solubilized organic solutes and the solid phase is the aquifer material under saturated, steady flow conditions. Sorption is influenced by the physical and chemical characteristics of the aquifer (ie., soil type, fraction of organic carbon), and the solute (ie., solubility, volatility, density).

Although sorption is a major component in the

attenuation of solutes in the subsurface, the fundamental






14


processes of solute-soil interaction and the thermodynamics of this process are not completely characterized. Therefore, sorption is used in this study as a generic term to describe solute retention (ie. uptake of solute), regardless of whether the process is one of adsorption, absorption or partitioning (Woodburn, 1985). Desorption is used here to describe solute removal from the solid phase.

3.4.1 Sorption Processes

The attractive forces acting to effect sorption of

hydrophobic compounds onto natural sorbents were reviewed by voice and Weber (1983). The major theory is discussed below.

Bonding forces in sorption may be both physical and

chemical, though both are basically electrostatic in nature. Physical sorption results from Van der Waals forces. The strength of these interactions is generally on the order of 1-2 Kcal/mole. These energies may be augmented by a thermodynamic gradient driving hydrophobic molecules out of solution. This is based on entropic considerations (solvophobic theory).

Chemical sorption is the interaction between specific sites of the sorbent and individual solute molecules. This approximates a true chemical bond with heats of adsorption between 15-50 Kcal/mole. Voice and Weber (1983) point out that it is difficult to assess the importance of each type of bonding. The heterogeneous nature of natural sorbent materials is largely unknown, and sorption processes probably involve all types of interactions.







15

3.4.2 Sorption Equilibria

Two experimental techniques are widely used to evaluate the @S1 @t term in equation [1.1]. These are batch equilibrium and soil column methods. Batch studies allow the evaluation of the linearity of the sorption isotherm and their use is well documented (Schwarzenbach and Westall, 1981, Chiou et al., 1979). The most widely used models to describe sorption equilibria in groundwater systems are the linear [3.3] and Freundlich models [3.4] (Miller and Weber, 1984):

S =K d* C [3.3]

S= K f Cn (n < 1) [3.4]

where S (ug/g) and C (ug/L) are the adsorbed phase and solution phase concentrations respectively at equilibrium, K d (L/g) is the linear sorption coefficient, K f (L/g) is the Freundlich sorption coefficient (both K dand K indicating sorption capacity) and n is an empirical constant (indicating sorption intensity). The linear model is in effect, a special case of the Freundlich model where n=l. The Freundlich equation is often linearized (log transformed) to facilitate calculation of variables K f and n in batch studies:

log S =n *log C +Log K f [3.5]

In column studies K dis evaluated through the retardation factor (R). The mass transport equation for reactive solutes under steady flow is described by equation [3.6]:







16



2 2
SC/3t + p/0 3 S/Dt Dh C /3x v [3.6]



where p is the bulk density, 0 is the volumetric water content and S is the sorbed phase concentration. Note that equation [3.6] is equivalent to equation [3.1] with the addition of the sorption term ;S/ ;t. Assuming linear, reversible sorption, the sorbed concentration of a solute is related to the aqueous concentration of the solute by the relationship:

S/3t = Kd Dc/at [3.7]



Substitution for ;S/ 3t in equation [3.6] with equation [3.7] yields the relationship:

aC/at + Kd aC/at (p/G) = Dh a2C/ x2 v aC/ax [3.8]

After separation of variables equation [3.8] becomes aC/at [ 1 + p Kd/e] = Dh 2C/x2 v aC/ax [3.9]

and by defining the retardation factor (R) as R = 1 + p Kd/0 [3.10]

sQbstitution of equation [3.10] into [3.9] results in the incorporation of the retardation factor (R) into the mass transport equation for solute transport under saturated steady flow conditions:

R ac/ t = Dh a2C/ax2 -v aC/ax [3.11]

Analysis of equation [3.10] indicates that the value of R is largely dependent on Kd for a homogeneous aquifer system or laboratory column. Determination of R from soil







17

column studies leads to the evaluation of Kd from equation [3.10]. Nkedi-Kizza et al. (1987) compared techniques for the calculation of R from soil column leaching experiments and from batch isotherm experiments. Values of R calculated by determining the area above the breakthrough curve were shown to be equivalent to R values calculated by using equation [3.10].

3.4.3 Sorption Estimators

Recently, approximation methods based on the assumption of partitioning as the dominant method of solute interaction have become common (Karickhoff et al., 1979, Chiou et al., 1979, Kenaga and Goring, 1980, Chiou et al., 1983). Their use is largely a result of the time and difficulty in the accurate measurement of sorption coefficients (Kd), and the general lack of data on hydrocarbon sorption to environmental sorbents. These authors note a correlation between the fractional organic carbon content of the sorbent material (f oc) and Kd. The Kd normalized to foc of the sorbent is described as K where: oc
Koc = Kd /foc [3.12]

Values of Koc is well correlated with aqueous solubility

(WS) (Chiou et al., 1979) and the octanol-water partition coefficient (K ow) (Karickhoff et al., 1979). These authors suggest that the solute-sorbent interaction is a partitioning process rather than an interaction between solute and the mineral surface. Evidence for partitioning is partially supported by the hydrophobic character of soil






18


organic matter, and by solvophobic theory (Rao et al., 1985). The general relationship between K ocand. K oand WS takes the form (Curtis et al., 1986):

Log K = a Log K ow+ Log if oc+ b [3.13]

Log K = c Log WS + Log fo + d [3.14]

where a,b,c, and d result from regression analysis of laboratory isotherm data and depend on the solute-sorbent system.

However, there are significant limitations on the use of these estimators, and the basis of partitioning as a sorption mechanism is questionable (Milgelgrin and Gerstl, 1983). In a strict sense, these relationships hold only for those compounds and sorbents used in the original studies (i.e., these are empirical relationships). This is reflected in orders of magnitude variation in estimates of sorption using these relationships. Application of the partitioning models may not be appropriate in experimental systems with solutes and sorbents which are different from those used to develop these models. In addition, these equations may not apply at organic carbon fractions less than 0.1% (Curtis et al., 1986). Rao and Jessup (1983) noted that the use of K octo estimate sorption can lead to significant errors with soils with very low (less than 0.1%) organic carbon contents.

Milgelgrin and Gerstl (1983) reviewed the evidence for partitioning and noted that a correlation between the organic carbon content of the soil and sorption was not







19

universally significant. These authors cited several studies where removal of organic carbon from a soil actually increased the amou nt of sorption, or had no negative effect on the sorption values. These authors suggested that molecular structure of the solute may be a better predictor of sorption to sediments than water solubility or octanol/water partition coefficients. This results from the observation that with a relatively rigid adsorbing surface, the conformation of the solute molecule will greatly affect its adsorption (i.e., steric effects), but not its partitioning between an organic phase and water.

Recently, first order molecular connectivity indexes

X) were shown to be well correlated with K ocvalues

(Sabljic, 1984, Sabljic, 1987). Molecular connectivity is described as a quantitative measure of the area occupied by the projection of the non-hydrogen skeleton of a molecule. The correlation between K ocand the first order molecular connectivity index supports the contention that the process of soil sorption may be viewed as an attractive interaction between two planes, with the magnitude of the interaction directly proportional to the surface area of the molecule. This suggests that the soil sorption and partitioning process reflect different mechanisms. An accurate model of sorption may include both partitioning and surface area dependent affects.

The relationship between K ocand 1X is (Sabljic, 1987):






20


Log K = 0.53 *X + 0.54 [3.15]

This relationship is based on literature values of K from oc
laboratory experiments with 72 compounds covering a broad range of polarities and classes, and a variety of sorbent systems. The correlation coefficient is 0.976 which explains 95.2% of the variance.

3.4.4 Desorption

In most cases sorption is considered to be completely

reversible, that is, the adsorption-desorption isotherms are reversible and single valued. However, several investigators report desorptions which display hysteresis in batch studies (Bailey and White, 1970, Boucher and Lee, 1972, Carringer et al., 1975, DiToro and Horzempa, 1982). Van Genuchten et al. (1974) found that the exponent for desorption is concentration dependent, and described the hysteretic behavior by using separate isotherm equations for sorption and desorption:

Ss = Kds C ns [3.16]

Sd = K dd Cd nd [3.17]

where subscripts s and d indicate sorption and desorption respectively. Hysteresis in column studies was noted by Schwarzenbach and Westall (1981), although the reaction was termed reversible, since all the solute was eventually eluted from the column.






21



3.4.5 Sorption Kinetics

Hysteretical behavior may actually be a manifestation of sorption-desorption kinetics. Rao and Jessup (1983)

noted that the influence of non-singular isotherms (ie., isotherms which display hysteresis) on solute movement may be less significant than the effects of sorption nonequilibria. In a study of the transport of pesticides at high concentrations, Rao and Davidson (1979) noted that the position of an adsorbed solute in a breakthrough curve was governed by the nature of the equilibrium adsorption isotherm equation, whereas the shape of the curve was defined by the kinetics of the sorption-desorption process.

Sorption reactions between hydrophobic pollutants and

sediments are generally rapid and not rate limited (Weber et al., 1983). Rao and Davidson (1980) concluded that many sorption reactions are complete within one minute in batch slurry experiments, although longer times to equilibrium were noted in several studies (Karickhoff et al., 1979, Miller and Weber, 1984). Schwarzenbach and Westall (1981), in a comparison of solute breakthrough at various flow velocities, concluded that K d values -from column experiments where velocity was less than 10- cm/second were similar to K values from 18 hour equilibrium batch studies.

3.4.6 Aromatic SorptionValues From The Literature

There are few data in the literature addressing

sorption of dissolved gasoline components in the subsurface. Much of the research involved aromatic compounds in single







22

solute experiments, simple mixtures, or data from crude oil studies.

Houzim (1978) observed a decrease in sorption in the order alkenes > aromatics > cycloalkanes > alkanes. Nathawani and Phillips (1977) in a study of hexadecane, oxylene, toluene and benzene in crude oil on soils of varying organic matter presented sorption coefficients based on Freundlich isotherms. Rodgers et al. (1980) reported the adsorption and desorption of benzene on several soils and clays at 25 C. The aqueous phase concentration range was 10 to 1000 ug/L. Sorption of benzene was minimal, except on aluminum saturated clay. These data are summarized in Table 3-2.

Wilson et al. (1981) evaluated the sorption of toluene on a fine sand in a column study. A retardation factor less than 2 for the concentration range of 200-900 ug/L was reported. This indicates the relatively low retardation potential of sandy aquifers. The retardation factor describes the extent of solute transport relative to water. The retardation factor for water is defined as unity. Solutes with large retardation factors are less mobile and and their movement is retarded, relative to that of water.

Schwarzenbach and Westall (1981) presented data for the sorption of several chlorinated and alkyl benzenes on twelve natural aquifer materials with varying amounts of organic carbon. The initial concentrations of the alkylbenzene components were 20 ug/L. Sorption coefficients from batch












Table 3-2. Summary of adsorption data for aromatic hydrocarbons.



Percent Benzene Toluene o-Xylene
Organic
Soil Content 1/n K 1/n K 1/n K


Silty Clay 16.2 1.272 3.23 1.008 3.52 0.947 11.03

Sandy Loam 10.8 1.298 0.583 1.002 2.69 0.707 4.77

Silty Clay 1.7 1.366 0.003

Silt Loam 1.0 1.51 0.028 0.996 0.931 1.098 0.62

Silty Clay Loam 2.6 0.89 2.4

Silty Clay Loam 1.8 0.94 1.8

Al saturated
Montmorillonite 0 1.08 30.9

Cu saturated
Montmorillonite 0 0.99 4.4


Adapted from Brookman et al., 1985.







24

studies of a soil with low organic carbon (0.0015 g o/g soil) are shown in Table 3-3.

As may be noted from this short review, most of the above studies involve data from individual components or from oil based products. Given the differences in composition among these petroleum products and gasoline, extrapolation may be insufficient to provide accurate data (Brookman et al., 1985).


3.5 Biodegradation of Aromatic Hydrocarbons in Groundwater


Biological activity is an important process in the attenuation of gasoline hydrocarbons in the subsurface environment. This realization is only recent. Early techniques for the enumeration of microbes in the subsurface (Waksman, 1916) underrepresented the numbers of microbes in the subsurface, showing a decline in population with depth. These data resulted from the use of nutrient rich growth media, inappropriate for the enumeration of groundwater bacteria (Wilson and McNabb, 1983).

Recent work shows that more substantial populations of heterotrophic organisms exist in shallow water table aquifers than were previously thought. Wilson et al. (1983a) demonstrated that the numbers of organisms were relatively constant to a depth of six meters in a shallow water table aquifer. The populations of heterotrophic bacteria were estimated to be approximately 10 6 organisms/gram dry weight soil (Ghiorse and Balkwill, 1985).







25


Table 3-3. Sorption coefficients of selected aromatic
hydrocarbons on low organic carbon soil.



Kd

Compound average standard deviation




Toluene 0.37 0.12

p-Xylene 0.50 0.10

1,3,5-Trimethylbenzene 1.00 0.16

1,2,3-Trimethylbenzene 0.95 0.11


Source: Schwarzenbach and Westall, 1981.








26
A review of the techniques for the enumeration and estimation of microbial biomass were presented by Atlas (1982) and Webster et al. (1985). Bouwer and McCarty (1884) noted that the majority of bacterial activity was associated with bacteria attached to surfaces. This results in the formation of biofilms, which are favored in low substratehigh surface area conditions. The biofilm may also present an active surface with solutes sorbing to the surfaces of microbial cells. In terms of the advection-dispersion models, the rates of biological degradation are incorporated into the model through the sink term Qi' which describes the microbial degradation of solutes from the aqueous phase. Qi is defined as:
Qi = -k E C [3.18]

where k is the rate of biological degradation (T-), 0 is the volumetric water content (ml/cm 3)and C is the solution phase concentration of a solute (ug/L).

3.5.1 Environmental Factors Affecting Biodegradation

Many factors can affect the transformation of organic

contaminants in the subsurface. McCarty (1984) included low substrate concentrations, toxic conditions, molecular structure of the substrate, inaccessibility of the substrate, and absence of essential arowth fact-rs Biological activity is often limited bv certain met c li requirements of the cell, supplied from the environment. Important geochemical properties include OH- redox potential, nitrogen and phosphorus concentrations and the






27


availability of an appropriate electron acceptor. Oxygen is used as the ultimate electron acceptor for aerobic degradation processes and is often a limiting factor in the degradation of hydrocarbons. Molecular oxygen is also essential to the aerobic metabolism of aromatic compounds, because it is incorporated into the structure of the metabolic products (Evans, 1977). The biochemistry of the aerobic metabolism of aromatic compounds is well established (Dagley, 1975). The first step in this metabolic pathway

is the removal of side chains, followed by the enzyme (oxygenases) mediated hydroxylation of the aromatic ring. Assuming 50% conversion of carbon to biomass and incomplete oxidation of the hydrocarbon molecules, two parts of oxygen are required for the degradation of each part hydrocarbon (Wilson et al., 1986). The complete oxidation of hydrocarbon molecules to CO 2and H 20 mayrqieteeo four parts of oxygen per part hydrocarbon.

There is some evidence for the anaerobic biodegradation of aromatic compounds in the environment. In the absence of oxygen, nitrates, sulfates and CO 2 become electron acceptors. Bouwer and McCarty (1984) presented a review of these processes. Nitrate respiration (Psuedomonas and Moraxella .22.*) and methanogenic fermentation processes can reduce the benzene nucleus followed by hydrolysis to yield aliphatic acids (Evans, 1977). Wilson and Rees (1985) showed the anaerobic degradation of benzene, toluene, xylenes and alkylbenzenes under methanogenic conditions.






28


Over a six week period only toluene showed substantial degradation, but after 40 weeks, benzene was reduced by 72%, toluene by 99%, ethylbenzene by 74% and o-xylene by 78%. Nutrient addition decreased the rate of hydrocarbon removal. The metabolic products from the anaerobic degradation of the aromatic molecules were not investigated. Nitrate respiration of xylene in a river alluvium was demonstrated by Kuhn et al. (1985). However, anaerobic biotransformations occur extremely slowly (months), relative to aerobic processes which may be completed in a matter of

hours (Wilson, 1985).

Physical properties of the aquifer also play an important role in determining the extent of microbial degradation. Porosity and hydraulic conductivity are significant parameters since the resupply of oxygen, substrate and nutrients to the microbial cells must come via the groundwater.

The concentration of the contaminant substrates is an important factor in the extent of biodegradation. High concentrations may result in incomplete degradation resulting from rapid depletion of oxygen and high substrate concentrations may also lead to increased acclimation times. Jensen et al. (1985) demonstrated an increase in the time required for acclimation (lag time) of bacterial cultures with increasing concentrations of napthelene. Lag times prior to substantial microbial degradation of a solute or nutrient reflects the time required by the indigenous






29


microflora to adapt to the added substance. Adaption is a phenomenon rather than a mechanism or process, and the term refers to an increase in the rate of biotransformation of a

substance resulting from exposure to that substance (Wilson et al., l983b). Low solute concentrations may result in the occurrence of a threshold limit, below which the microflora are unable to utilize the solute with out a cosolute (Wilson and McNabb, 1983). Jensen et al. (1985) demonstrated the degradation of aromatic molecules to less than 1 ug/L, implying that there was a very low threshold limit for the aromatic hydrocarbons. The relationship between concentration and biodegradation was reviewed by Alexander (1985). He stressed the importance of studying contaminant levels that exist in the environment.

3.5.2 Aromatic Biodegradation Values From the Literature

McKee et al. (1972) reported the oxidation of gasoline by Pseudomonas and Arthrobacter under aerobic but not anaerobic conditions. Degradation of gasoline by Pseudomonas was reported by Williams and Wilder (1971), and Litchfield and Clark (1973) showed significant numbers (10 4 cells/mL) of hydrocarbon degrading bacteria in groundwater contaminated with petroleum hydrocarbons from twelve sites. Bacterial populations appeared to be related to the concentrations of hydrocarbons. These data indicate the adaptation of microbial communities to the changing nutrient source (i.e., gasoline). The two major mechanisms of adaptation are induction of metabolic pathways, or the







30

activation or transfer of plasmids (Litchfield, 1986). This ability of microorganisms to adapt to the presence of contaminants forms the basis of in-situ biodegradation.

Several researchers have reported the biodegradation of aromatic compounds in groundwater. One shortcoming of most of this research is the lack of degradation rate coefficient data, required for use in groundwater transport models, and insufficient data on solute concentrations.

Jamison et al. (1976) reported the use of benzene as a sole carbon source. No rate coefficient data were given. McKenna and Heath (1976) noted the slow oxidation of benzene by P. putida. Delfino and Miles (1985) showed the degradation of benzene in 16 days under aerobic conditions in Floridan groundwater with an eight day lag phase. Ethylbenzene was degraded as a sole carbon source (Gibson and Yeh, 1973), but no rate data were given. Schwarzenbach et al. (1983) found toluene rapidly degrades within several meters in a study of river water infiltration to groundwater but rate and initial concentration data were not specified.

Kappeler and Wuhrmann (1978b) in a study of gas oil degradation reported that nitrogen and oxygen were the. limiting factors in hydrocarbon degradation. Addition of NH 4Cl resulted in further microbial degradation, and cell densities were on the order of 10 6/mL. Lag times of 5-6 days were noted in the batch experiments. Kappeler and Wuhrmann (1978a) showed that microbes from uncontaminated groundwater can attack gas oil components. Lag times of 1






31

day at 25 C and 5 days at 10 C were reported in column studies with mixed autochthonous flora from clean groundwater. The meta and para isomers of xylene and 1,2,4trimethylbenzene were degraded more rapidly than o-xylene, 1,2,3-trimethylbenzene or 1,3,5-trimethylbenzene. These studies by Kappeler and Wuhrmann (1978a,b) make up the bulk of the work on degradation of alkyl substituted benzenes.

3.5.3 In-situ Biodegradation

Application of in-situ bioremediation technology for

the renovation of hydrocarbon contaminated aquifers is based primarily on the work of Raymond et al. (1975a,b) and Raymond et al. (1977) at Suntech. Nutrients and oxygen were introduced with injection wells, and circulated through the aquifer with pumping wells. This technique and other bioremediation methods were reviewed by Wilson et al. (1986). These authors noted that studies are needed to investigate the effectiveness of natural biorestoration and to evaluate whether enhancement of natural processes is possible or desirable.
Transport of sufficient oxygen to subsurface microbes is a major technical problem. Oxygen is only slightly soluble in water and is quickly depleted during aerobic biodegradation. Oxygen addition by air sparging, oxygen sparging and the use of hydrogen peroxide are documented in the literature (Lee and Ward, 1984). The use of hydrogen peroxide appears particularly advantageous (TRI, 1982). Hydrogen peroxide is relatively inexpensive, nonpersistent







32

and is more soluble in water than air or molecular oxygen. However, it is also cytotoxic and may be chemically reduced, especially in the presence of iron salts. The biological decomposition of hydrogen peroxide is enzymatic:


catalase
2H2 02 --------- > 2H 20 + 02 [3.18]

peroxidase
H202 + XH2 -----------> 2H 20 + X [3.19]



where X is a biological reducing agent. Non-enzymatic decomposition occurs most frequently in the presence of iron salts:


Fe++ + H202 ------> Fe+++ + OH- + OH' [3.20]

OH* + H202 ------> H20 + H+ + 02 [3.21]



Britton (1985) reported that hydrogen peroxide was

relatively stable in combination with phosphates, even in the presence of moderate iron concentrations, and that bacterial populations can tolerate H202 concentrations up to 500 mg/L. Hydrogen peroxide was shown (Britton, 1985) to increase microbial counts by 102, but there was no reported increase in hydrocarbon removal.

3.5.4 Measurement of Microbial Activity

The reduction of INT (2-p-iodophenol-3-p-nitrophenyl-5phenyl tetrazolium chloride) to INT-formazan by the electron transport system is a function of cell respiration, and is widely used as a general measure of microbial activity.







33

This technique is recommended as an index of general microbial activity of soil microorganisms (Klein et al., 1971).

Reduction of INT to INT-formazan is a sensitive assay for dehydrogenase activity. The INT-formazan is easily extracted from sediments and soils by methanol, and the INTformazan complex is stable. Trevors et al. (1982) found a high correlation between electron transport system activity and oxygen consumption. Klein et al. (1971) presented a rapid and simple procedure for the determination of dehydrogenase activity using INT in soils with low organic carbon.



3.6 Summary



This literature review has presented some of the basic principles required as a basis for the discussion of the experimental work reported in this dissertation, and has highlighted some of the important findings relative to the dispersion, sorption and biodegradation of aromatic compounds in groundwater systems.
















CHAPTER IV
MATERIALS AND METHODS


4.1 Introduction


This chapter discusses the materials and experimental

methods employed during this study. The field site, and the solutes and sorbets are described followed by a description of the chromatographic systems. Laboratory experiments for the determination of hydrolysis, sorption and biodegradation parameters are discussed. Finally, the field procedures and experiments are discussed.



4.2 Site Description



The field research site used for a portion of this study was located at the Citrus Research and Education Center (CREC) at Lake Alfred, Fl. The site was located in the Trail-Ridge Lake Wales Ridge system of hills containing deep internally drained lake basins. Unconsolidated deposits in the area consisted of sand and sandy clays up to 150 ft thick above the limestone bedrock. The geology was marked by many sinkholes formed through subsidence of the unconsolidated deposits into solution cavities in the limestone (Spangler, 1984).


34







35


The research site was located on the rim of an ancient sinkhole. The surficial aquifer was composed of sand and clayey sands. An continuous clayey confining layer of uneven depth was present between 7 to 12 ft below land surface. This layer supported a saturated zone between 3 to 6 ft in thickness. Local relief was from 156 ft (above mean sea level) at the top of the hill at the eastern boundary of the site, to 131 ft in the wetland area at the west edge of the site. A site map is shown in Figure 4-1. The surficial aquifer was comprised of medium angular grained sands and fill material. The hydrology of the site was discussed by Killan (1987).

The surficial aquifer was contaminated during the

spring of 1983 by the loss of 7500-8000 gallons of leaded gasoline from a storage tank. Free floating gasoline was removed by surface skimming as of May 1985. The outline of the contaminated area as of October, 1986 is shown in Figure 4-2. The plume was defined by determination of explosive gas concentrations in bore holes throughout the site. These data were confirmed by GC analysis of soil cores and the use of ground penetrating radar. These techniques were described in detail by Killan (1987).


4.3 Aquifer Material



Aquifer materials used in this research were obtained

from the field research site at the IFAS-Citrus Research and Education Center at Lake Alfred Florida. A site map is






















AIDE 2L. BLDG 22N .








IPWRI
EL~GPAP- ~ aIM-IFENCELINE

PREVIOUS SITE OF
oNI'9 GASO L INE TANK

OflAP- 10


Pjjjjjj7 p-i- 0 II i ALE5 I












RRE AES-9


REETA AC C PROJECT







P_.








37










BLDG 24 1 N



0 20 40




BLDG *,i oHM-1
FEET





14 RAP-8 PREV!'US SITE OF

I j CAS2LIt; ,z

o RAP- 10
RAP-7 o RAP-6 a S
P---Fo
R A R AUP 5 P Eu


BLDG 10

a o .. .:_ P----5'


/ -P-4


WASH HM-3
RACK
o RAP-1 / \
RAP-2 O / *UF-2M 00,-2



BLDG 31 LD 5I P-3 e o a

3 \
jU-3


IFAS-CREC o
GROUNDWATER POLLUTION REMEDIAL ACTION PROJECT
EES POLLUTANT
PLUME DELINEATION
OCTOBER 1986 '4 ET L A D



Figure 4-2. Extent of the hydrocarbon plume at the
field research site as of October, 1986.







38

shown in Figure 4-1. All experiments were carried out with subsamples of the same aquifer material. The sample was collected with a stainless steel auger just below the water table at a depth of about 4 feet, approximately 10 feet east of Well RAP-1. Care was taken to avoid contamination with surface materials by removing one foot of top soil, and through careful handling of the auger. The aquifer material was oven dried at 105 C for 24 hours, sieved through 2 mm standard sieve and stored, covered, at room temperature. Prior to use, the aquifer material was autoclaved for 90 minutes on each of three consecutive days to sterilize the materials.

Prior to sterilization and drying, selected physical

and chemical properties of the aquifer materials used in the laboratory studies were characterized (pH, particle density, particle size analysis, percent organic carbon, bulk density, hydraulic conductivity, and water content) using standard methods of soil analysis (Black, 1965).



4.4 Choice of Solutes



Gasoline contaminated well water from the Lake Alfred research site was used as the source of dissolved solutes for the majority of experiments in this study. With the exception of a single solute column sorption experiment with benzene spiked in to RAP-2 water, all experiments were performed with mixtures of dissolved hydrocarbons at







39


concentrations occurring in the field. These concentrations are the result of the solubilization and subsequent weathering of gasoline hydrocarbons into groundwater. Well OHM-4 was used as the source of water for these experiments. This well was chosen based on consistently high levels of dissolved aromatic hydrocarbons. Hydrocarbon free groundwater was obtained from a non-contaminated portion of the aquifer (Well RAP-2). Hydrocarbon concentrations in these waters were monitored monthly. Well RAP-2 remained free of aromatic hydrocarbons throughout the course of these experiments. Concentrations of aromatic hydrocarbons varied in Well OHM-4 but remained high enough to provide samples for laboratory experiments.

Water samples were collected with a 5.1 cm (2") id poly vinyl chloride (PVC) bailer, following removal of five well volumes to allow collection of a representative sample. Well volumes were calculated based on the diameter of the well, and the depth of water in the well. These water samples were collected in four liter brown glass bottles transported on ice, and stored at 4 C upon arrival at the laboratory. The pH of these well waters ranged from 6 to 7. The conductivity was approximately 300 umhos. Total phosphate was 0.4 mg/L for RAP-2 and was 0.65 mg/L for well 0HM-4. Nitrate was 0.29 mg/L in well RAP-2 and 0.20 in well

OHM-4.







40

The single solute column experiment with benzene used RAP-2 water spiked with benzene (Aldrich, gold label 99.9%) to yield a solution of 4000 ug/L benzene.


4.5 Hydrocarbon Analyses



Gas chromatographic analyses of hydrocarbons for this study were performed on two systems. These are described below.

4.5.1 GC/MS Analyses

Field samples collected before September, 1986, and the initial hydrolysis vials were analyzed for volatile aromatic constituents using a Hewlett Packard model 5985B GC/MS/COMP system equipped with a 10 port Tekmar Automatic Liquid Sampler (ALS) and Liquid Sample Concentrator (LSC) purge and trap system. EPA method 624 was used. Separation of analytes was achieved with a 0.32 mm i.d., 30 meter long, DB-5 (1 um film thickness) fused silica capillary column (J & W Scientific), with manual liquid nitrogen cryofocusing. The 1,4 isomer of dichlorobenzene was used as an internal standard. Response factors for benzene, toluene, ethylbenzene and o-xylene were determined relative to the internal standard and used for quantitation. Response factors for meta and para xylene were assumed to be the same as the ortho isomer. A response factor of 1 was assumed for the C9H12 hydrocarbons. Chromatographic conditions were as follows:








41
mass range 45-450 amu
Temp 1 30 C
Temp 2 280 C
Rate 5 C/min
Hold time 10 minutes
Cryofocus time 5 minutes Pre-cool 2 minutes


4.5.2 GC Analyses

Hydrocarbon analyses were performed on a Perkin Elmer model 8410 gas chromatograph with a flame ionization detector and microprocessor data system. Samples were concentrated by purge and trap with a Tekmar LSC/ALS system employing a modified version of EPA method 602. Analytical separation was achieved with a 0.53 mm i.d., 30 meter long, fused silica Megabore DB-l (100% methylpolysiloxane) column (J & W Scientific) with a 3 um film thickness.

Benzene, toluene, ethylbenzene, o-xylene and m,p-xylene were quantified using the internal standard method (1,4 dichlorobenzene) during August and September 1986 for monthly analysis of field samples and for day = 0 hydrolysis ampules. After this date, eight isomers of C9H12 were identified and confirmed by analysis of individual standards and were quantified in all chromatograms along with BTEX (benzene + toluene + ethylbenzene + m,p,o-xylene) compounds. The internal standard was changed from 1,4-dichlorobenzene to chlorobenzene to avoid co-elution problems. A complete description of this analytical method and a summary of the quality control parameters for this method are in Appendix A.







42

The meta and Para isomers of xylene were not resolved on either chromatographic system employed in this research. The combination of these analytes was reported as m,pxylene. Likewise, 3-ethyltoluene and 4-ethyltoluene were not resolved with the analytical system employed in this study, and the combined concentrations of these analytes were reported in this study with the abbreviation 3,4ethyltoluene.



4.6 Hydrolysis Studies



Hydrolysis studies were performed in 5 mL glass ampules (Fisher Scientific). Ampules were rinsed with methanol and oven dried at 105 C .Ten microliters of hydrocarbon contaminated groundwater were spiked into ampules containing

5 mL of buffer solution. Buffer solutions were prepared with non contaminated well water, and the pH was adjusted to PH = 2.0, 7.0, 9.2, and 12.0 with 0.01 M phosphate buffers. The ampules were sealed with an ampule sealer (Oceanographic International, College Station, TX), and autoclaved (1 hour at 120 C). One set of ampules was analyzed at time zero. Another set of ampules was stored in the dark at 20, 40 and 60 C and analyzed by gas chromatography (GC) after 60 days.







43

4.7 Batch Sorption Studies



Sorption batch studies were performed in 40 mL VOA

vials with Teflon coated septa (Fisher Scientific). Vials were first filled with 60 g of aquifer material, and then autoclaved at 120 C for 1 hour on each of three consecutive days.

Water from well OHM-4, containing a mixture of

dissolved aromatic hydrocarbons, was used in the batch sorption experiments. As a result, all these experiments are multisolute, at concentrations representative of those found across the aquifer at Lake Alfred.,

4.7.1 Sorption Experiments

Water used in the sorption experiments was filter

sterilized through 0.2 um membrane filters (Gelman Metricel) and then added to each vial. The range of solute concentrations was achieved by dilution of Well OHM-4 water with Well RAP-2 water at ratios between 1:1 to 1:1000. Each dilution was performed in triplicate. Non-soil controls (solute water with no soil) were also set up in triplicate. To minimize headspace, the vials were premixed on a rotary tumbler for approximately 1 hour to remove interstitial air and to disperse the foam that formed during mixing. The vials were then opened, completely filled with sample and recapped. A high solids to solution ratio (2.9 g/ 9 ) was used to maximize the fractional decrease in solution







44

concentration owing to sorption, and to more closely simulate natural aquifer conditions.

vials used in sorption experiments were equilibrated at room temperature (20 + 2 C) on a rotary tumbler at approximately 20 rpm for 18 hours, and then centrifuged at 800 G for 30 minutes. Samples were analyzed by purge and trap/gas chromatography. Vials used in the batch sorption kinetic rate study were sampled at 1, 2, 4, 8, 16, 24, 36 and 48 hours.

4.7.2 Desorption experiments

Desorption experiments were conducted subsequent to a sorption experiment. Following centrifugation and sampling for sorption losses, approximately 10 mL of supernatant were removed and replaced with hydrocarbon free water (Well RAP2). The vials were re-equilibrated for 24 hours on the rotary tumbler, centrifuged and sampled. Each vial was only desorbed one time. These experiments were not designed to calculate desorption isotherms or test isotherm nonsingularity.

4.7.3 Calculation of Sorption Coefficients

The amount of solute sorbed to the aquifer material (ng solute/gram soil) was calculated by determining the difference between the solution concentration of the nonsoil blanks and the soil containing vials. The amount of solute lost was divided by the solution to soil ratio to normalize the data to a ng/gram basis. Sorption coefficients were calculated by fitting isotherm data to three models; linear, linear with intercept forced through







45

zero, and the log normalized (Freundlich) models (Miller and Weber, 1984).



4.8 Column Sorption Studies



4.8.1 Experimental Procedures

Leaching column experiments were performed with a 25 x 250 mm glass preparative chromatography column (Altex cat. no. 252-18) with a Teflon coated adjustable plunger (NkediKizza et al., 1987). Aquifer material was dry packed into the column which was then autoclaved at 120 C for 1 hour. The solutes were pumped from 2.6 L Teflon gas sampling bags (Alltech Associates, Deerfield, IL) with a Gilson model 302 HPLC pump fitted with a model 5s pump head (Gilson Medical Electronics, Middleton-, WI). The flow range of this system was 0.005 5.00 mL per minute. All transfer lines and connections were Teflon or stainless steel to minimize interaction of solutes with reactive surfaces. Column length was adjusted to 5.0 cm. Flow rates through the column were set at 1 ml/min (0.204 cm/mmn) for sorption studies. Column effluent breakthrough curves (BTCs) were measured under steady saturated water flow conditions with continuous application of solute containing water.

Effluents from the sorption columns were collected

manually in 1 ml crimp seal vials. These column effluents were either analyzed immediately or stored at 4 C in 1 mL







46

crimp seal vials with Teflon coated septa for later analysis. All samples were analyzed within 48 hours.

The breakthrough of an unretained solute was determined for each column using calcium chloride (1 ml/min columns). Breakthrough curves were determined by spiking hydrocarbon free groundwater from Lake Alfred (RAP-2) with chloride (600 mg/L CaCL 2). Chloride analyses were performed with a chloridometer automatic titrator (Buchler-Cotlove). Chloride ion was not expected to be adsorbed owing to the low cation exchange capacity of the Lake Alfred soil.

well water used in the sorption experiments was

filtered through 0.2 um membrane filters (Gelman Metricel) directly into the Teflon bags. The bags were autoclaved prior to each use. Columns were saturated with filter sterilized water from well RAP-2 prior to the input of solute containing water.

4.8.2 Estimation of Retardation Factor (R) in Columns

Three methods were used to estimate the value of R from the column data. In method 1, retardation factors (R b) were calculated by fitting the solution of Brenner (1962) to the column effluent curves. Peclet numbers used for these calculations were determined from the breakthrough of the non-retained solutes having retardation factors equal to unity. Method 2 was based on the conservation of mass principle. This method calculated retardation factors (Ra by evaluating the area above the breakthrough curve using Simpson's Rule (Swokowski, 1975). The R value was assumed








47
equal to the area above the BTC when the effluent concentration (C) divided by the influent concentration (C 0) was plotted vs pore volume as described by equation [4.1] pvma

R = f [ 1-C/C 0] dpv [4.1]


where pvma is the total number of pore volumes displaced through the column, and pv is pore volumes (Nkedi-Kizza et al., 1987). This method assumed a mass balance existed in the soil columns. The third method set the retardation factor (R pv) to equal the number of pore volumes required for the effluent concentration of each analyte to reach 0.5 of the influent concentration. The use of this method assumes that the breakthrough curve is symmetrical and sigmoidal, and that equilibrium conditions exist between the solution and sorbed concentrations during leaching through the column (Nkedi-Kizza et al., 1987). The value of K d was calculated from the various R values with equation [3.10].



4.9 Hydrogen Peroxide Evaluation



The reaction rate of hydrogen peroxide in the aquifer

environment was simulated by monitoring the dissolved oxygen

(DO) (YSI model 5739 probe and YSI model 54A DO meter), redox potential (platinum redox electrode, Fisher Scientific) and pH (gel membrane electrode, Fisher Scientific) of well water and aquifer material in a 3 arm 500 mL reaction flask. Contaminated well water was







48

equilibrated at room temperature (20 :L 2 C) in the sealed flask. Hydrogen peroxide (50%) was added undiluted in microliter quantities and at various dilutions. Aquifer material was then added to assess the ability of the material to catalyze the reaction. The 50% hydrogen peroxide stock was titrated with 0.01N potassium permanganate (Dupont, 1984) to check the strength of the stock solution. The standardized stock was then used to make the appropriate dilutions without further calibration.



4.10 Batch Biodegradation Studies



4.10.1 Experimental Procedure

Batch biodegradation experiments were performed in 40 mL VOA vials as described for the batch sorption experiments.

Well water from OHM-4 was used as the source of both dissolved aromatic hydrocarbons and bacteria in these studies. The water was not filtered prior to use. This experiment was designed to evaluate the ability of adapted groundwater bacteria to degrade mixtures of dissolved aromatic solutes at field scale concentrations. The experimental design for batch biodegradation experiment number 1 is shown in Table 4-1. Seven treatments were set up, with 15 replicate vials per treatment. water from Well OHM-4 was added (350 mL) to a 500 mL erlenmeyer flask, and then amended with hydrogen peroxide (50%), ammonium chloride







49

Table 4-1. Experimental design for batch biodegradation
experiment #1.


-- ------------------------------------------------------Hydrogen Sodium
Peroxide NH4 C1 Azide
Treatment (mg/L) (mg/L) (mg/L)
-- ------------------------------------------------------IA none none none

IB 17 none none

IC 68 none none

ID none 18 none

IE 17 18 none

IF 68 18 none

1G none none 1.25







50

(Reagent grade, Fisher Scientific) and 10% (w/v) aqueous solution of sodium azide (Fisher Scientific) as outlined in Table 4-1. Triplicate samples were analyzed for each treatment at 0, 3, 7, 15, and 31 days. Treatment number 1G was a sterile control. Hydrogen peroxide was added based on data from the hydrogen peroxide evaluation experiment and on data from Britton (1985), who demonstrated that cytotoxicity was minimal at hydrogen peroxide concentrations less than 100 mg/L. Ammonium chloride was added based on data from Mitchell (1974) who found that ammonia nitrogen is assimilated quickly during microbial growth. Ammonia (as NH 4 CL) was added to achieve quantities calculated to meet nitrogen requirements of the bacteria.

Biodegradation experiment number 2 was designed to

evaluate the efficacy of oxygen gas in addition to hydrogen peroxide (Table 4-2). Sterile controls were maintained in treatments 2C, 2F and 21. Ammonium chloride and hydrogen peroxide were added as in biodegradation experiment #1. oxygen was added by bubbling 0 2 gas into a closed 3 liter flask filled with 1200 mL of contaminated well water. A valve allowed for pressure relief. Water was released through a glass tube at the bottom of the flask, fitted with a teflon stopcock. Vials were filled as described in the sorption experiments. The vials used in both batch biodegradation experiments were placed in an incubator (20 1

1 C) and inverted once every two days to provide mixing. Samples were taken at 0, 2, 7, 14, 21 and 35 days.








51



Table 4-2. Experimental design for batch biodegradation
experiment #2.



Sodium
Oxygen NH4Cl Azide
Treatment # addition (rng/L) (mg/L)

2A air none none

2B air 18 none

2C air none 1.25

2D 60 mg/L H 20 none none

2E 60 mg/L H 20 218 none

2F 60 mg/L H 2 02 none 1.25

2G 0 2 saturation none none

2H 0 2 saturation 18 none

21 0 2 saturation none 1.25







52


Following sample removal for GC analysis, dissolved oxygen was measured in each batch biodegradation vial (batch experiments 1 and 2) with a YSI model 5739 DO probe and YSI model 54A Do meter (Yellow Springs Instruments Co.).

Microbial activity was assessed through the measurement of INT reduction to INT-formazan (Klein et al., 1971). Ten grams of soil from each vial were placed in sterile 50 mL Erlenmeyer flasks. Each flask was amended with 1 mL distilled water and 1.5 mL of 0.4% (w/v) aqueous solution of filter sterilized (0.2 um Gelman Metricel membrane filters) INT (Eastman-Kodak Co.). The soil was mixed with a sterile glass rod, capped with aluminum foil and incubated at 20 C for 72 hours. Sterile controls were prepared by autoclaving several flasks for 3 consecutive days for 90 minutes. Approximately 3 grams (dry weight) of soil were removed from each flask following incubation and placed in a test tube. Ten mL of methanol were added to each tube and the contents were mixed on a vortex mixer for 1 minute, then centrifuged at 800G for 20 minutes. The INT- formazan in the methanolic extract was measured spectrophotometrically at 480 nm against a methanol extract of soil containing no INT. The INT-formazan concentration was derived from a standard curve of INT-formazan in methanol.


4.10.2 Calculation of Biological Rate Constants

Aqueous concentration data from the batch

biodegradation vials were used with the regression equations from the Freundlich fit of the batch desorption data to







53

calculate the amount of solute lost to sorption in each batch vial. The extent of the sorption loss correction varied with the concentration of the analyte and the sorption parameters K fdand n. This correction factor added as much as 20% to the measured concentration values. These predicted losses resulting from sorption were added to the aqueous concentration for each analyte in each vial to calculate the total concentration of each solute in the vial (C t). These C t values were employed to obviate the need for simultaneous calculation of biodegradation on both sorbed and aqueous concentrations and any calculation of rates of sorption.-desorption during biodegradation. The Ctvalues were used to model the biological rate coefficients. The rate data were fitted to zero order, first order, second order and mixed order rate equations (Levenspiel, 1972), and to the Thomas slope method (Thomas, 1950).



4.11 Column Biodegradation Studies



4.11.1 Experimental Procedure

Column biological degradation experiments were

performed with the same column system described in section 4.8. Two flow rates were used in these experiments. These were 1 ml/min (0.680 cm/mmn) and 0.90 ml/hr (0.010 cm/mmn). Columns operated at 0.90 ml/hr were fitted with a low dead volume in-line septa. Effluent was withdrawn with a 50 ul syringe (Hamilton Co.) and analyzed immediately. Effluents







54

from the 1 mL/min columns were collected and analyzed as described in section 4.8. Breakthrough curves for a non retained solute were obtained with tritiated water (0.01 uci 3H for 0.90 ml/hr columns) or CaCI2 (1 ml/min columns). Analyses of 3H 20 effluents were performed on a Delta 300 model 6890 Liquid Scintillation Counter (Cearle Analytical) sing Scintiverse II scintillation cocktail (Fisher Scientific). Columns operated for biodegradation experiments were set up in the same manner as the sorption columns. Solute containing water was filtered through 0.45 um membrane filters (Gelman Metricel) to remove particulates. A standing microbial population was developed in the columns operated at 1 ml/min by inoculation with water from well OHM-4.

4.11.2 Calculation of Rate Constants

Rate constants for the biological degradation of aromatic solutes from column breakthrough curves were determined by application of the first order rate equation to the breakthrough curve data at steady state. Microbial degradation processes are often assumed to be first order (Bossert and Bartha, 1984). Substitution of equation [3.18] into equation [3.11] incorporates the degradation term into the one dimensional mass transport equation:



RC/ Dt = Dh C/ax v 3C/3x k C [4.2]







55

Dividing all terms of equation [4.2] through by R and defining D. = D/R, v. = v/R and k* = k/R, equation [4.2] becomes



C/ a t = Dh* C/2 v.- aC/ax k. C [4.3]



at steady state conditions where aC/at = 0, equation 4.3 reduces to:



Dh 2 C/ 2 v @C/ a x + k C = 0 [4.4]



For steady state conditions there is no sorption effect since the R term cancels out and the rate of biodegradation

(k) may then be calculated by application of the first order rate equation to the portion of the BTC which is at steady state. The first order rate equation for this system is:



C/C = e -kt [4.5]

For a column of length x, and with a pore water velocity of v, time may be expressed as

t = x/v [4.6]

and substitution of [4.6] into [4.5] and rearrangement allows calculation of the rate constant for biodegradation:



k = ( ln C/C0 ) v/x [4.7]







56

Average C/C 0 values were calculated from the regions of the solute breakthrough curves where C/ t = 0. This derivation assumes that microbial degradation occurs only from the aqueous phase, and that dispersion is negligible.



4.12 Field Studies



4.12.1 Aquifer Characterization

A tracer experiment was conducted to measure seepage

velocities and obtain better estimates of aquifer hydraulic conductivity and field scale dispersion. RAP-9 was used as the dosing well. The following steps outline the experimental procedure:

1. A tracer solution was prepared by dissolving 50 lb (23 kg) of technical grade ammonium chloride in 55 gal (208 L) of tap water. The resulting concentration was 109,000 mg/L ammonium chloride.

2. The ammonium chloride solution was injected into the dosing well and simultaneously diluted with tap water at a metered rate of 1 gallon per minute (gpm). Dosing continued for 15.8 hours, resulting in a total dose volume of 1,035 gallons of tracer solution.

3. Detection of the tracer was monitored in

wells RAP-10 and RAP-11 using a conductivity meter with a field probe. Measurements were obtained at one half- to one-hour intervals for the first 24-hour period. Wells P-







57

6, P-7, UF-lE, RAP-4, OHM-4, EJF-2M and UF-3W were also monitored periodically for the following two weeks.

The breakthrough of the tracer was calculated in pore volumes using the equation

pv = vt/L [4.8]

where pv is pore volumes, t is time (hours), L is the distance between RAP-9 and RAP-10 (5 ft) and v is the seepage velocity (ft/hour)from work by Killan (1987).

4.12.2 Water Quality Monitoring

Samples for hydrocarbon analysis were taken from

selected monitoring wells monthly from February 1, 1986 to June 1987. Sampling procedures are detailed in Appendix B. Hydrocarbon analyses were as described previously using the three chromatographic methods as they became available. The pH, temperature, dissolved oxygen, and conductivity were measured periodically in selected wells. Sampling procedures are detailed in Appendix B.

Total phosphorus concentrations were determined in all monitoring wells (EPA method 365.1). All phosphorus forms were converted to orthophosphate by autoclaving with potassium permanganate in an acidic medium. Orthophosphate was determined spectrophotometrically at 880 nm with a Perkin Elmer model 552 spectrophotometer.

Chloride was determined colorometrically in each

monitoring well over several months to determine background levels of chloride via EPA method 325.1. Average background concentrations were 20 + 8 mg/L. Nitrate was measured with






58


an Orion nitrate electrode via standard method 418b (APHA, 1980).

4.12.3 Microbial analyses

Viable microbial cells were enumerated by plate count

technique using dilute soil extract agar (DSEA) media. This technique was developed based on work by Ghiorse and Balkwill (1983) and Wilson et al. (J 983).

DSEA was prepared by autoclaving 100 g of surface soil in 100 mL of distilled water for one hour at 120 C. The supernatant was filtered (Whatman glass fiber filters) to remove particulates and diluted ten fold with distilled water and amended 1.5% (w/v) with agar (Fisher scientific).

Ten grams of subsurface material were suspended

aseptically in 100 mL 0.1% sodium pyrophosphate (Fisher Scientific) then appropriate dilutions were plated in triplicate on DSEA media. All plates were incubated aerobically at 27-30 C for ten days.















CHAPTER V
RESULTS AND DISCUSSION


5.1 Introduction


This chapter will review the results of all experiments performed as part of this dissertation research. The presentation of results and the interpretation of the data for each major experimental section are grouped together to avoid loss of continuity. Hydrolysis of aromatics in groundwater is discussed first, followed by the results and discussion of the batch and column sorption experiments. Batch and column biodegradation experiments are addressed next*t followed by the presentation of field data, and the correlation of field data with laboratory experiments.


5.2 Hydrolysis of Aromatic Hydrocarbons


The results of initial measurements (time = 0) of the hydrolysis ampules were inconclusive, resulting from overdilution of the samples. Several analyses were below the limit of detection of the GCMS analytical system, therefore no conclusive statements may be made relative to the rates

of aromatic hydrolysis.

Statistical analysis of data from ampules after 60 days of temperature controlled storage indicated that for a given temperature, there was no significant (student's t-test,


59







60

0.05 level) change in concentration of analytes over the pH range tested (pH 2,7,9,12).

only one compound, l,2,3-trimethylbenzene, demonstrated a significant (student's t-test, 0.01 level) temperature effect at pH values of 7,9 and 12. This change in concentration occurs only at 40 C, and the concentration values at 20 and 60 C are equivalent for all pH values. These data are not consistent with data from other aromatic compounds in this study, which showed no change in concentration with varying temperatures. The apparent loss of solute seen for l,2,3-trimethylbenzene was likely the result of working near the detection limit of the analytical system, or the result of experimental error.

The absence of concentration differences across a wide range of pH and temperature for the 60 day ampules implies that hydrolysis was not a significant mechanism for removal of aromatic hydrocarbons. This was expected, owing to the resistance of aromatic structures to nucleophilic attack by water. This results from the electronegativity associated with the delocalization of electrons in the pi bonds of the aromatic nucleous. McCarty (1984) has noted that chemical

hydrolysis may occur, but that for most compounds this process was slow relative to biological removal rates. In addition, hydrolysis results in simple changes in the molecular structure, whereas biological transformations often result in the mineralization of organic compounds to carbon dioxide and water.







61



5.3 Characterization of Aquifer Materials



An analysis of a sub-sample of the aquifer materials

used in the laboratory experiments is presented in Table 51. All experiments with aquifer material were performed with subsamples of well-mixed aquifer material. Single size fractions of aquifer material were not used since extrapolation from one size fraction to another has been shown to lead to errors in the estimation of sorption values (Abdul et al., 1986). Unwashed, natural sorbent material from the Lake Alfred site was used in this study to more closely approximate field conditions. The organic carbon content of this material was low, and particle size analysis indicated the dominance of fine to medium grained sands. The pH of the aquifer material was in the range suitable for biological degradation, and was consistent with the pH values in the well water.



5.4 Batch Sorption Studies



5.4.1 Sorption Rate Studies

Rate studies were conducted to determine the sorption kinetics of the selected aromatic solutes with Lake Alfred aquifer material. These experiments established the equilibration time for the sorption isotherms. The approach to equilibrium is shown in Figure 5-1. These curves are







62





Table 5-1. Selected physical and chemical Properties
of the Lake Alfred aquifer material.


--- -----------------------------------------------------Parameter Value


pH 7.4 (0.01M CaCl )
2
Particle Density 2.6 g/mL

Water Content (by weight) 24%

Organic Carbon 0.015%

Bulk Density 1.4 g/mL

Particle Size Analysis

clay 1.8%

silt 1.7%

very fine sand 3.0%

fine sand 38.2%

medium sand 47.0%

coarse sand 8.2%

very coarse sand 0.2%

--- ------------------------------------------------------




















al
10


C B-.
8








-3
4J S 3 33 2





0 I

0 20 40 60 80 100 120

TIME (HOURS) o BNZ + TOL o EBZ A mp-X"/L x o-XYL


Figure 5-1. Approach to equilibrium for several aromatic solutes on
Lake Alfred aquifer material.







64

marked by an initial rapid sorption, and equilibrium conditions are established within several (4 to 8) hours. These data are in agreement with Weber et al. (1983) who stated that sorption reactions with natural sorbets were generally rapid and not rate limited. Based on these data an equilibration time of 18 hours was chosen. Eighteen hours was chosen to maximize the time for sorption yet minimize the time for losses from the system (ie., via diffusion of solutes through the Teflon septum). This was equivalent to time scales used in previous studies (Chiou et al., 1979, 1983; Schwarzenbach and Westall, 1981). Longer equilibration times were not possible using this experimental technique since losses in non-soil blanks after

3 days made it difficult to differentiate between sorption and loss from the system. The equilibration time used in this study did not guarantee that the sorption process was complete, but that it was complete to the extent that it could be accurately measured.

5.4.2 Batch Sorption Isotherm Data

Data for the equilibrium batch sorption isotherms are presented in Appendix C. Solution concentrations are in ug/Lj and sorbed concentrations are in ng/g. Three models were fitted to these data using the method of least squares regression analysis. These models were the linear, linear with suppressed fit (forced through the origin), and the Freundlich (log-log transformed). The results of these analyses for the linear models are presented in Table 5-2







65


Table 5-2. Regression parameters for the analysis of
average values of equilibrium batch isotherm
sorption data with the linear model.


Sb
C
Compound Na (ug ) Kd stdc y-intd, std r


Benzene 14 950 0.066, 0.005 1.5, 4.28 0.914

Toluene 14 4200 0.049, 0.010 10.9, 65.6 0.694

m,p-Xylene 16 4300 0.095, 0.005 3.4, 28.7 0.961 o-Xylene 16 2500 0.097, 0.004 3.1, 10.8 0.979

3 or 4 ETe 11 935 0.087, 0.012 3.8, 12.6 0.861

1,3,5-TMBf 11 460 0.142, 0.008 1.6, 3.92 0.973

2-ET9 11 373 0.106, 0.011 0.81, 4.66 0.910

1,2,4-TMBh 10 1600 0.131, 0.006 4.6, 10.6 0.981 1,2,3-TMBi 10 558 0.124, 0.010 1.7, 6.10 0.951

anumber of data points
b
maximum concentration c standard deviation dy-intercept

3 or 4 Ethyltoluene f1,3,5-Trimethylbenzene 92-Ethyltoluene h,2,4-Trimethylbenzene i1,2,3-Trimethylbenzene








66

and Table 5-3. The Freundlich regression parameters are presented in Table 5-4.

There is no significant difference (student's t-test,

0.05 level) between sorption coefficients predicted with the linear model and those predicted with the linear model with suppressed intercept. The sorption coefficients are determined form the slope of the linear isotherms. In addition, statistical determination of the confidence intervals of the y-intercepts indicate that there is no significant difference between the predicted value of the yintercept in the linear model and zero at the 0.05 significance level, confirming that these two models are analogous. Equivalence between these two models is expected since the sorbed concentration should equal zero when no solute is added to the system. A non zero intercept is an indication of nonlinearity in the isotherm. In most cases both linear models fit the data well as evidenced by the relatively high coefficients of determination (r 2 ). Based on these analyses, the isotherms for the sorption of aromatic solutes from Lake Alfred water onto Lake Alfred aquifer material were concluded to be linear. The coefficients of determination for toluene in both linear models were substantially lower than for other compounds in this study. The linear model with suppressed intercept accounted for only 63.6% of the total sum of squares deviations about the means for the 14 values in the toluene isotherm. This suggested that this model was not








67


Table 5-3. Regression parameters for the analysis of
average values of equilibrium batch isotherm
sorption data with the linear model
(suppressed intercept).

b
a ma c d 2
Compound N (ugL) Kd, std y-intd r


Benzene 14 950 0.069, 0.005 0 0.904

Toluene 14 4200 0.051, 0.009 0 0.636

m,p-Xylene 16 4300 0.096, 0.004 0 0.960

o-Xylene 16 2500 0.099, 0.003 0 0.978

3 or 4 ETe 11 935 0.093, 0.010 0 0.850

1,3,5-TMB 11 460 0.146, 0.007 0 0.969

2-ET9 11 373 0.108, 0.009 0 0.908

1,2,4-TMBh 10 1600 0.135, 0.005 0 0.978

1,2,3-TMB 9 558 0.128, 0.008 0 0.948

anumber of data points
b
maximum concentration

c
standard deviation

d
y-intercept

e3 or 4 Ethyltoluene f1,3,5-Trimethylbenzene 92-Ethyltoluene h,2,4-Trimethylbenzene i1,2,3-Trimethylbenzene 1,2,3-Trimethylbenzene








68


Table 5-4. Regression parameters for the analysis of
average values of equilibrium batch isotherm
data with the Freundlich model.

--- -----------------------------------------------------b
C log loge d e 2
Compound Na (ug L) Kf, std n std r

Benzene 14 950 -0.857, 0.217 Q.901, 0.071 0.952

Toluene 14 4200 -0.783, 0.260 0.876, 0.076 0.917

m,p-Xylene 16 4300 -0.758, 0.110 0.916, 0.031 0.984 o-Xylene 16 2500 -0.873, 0.098 0.966, 0.026 0.990

3 or 4 ETf 11 935 -0.702, 0.158 0.904, 0.054 0.958 1,3,5-TMB9 11 460 -0.605, 0.081 0.921, 0.029 0.991 2-ETh 11 373 -0.951, 0.255 0.993, 0.088 0.934

1,2,4-TMBi 10 1600 -0.641, 0.099 0.937, 0.035 0.989 1,2,3-TMBj 9 558 -0.623, 0.078 0.918, 0.028 0.995


--- ------------------------------------------------------anumber of data points maximum concentration clog standard deviation of Kf values dFreundlich exponent

e standard deviation of Freundlich exponent f3 or 4 Ethyltoluene

gl,3,5-Trimethylbenzene h2-Ethyltoluene

1,2,4-Trimethylbenzene Jl,2,3-Trimethylbenzene








69
appropriate for estimation of sorption. However, analysis of variance with a global F-test indicated that the model was useful for predicting sorption at the 0.01 significance level. Therefore, the linearity of all isotherms was confirmed. Linear isotherms have been noted by several authors (Schwarzenbach and Westall, 1981, Chiou et al., 1979, Karickhoff et al., 1979) and the data presented in this study are in agreement with these studies.

Curtis et al. (1986) noted that the use of the linear regression technique was not statistically rigorous since variance in the dependent variable was not distributed uniformly across the observed concentration range. These authors suggested that a least squares fit on the log transformed data (Freundlich model) gives a better approximation by providing a more uniform distribution of variance. The Freundlich model provided a good fit to the data in this study (Table 5-4) as evidenced by the high coefficients of determination for the Freundlich model. The Freundlich isotherm explained between 91.7 to 99.5% of the variance in the data, and provided a slightly improved fit to the isotherm data relative to the linear models. Ther2

value for toluene was 0.917, which was much improved over the coefficient of determination for toluene in the linear model. The log K f values for the study compounds are also presented in Table 5-4. Values for several components (ethylbenzene, and the propylbenzenes) were not included in the table owing to their low concentrations in Well OHM-4







70

water on the day samples were collected for this study. The linearity of these isotherms was confirmed by the values of the regression coefficients and the Freundlich exponents

(n), both of which were close to unity. As n approaches unity the models should converge since the linear model is in effect a special case of the Freundlich model.

A comparison of the Freundlich and linear models is presented in Table 5-5. The deviation between predicted amounts of sorption for the linear model with suppressed intercept and Freundlich models are expressed as ratios between the calculated sorbed concentrations. This method was used to evaluate the predictive equivalence of both models over the concentration ranges encountered in this study. This method was chosen, since direct comparison of K d and K f values may be misleading owing to the log transformation of the data in the Freundlich isotherm model. The largest deviations occurred for toluene at 1 ug/L. In general the ratios approached unity as the concentrations increased, but diverged in the range between 1 to 50 ug/L. This comparison indicates that the models, were essentially similar, as is predicted from the values of the Freundlich exponent (n). As n approaches unity, the Freundlich isotherm approaches the linear isotherm. The convergence of these models is confirmed by an examination of 2ethyltoluene in Table 5-5. This compound has the highest Freundlich constant (n = 0.993) and the ratios of predicted








71


Table 5-5. Ratio of sorbed concentrations calculated
from Freundlich and linear equilibrium models




concentrations (yg/L)

Solute 1 50 100 500 1000


Benzene 2.01a 1.73 1.27 1.09 1.01

Toluene 3.23 1.97 1.81 1.48 1.36

m,p-Xylene 1.81 1.30 1.23 1.08 1.01

o-Xylene 1.35 1.18 1.16 1.09 1.07

3 or 4 ETb 2.14 1.48 1.38 1.18 1.10

1,3,5-TMBc 1.70 1.25 1.18 1.04 0.99

2-ETd 1.04 1.01 1.00 0.99 0.98

1,2,4-TMBe 1.69 1.34 1.28 1.15 1.10

1,2,3-TMB 1.88 1.35 1.27 1.12 1.05

athe ratio of the amount sorbed as calculated from the Freundlich model to the amount sorbed predicted from the linear model with suppressed intercept, at the same solution concentration.
3 or 4 Ethyltoluene

C,3,5-Trimethylbenzene

d2-Ethyltoluene

el2,4-Trimethylbenzene
f,2,3-Trimethylbenzene







72

sorption from the two models are consistently close to one over the entire concentration range tested.

Freundlich isotherms for benzene and toluene are shown in Figures 5-2 and 5-3. Graphs of Freundlich isotherms for the remaining solutes are presented in Appendix C. Average values are plotted in Figures 5-2 and 5-3 and error bars showing one standard deviation in the experimental determination of the sorbed concentrations are presented to give an indication of the variance in these data. Standard deviations for all compounds are shown in Appendix C. The influence of dissolved organic carbon was not assessed during this study. However, based on the work of Curtis et al., (1986) with a sandy aquifer material (0.02% organic carbon), organic carbon in this study was not expected to decrease the values of K d by more than 5%. Water from the Lake Alfred aquifer was used in these experiments, and the organic carbon in solution was assumed to be in equilibrium with the organic carbon on the aquifer material. Therefore, dissolution of additional organic carbon into solution should have been minimal, and K d should not be greatly affected. This hypothesis was confirmed by evaluation of the partitioning model as a predictive technique for sorption of aromatic solutes to the Lake Alfred aquifer material in section 5.6. The interaction between organic carbon and the solutes was shown to be low.





















2--7









0.4-





1- -,

-Os



F0 0. 1 1 2242 LOO SO-O OCNRTO
SO )J:o1oprj


Fiur 5-2Fenlc sopiniohr fo bezn ateu irum





























Li 1.



00


0








0 12 3 4

100 SOLUTION CONCENTRATION 1)SORPTION > DESORPTION


Figure 5-3. Freundlich sorption isotherm for toluene at equilibrium.







75

5.4.3 Batch Desorption Experiments

Desorption data are also presented in Figures 5-2 and 5-3t fit with the Freundlich type model. Visual inspection of the desorption data suggests some degree of irreversibility or some difference in desorption kinetics based on the upward displacement of the desorption regression lines. However, the calculated values of the partition coefficient for desorption with the linear type model (Table 5-6) and for the linear type model with suppressed intercept (Table 5-7) were not significantly different from sorption values (Kd) at the 0.05 probability level. Desorption coefficients from the Freundlich type model (K fd ) were also not significantly different from K f values at the 0.05 level (Table 5-8). Statistical analyses of the models used to evaluate the desorption coefficients indicated that all three models gave excellent fit to the data, as evidenced by the high coefficients of determination.

These data suggested the reversibility of the sorption process, and demonstrated that the hysteretical behavior of the desorption data were not significant. This was consistent with a majority of the published literature on sorption of organic compounds to natural sorbets (Miller and Weber, 1984).

For purposes of discussion, the Kd values from the linear model with suppressed intercept are used in the following sections. As discussed earlier, these data were








76


Table 5-6. Regression parameters for the analysis of
average values of equilibrium batch
desorption data with the linear model.

b
--- -----------------------------------------------------a C btcd 2
Compound Na ( bW) Kdd, std y-intd std r


Benzene 5 950 0.248, 0.006 2.2, 4.18 0.998

Toluene 8 4200 0.303, 0.011 4.13, 55.8 0.992

m,p-Xylene 9 4300 0.186, 0.006 13.3, 30.1 0.993

o-Xylene 9 2500 0.152, 0.012 11.0, 31.1 0.955

3 or 4 ETe 9 935 0.250, 0.018 -2.9, 18.4 0.968

1,3,5-TMBf 8 460 0.194, 0.004 1.5, 1.62 0.998

2-ET9 7 373 0.566, 0.010 0.78, 2.64 0.999

1,2,4-TMBh 10 1600 0.199, 0.005 3.3, 7.62 0.996

1,2,3-TMB 9 558 0.219, 0.032 1.1, 20.3 0.871

-- -------------------------------------------------------anumber of data points maximum concentration Standard deviation

dy-intercept

e3 or 4 Ethyltoluene

f1,3,5-Trimethylbenzene 92-Ethyltoluene
h,2,4-Trimethylbenzene i1,2,3-Trimethylbenzene







77



Table 5-7. Regression parameters for the analysis of
average values of equilibrium batch
desorption data with the linear model
(suppressed intercept).

b
C2 a ax c d 2
Compound Na ug/L) Kdd, std y-int r


Benzene 5 950 0.251, 0.004 0 0.998

Toluene 8 4200 0.304, 0.008 0 0.992

m,p-Xylene 9 4300 0.190, 0.005 0 0.992

o-Xylene 9 2500 0.159, 0.010 0 0.951

3 or 4 ETe 9 935 0.256, 0.014 0 0.967

1,3,5-TMB 8 460 0.1968 0.003 0 0.997

2-ET 7 373 0.570, 0.007 0 0.999

1,2,4-TMBh 10 1600 0.202, 0.004 0 0.996

1,2,3-TMB 9 558 0.221, 0.022 0 0.870

anumber of data points maximum concentration standard deviation d.
y-intercept e3 or 4 Ethyltoluene f1,3,5-Trimethylbenzene 92-Ethyltoluene h1,2,4-Trimethylbenzene i1,2,4-Trimethylbenzene 11,2,3-Trimethylbenzene








78


Table 5-8. Regression parameters for the analysis of
average values of equilibrium batch
desorption data with the Freundlich model.

b
C b log log
Compound Na (m L) Kf, std n stde r


Benzene 5 950 -0.635, 0.168 1.02, 0.079 0.982

Toluene 8 4200 -0.478, 0.039 0.992, 0.019 0.998

m,p-Xylene 9 4300 -0.561, 0.096 0.963, 0.043 0.986

o-Xylene 9 2500 -0.159, 0.263 0.774, 0.099 0.891

3 or 4 ETf 9 935 -0.692, 0.068 1.029, 0.030 0.994

1,3,5-TMB9 8 460 -0.569, 0.051 0.956, 0.025 0.996

2-ETh 7 373 -0.657, 0.079 0.983, 0.046 0.989

1,2,4-TMBi 10 1600 -0.658, 0.122 0.997, 0.056 0.981 1,2,3-TMBj 9 558 -0.624, 0.092 0.988, 0.038 0.990

anumber of data points
b
maximum concentration clog standard deviation of Kf values dFreundlich exponent e standard deviation of Freundlich exponent

3 or 4 Ethyltoluene 91,3,5-Trimethylbenzene
h
2-Ethyltoluene

il,2,4-Trimethylbenzene Jl,2,3-Trimethylbenzene








79
or linear models, and this model is more convenient for the application of equation [3.10].



5.5 Breakthrough Curves for Aromatic Solutes



5.5.1 Measurement of Column Dispersion

Breakthrough curves (BTCs) for a non-retained solute were determined for each column used in these experiments. Analysis of these data allowed the determination of the Peclet number used to model the breakthrough of the aromatic solutes. Evaluation of these data also allowed the calculation of dispersion in the column. Chloride and tritiated water were used in these experiments.

Dispersion (D h) was calculated from the slope of a plot of C/Co vs pore volumes (pv) at pv = 1. according to the equation (Rao, 1985):



D h v L/ 4 pi B 2 [5.1]



where D h is the hydrodynamic dispersion coefficient (cm 2 min), v is the flow velocity (cm/mi, L is the length of the column (cm) and B is the slope of the BTC at C/Co =1. This assumes a sigmoidal shaped curve, and this assumption was valid for these breakthrough curves. A typical

breakthrough curve is shown in Figure 5-4. Some values of D hare presented in Table 5-9. Columns with flow rates of 1 mi/mmn exhibited higher values of D h since dispersion






















0.9 -1/

0.8


0.7


O 0.6



0.4


0.3

0.2
oa





0 2 4


POrE VOLUMES
El CHLORIDE Figure 5-4. Breakthrough curve for chloride for a 5 cm sorption column.







81


Table 5-9. Values of dispersion coefficients calculated
from the breakthrough curves of unretained
solutes in laboratory columns.

---- ----------------------------------------------------Flow Velocity Dispersion (D h) a st
Tracer (mL/min) (cm/mmn) (cm /min) avgst


3 H 20 0.015 0.003 0.00053

3 H 20 0.015 0.003 0.00066

3H2 0 0.015 0.003 0.00040

0.00053 0.00013


Cadl 1.0 0.204 0.051

Cadl 1.0 0.204 0.013

Cadl 1.0 0.204 0.069

0.044 0.029
a - - - - - - - - - - - - - -
aaverage values of dispersion measurements b standard deviation of dispersion measurements







82


mi/mmn exhibited higher values of D h since dispersion increases with increasing pore water velocity (Roberts et al., 1985). It may be noted that the pore water velocity of 0.680 cm/mmn was equivalent to the seepage velocity in some portions of the aquifer at the Lake Alfred field site. These data are compared to field dispersion data in section

5.10.

5.5.2 Aromatic Solute Breakthrough Curves

Breakthrough curves for selected, dissolved aromatic

solutes in the column effluent (Well 0HM-4 water) are shown in Figure 5-5 (benzene) Figure 5-6 (toluene) and Figure 5-7 (n-propylbenzene). Breakthrough curves for these solutes are presented because they show the the breakthrough of the least retained compounds (benzene and toluene) and the most retained (n-propylbenzene). These solutes are presented separately to avoid overlap on a single plot, but are part of the multi-component mixture resulting from the solubilization of gasoline into groundwater at the Lake Alfred site. Graphical representations of the remaining solutes in the column effluent are shown in Appendix D. The changes in effluent concentration near the end of each breakthrough curve was consistent for each solute, reflecting the same relative variability. These deviations may be explained by heterogeneities in flow paths in the porous media, or by analytical error.

Calculated values of R, K d' and Ko based on the

analyses of the column data by curve fitting to Brenner


















1.2
13
1




I /


0.7
/ 7

0.6] 0.5

0.4

0.3-/


0.1 -j


0 2 4
0
T


PORE VOLUMES u CHLORIDE +- BENZENE

Figure 5-5. Breakthrough curve for benzene from Lake Alfred water (C = 4700 ug/L)
co
W)


















12

10





04/
0.7 / ''



0.5

0.4
0.3 ,

02

0./ /


0 24
PORE VOLUMES o CHLORIDE + TOLUENE

Figure 5-6. Breakthrough curve for toluene from Lake Alfred
water (C = 2600 ug/L) .
0



















1.2


1
L/o.9 f"
0.9

0.8

0.7

0.6 /
0.5 A1

0.4 -.

0.3 /

02 /
o 0 -- ------,



0 2 4

PORE VOLUMES O CHLORIDE + N-PROP'/LBENZENE

Figure 5-7 Breakthrough curve for n-propylbenzene from Lake Alfred
water (Co = 1000 ug/L).
01
u-I




Full Text
ug INT / gram dry weight soil
D AY S
TRT 2D + TUT 2E <> TKT 2F
Figure 5-21.
Electron transport activity in biodegradation treatments
2D, 2E and 2F.
141


LOO AMOUNT SORBED
LOO SOLUTION CONCENTRATION
SORPTION o DESORPTION
Freundlich sorption-desorption isotherm for benzene at
equilibrium.
189


18
organic matter, and by solvophobic theory (Rao et al.,
1985). The general relationship between K and K and WS
oc
takes the form (Curtis et al. 1986):
Log K = a Log K + Log f + b [3.13]
3 oc 3 ow ^ oc J
Log K = c Log WS + Log f + d [3.14]
where a,b,c, and d result from regression analysis of
laboratory isotherm data and depend on the solute-sorbent
system.
However, there are significant limitations on the use
of these estimators, and the basis of partitioning as a
sorption mechanism is questionable (Milgelgrin and Gerstl,
1983). In a strict sense, these relationships hold only for
those compounds and sorbents used in the original studies
(i.e., these are empirical relationships). This is
reflected in orders of magnitude variation in estimates of
sorption using these relationships. Application of the
partitioning models may not be appropriate in experimental
systems with solutes and sorbents which are different from
those used to develop these models. In addition, these
equations may not apply at organic carbon fractions less
than 0.1% (Curtis et al., 1986). Rao and Jessup (1983)
noted that the use of K to estimate sorption can lead to
significant errors with soils with very low (less than 0.1%)
organic carbon contents.
Milgelgrin and Gerstl (1983) reviewed the evidence for
partitioning and noted that a correlation between the
organic carbon content of the soil and sorption was not


1,3,5-Trimethylbenzene Sorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
202
22
326
46
70
3
175
30
19
1
44
1
10
6.4
17.5
3
2
1
4
a
267.4
4.09
459.7
28.31
15.8
0.97
45.97
a
3
0
9
2.11
1.3
0.14
4.5
a
0.65
0.12
2.29
a
0.3
0.11
1.15
0.6
amount
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentration
124
42.8
1.63
2.51
105
36.2
1.56
2.24
25
8.6
0.94
1.64
7.5
2.6
0.41
1.24
2
0.7
-0.16
0.60
192.3
66.3
1.82
2.66
30.17
10.4
1 .02
1.66
6
2.1
0.32
0.95
3.2
1.1
0.04
0.65
1.64
0.6
-0.25
0.36
0.85
0.3
-0.53
0.06
a
n = 1
202


5
requires detailed and usually site specific data for these
processes.
This dissertation presents a detailed investigation of
the attenuation of selected dissolved aromatic gasoline
hydrocarbons in a typical sandy surficial aquifer in
Florida, using a variety of batch and column techniques.
Sorption coefficients and biological and abiotic degradation
rates from laboratory studies are presented. These studies
simulated conditions at a contaminated field site and
included experiments to assess various treatment
alternatives. Actual field data are summarized, and
compared to the laboratory data.
The improved understanding obtained from the collection
and analysis of these data should aid in the formation and
improved use of predictive models describing the movement
and reaction rates of water soluble components of gasoline
in shallow groundwater systems and aid in the selection of
appropriate groundwater reclamation technologies.


APPENDIX A
CHROMATOGRAPHIC CONDITIONS AND QUALITY CONTROL
PARAMETERS FOR THE ANALYSIS OF AROMATIC HYDROCARBONS
This appendix lists the chromatographic conditions used
in the gas chromatographic analysis of aromatic hydrocarbons
on the Perkin Elmer 4100 gas chromatograph. Following the
GC parameters, summary guality control data is presented for
chromatographic analyses performed during the course of
these studies.
179


APPENDIX C
ISOTHERM DATA FOR THE SORPTION OF STUDY COMPOUNDS
TO LAKE ALFRED AQUIFER MATERIAL
Batch isotherm data is presented for each compound
in this study. Freundlich isotherms for each compound are
also shown.
186


55
Dividing all terms of equation [4-2] through by R and
defining D* = D/R, v* = v/R and k* = k/R, equation [4.2]
becomes
3 C/3t = Dh* 32C/ gx2 v* g C/ gx k* C [4.3]
at steady state conditions where SC/9t = 0, equation 4.3
reduces to:
D 92C/ 9 x2 v 9C/ 9 x + k C 0 [4.4]
h
For steady state conditions there is no sorption effect
since the R term cancels out and the rate of biodegradation
(k) may then be calculated by application of the first order
rate equation to the portion of the BTC which is at steady
state. The first order rate equation for this system is:
C/C = e ~kt [4.5]
o
For a column of length x, and with a pore water velocity of
v, time may be expressed as
t = x/v [4.6]
and substitution of [4.6] into [4.5] and rearrangement
allows calculation of the rate constant for biodegradation:
k = ( In C/Cq ) v/x [4.7]


22
solute experiments, simple mixtures, or data from crude oil
studies.
Houzim (1978) observed a decrease in sorption in the
order alkenes > aromatics > cycloalkanes > alkanes.
Nathawani and Phillips (1977) in a study of hexadecane, o-
xylene, toluene and benzene in crude oil on soils of varying
organic matter presented sorption coefficients based on
Freundlich isotherms. Rodgers et al. (1980) reported the
adsorption and desorption of benzene on several soils and
clays at 25 C. The aqueous phase concentration range was 10
to 1000 ug/L. Sorption of benzene was minimal, except on
aluminum saturated clay. These data are summarized in Table
3-2.
Wilson et al. (1981) evaluated the sorption of toluene
on a fine sand in a column study. A retardation factor less
than 2 for the concentration range of 200-900 ug/L was
reported. This indicates the relatively low retardation
potential of sandy aquifers. The retardation factor
describes the extent of solute transport relative to water.
The retardation factor for water is defined as unity.
Solutes with large retardation factors are less mobile and
and their movement is retarded, relative to that of water.
Schwarzenbach and Westall (1981) presented data for the
sorption of several chlorinated and alkyl benzenes on twelve
natural aquifer materials with varying amounts of organic
carbon. The initial concentrations of the alkylbenzene
components were 20 ug/L. Sorption coefficients from batch


LOO AMOUNT SORBED
LOG SOLUTION CONCENTRATION
a SORPTION o DESORPTION
Freundlich sorption-desorption isotherm for 1,2,4-Trimethylbenzene
at equilibrium.
210


40
The single solute column experiment with benzene used
RAP-2 water spiked with benzene (Aldrich/ gold label 99.9%)
to yield a solution of 4000 ug/L benzene.
4.5 Hydrocarbon Analyses
Gas chromatographic analyses of hydrocarbons for this
study were performed on two systems. These are described
below.
4.5.1 GC/MS Analyses
Field samples collected before September/ 1986/ and the
initial hydrolysis vials were analyzed for volatile aromatic
constituents using a Hewlett Packard model 5985B GC/MS/COMP
system equipped with a 10 port Tekmar Automatic Liquid
Sampler (ALS) and Liquid Sample Concentrator (LSC) purge
and trap system. EPA method 624 was used. Separation of
analytes was achieved with a 0.32 mm i.d./ 30 meter long,
DB-5 (1 urn film thickness) fused silica capillary column
(J & W Scientific), with manual liquid nitrogen
cryofocusing. The 1,4 isomer of dichlorobenzene was used as
an internal standard. Response factors for benzene,
toluene, ethylbenzene and o-xylene were determined relative
to the internal standard and used for quantitation.
Response factors for meta and para xylene were assumed to be
the same as the ortho isomer. A response factor of 1 was
assumed for the C^H-^ hydrocarbons. Chromatographic
conditions were as follows:


CATE
CAYS
Benzere
Tblusre
EtbBZ
m,p-XYL
o-XYL
02-01-66
0
10867
418
859
02-27-86
26
8747
663
1719
604
03-07-86
34
13297
1212
921
3079
367
03-20-86
47
14854
6645
1032
4475
997
03-27-86
54
13603
437
1722
04-25-86
82
14534
1494
1256
3503
827
05-23-86
111
15222
534
759
2785
286
06-25-86
144
4569
20140
5730
4855
2749
07-18-86
167
10489
2786
342
2895
766
08-28-86
208
17751
09-19-86
229
11652
1186
532
10-22-86
262
13630
454
2990
961
3%
11-23-86
294
9387
59
1227
266
180
12-10-86
311
6679
68
12
279
24
02-20-87
383
10989
168
46
436
32
03-17-87
408
13441
228
12
573
26
04-29-87
451
4558
73
6
325
128
05-29-87
481
1823
365
330
1208
749
06-23-87
506
5875
124
136
250
71
WELL UF-3W
90FBZ rv-PBZ 3/4ET
135TMB
2ET
124TMB
123TMB
709
414
237
759
601
690
309
197
1313
453
847
433
276
1458
483
394
230
138
630
341
276
246
148
1625
582
697
322
54
.1179
483
17%
295
456
2252
643
460
69
92
955
207
20
379
975
46
128
29
193
15
20
19
18
48
25
112
30
51
21
87
18
27
5
67
34
101
30
56
17
23
303
116
113
274
168
11
8
74
25
46
56
66
305


PORE VOLUMES
Figure 5-24. Breakthrough curve for benzene in column biodegradation
experiment performed at a flow rate of 1 mL/min.
152


o
O
\
CJ
o
2 A
PORE VOLUMES
6
Breakthrough curve for m,p-xylene in column biodegradation
experiment performed at a flow rate of 1 mL/min.
282


given reaction mechanism depends on the nature of the
sorbent surface. Partitioning is probably more important in
soils with high organic carbon contents. The varying
degrees of sorption in soils with low organic carbon
contents reported by Milgelgrin and Gerstl (1984) reflect
the variation in the ability of mineral surfaces to sorb
organic compounds.
5.7 Comparison of Mixed Solute and Single Solute
Retardation .
Nkedi-Kizza et al. (1987) demonstrated the influence of
organic co-solvents on the movement of hydrophobic organic
compounds through soils. In this dissertation, the study
compounds were a multicomponent mixture of dissolved
aromatic solutes, resulting from the partial solubilization
of a leaded gasoline product into groundwater at the Lake
Alfred site. The presence of multiple solutes may affect
the sorption of a single component of the mixture either by
changing the solubility of the component or through
competitive sorption (Brookman et al., 1985). To evaluate
this possibility, a single solute (benzene, 4 mg/L dissolved
in RAP-2 well water) was passed through a soil column. The
breakthrough of this solute is shown in Figure 5-12.
Evaluation of the retardation factor for this column yielded
an R value of 1.4, which is equivalent to the R value for
benzene from the mixed solute sample. Based on these data,
no co-solute effect on benzene was observed. If a


127
xylene, 2-ethyltoluene, 1,3,5-trimethylbenzene and 1,2,3-
trimethylbenzene. All compounds showed a substantial
increase in half lives, except for m,p-xylene and 1,2,4-
trimethylbenzene. Throughout this study these compounds
were well degraded. These compounds were the most rapidly
removed compounds in the work of Kappeler and Wuhrmann
(1978a, 1987b). The changes in the degradation rates for
the other aromatic compounds may reflect a change in the
community structure of the well water bacteria. The
bacteria from the field site may be adapted to degrade
aromatic compounds that are usually thought to be
recalcitrant or degraded slowly (i.e., benzene). In
treatment 1A, benzene was rapidly and easily removed by the
bacterial community. However, by disrupting this community
by the addition of additional nutrients and hydrogen
peroxide, only the compounds which are more easily
biodegraded are removed. It may be possible that if these
experiments were carried out for longer incubation periods,
the microbial communities may have adapted to efficiently
degrade the remaining aromatic compounds.
5.9.7 Treatment 1G
This treatment was a sterile control. The DO in this
system remained at the initial levels (Figure 5-17),
indicating the sterility of the system. Losses from the
system are in the range of 25-50% for C^-Cg solutes, and 55-
65% for CgH-^2 solutes. These losses were most likely the
result of diffusion of the volatile components through the


WELL UF-2M
EME
EMS
Benzene
Toluene
Etrtoz
m,p-Xyl
o-Xyl
02-01-86
0
6219
14284
691
9942
4753
02-27-86
26
5388
15775
1199
9595
4111
03-07-86
34
8107
13061
1437
11205
4697
03-20-86
47
4777
20990
1437
9538
4146
03-27-86
54
4580
12128
1297
9932
4500
04-25-86
82
4735
14895
1879
14266
6245
05-23-86
111
3766
14273
2351
11923
5070
06-25-86
144
4905
26302
5579
9567
4356
07-18-86
167
2686
17064
2410
12591
5300
08-28-86
208
1736
20822
3171
12705
7867
09-19-86
229
2304
13536
2106
9913
5453
10-22-86
262
1468
15877
3410
13490
7321
10-25-86
265
1721
13209
2805
13295
7372
10-28-86
268
2840
14961
1443
9781
5460
11-04-86
275
2147
12812
2400
11649
6424
11-07-86
278
2576
14454
2625
11398
6158
11-19-86
290
2102
13374
2153
10042
54%
11-23-86
294
1795
16723
2565
10812
5867
12-10-86
311
2972
14801
2105
11072
5499
01-27-87
359
1632
9972
1309
8904
4356
02-20-87
383
3163
11290
20%
12586
5979
03-17-87
408
1164
6636
115
7261
3591
04-29-87
451
1058
4756
64
8239
4136
05-29-87
481
352
7327
1550
8242
3903
06-23-87
506
90
5494
2032
9250
3942
isoPBZ
n-PBZ
3,4ET
135TM8
2ET
1241M3
123T
3589
1387
1330
4567
1485
3664
1084
979
4203
1090
4426
1409
1202
5093
1399
4098
1389
1123
4659
1212
3664
1192
1143
4354
1221
5365
1622
1073
6357
1668
4342
1394
1179
5200
1151
4315
992
992
4261
858
4117
759
1024
4784
931
3380
7135
3585
1915
148
4605
2206
422
3621
2032
1522
4756
1363
164
363
3786
1690
1438
4852
1635
65
140
2691
1209
1113
3307
1071
111
342
3601
1774
1653
4644
1524
163
3521
2460
1485
2%3
2681
1389
97
255
2736
1134
1126
3488
1164
127
286
3248
992
1041
3394
1231
82
180
2378
835
730
2936
1060
58
83
2040
737
609
2504
978
2004
2006
5280
2590
2134
3621
2224
11
4
1530
579
470
1984
756
14
11
2023
7%
639
2592
1034
83
188
2271
877
666
2876
1074
78
162
2220
843
645
2606
987
304


Treatment #2B
DAY 21
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
208
761
17
152
388
498
1585
31
1584
1299
757
1516
37
379
744
avg
488
1287
29
705
810
std
224
373
8
628
375
%variance
46
29
29
89
46
Treatment #2B
DAY 34
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
68
142
11
154
118
9
29
1
8
24
324
353
9
28
165
avg
134
175
7
63
102
std
137
134
4
65
59
%variance
102
77
58
102
57
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
58
51
49
13
83
4.40
321
145
161
337
293
2.40
112
102
104
51
200
2.70
164
99
105
134
192
3.17
113
38
46
145
86
0.88
69
39
44
108
45
27.81
3,4ET
135TMB
2ET
124TMB
12 3 TMB
[DO]
36
12
18
26
32
3.40
5
2
7
2
10
3.60
15
19
24
2
41
3.00
19
11
16
10
28
3.33
13
7
7
11
13
0.25
69
63
43
113
47
7.48
249




312
Litchfield, C. (1986). An Overview of The In Situ
Bioreclamation of Ground Water; Principles, Practices and
Potential! Newark, Dl! E.I. dupont de Nemours and
Company.
Litchfield, C., and L. Clark. (1973). Bacterial Activity in
Ground Waters Containing Petroleum Products. Washington,
D.C.: American Petroleum Institute.
MacKay, D.M., P.V. Roberts, and J.A. Cherry. (1985). Transport
of Orqanic Contaminants in Groundwater. Environ. Sci.
Technol. 19(5): 384-392.
McCarty, P.L. (1984). Application of Biological Transformation
in Ground Water. Proceedings of Second International
Conference on Ground Water Quality Research, March 1984,
Tulsa, OK. Worthington, OH: National Well Water
Association.
McKee, J.E., F.B. Laverty, and R.M. Hertel. (1972). Gasoline
in Groundwater. Journal Water Pollution Control
Federation 44: 293-302.
McKenna, E.J., and R.D. Heath (1976). Biodegradation of
Polynuclear Aromatic Hydrocarbon Pollutants by Soil and
Water Microorganisms. University of Illinois, Champaign-
Urbana, Research Report No. 113.
Means, J.C., S.G. Wood, J.J. Hassett, and W.L. Banwart.
(1982). Sorption of Amino-and Carboxy-Substituted
Aromatic Hydrocarbons by Sediments and Soils. Environ.
Sci. Technol. 16: 93-98.
Milgelgrin, U., and Z. Gerstl. (1983). Reevaluation of
Partitioning as a Mechanism of Nonionic Chemicals
Adsorption in Soils. J. Environ. Qual. 12(1): 1-11.
Miller, C.T., and W.J. Weber. (1984). Modeling Organic
Contaminant Partitioning in Ground-Water Systems. Ground
Water 22,3: 584-591.
Mitchell, R (1974). Introduction to Environmental
Microbiology. Englewood Cliffs, N.J.: Prentice-Hall Inc.


1J
o
O
\
O
/ -
0.9 -
a& -
0.7 -
0.6 -
05 -
OA -
OJ -
0.2 -
OJ -
-B-B-B-Ejt
PORE VOLUMES
Breakthrough curve for n-propylbenzene in column biodegradation
experiment performed at a flow rate of 1 mL/min.
284


C / C o
PORE VOLUMES
BNZ + TOL o EBZ a MPX x OX
Figure 5-23. Breakthrough curves for aromatic compounds in column
biodegradation experiments performed at a flow rate
of 0.90 mL/hr.
148


C / C o
PORE VOLUMES
Figure 5-26. Breakthrough curve for 1,2,4-trimethylbenzene in column
biodegradation experiment performed at a flow rate of 1 mL/min.
154


82
ml/min exhibited higher values of since dispersion
increases with increasing pore water velocity (Roberts et
al. / 1985). It may be noted that the pore water velocity of
0.680 cm/min was equivalent to the seepage velocity in some
portions of the aquifer at the Lake Alfred field site.
These data are compared to field dispersion data in section
5.10.
5.5.2 Aromatic Solute Breakthrough Curves
Breakthrough curves for selected, dissolved aromatic
solutes in the column effluent (Well OHM-4 water) are shown
in Figure 5-5 (benzene) Figure 5-6 (toluene) and Figure 5-7
(n-propyIbenzene). Breakthrough curves for these solutes
are presented because they show the the breakthrough of the
least retained compounds (benzene and toluene) and the most
retained (n-propylbenzene). These solutes are presented
separately to avoid overlap on a single plot, but are part
of the multi-component mixture resulting from the
solubilization of gasoline into groundwater at the Lake
Alfred site. Graphical representations of the remaining
solutes in the column effluent are shown in Appendix D. The
changes in effluent concentration near the end of each
breakthrough curve was consistent for each solute,
reflecting the same relative variability. These deviations
may be explained by heterogeneities in flow paths in the
porous media, or by analytical error.
Calculated values of R, K, and K based on the
d oc
analyses of the column data by curve fitting to Brenner


LOO AMOUNT SORBED
LOO SOLUTION CONCENTRATION
a SORPTION o DESORPTION
Freundlich sorption-desorption isotherm for 1,3,5-Trimethylbenzene
at equilibrium.
204


16
2 o
ac/at + p/0 a s/st = Dh sc /ax v ac/ax [3.6]
where p is the bulk density, 0 is the volumetric water
content and S is the sorbed phase concentration. Note that
equation [3.6] is equivalent to equation [3.1] with the
addition of the sorption term aS/ at. Assuming linear,
reversible sorption, the sorbed concentration of a solute is
related to the aqueous concentration of the solute by the
relationship:
3 S/3t = Kd 3 C/9t [3.7]
Substitution for 3S/ at in equation [3.6] with equation
[3.7] yields the relationship:
ac/at + Kd ac/at Cp/e) = Dh a2c/ax2 v a c/ax [3.8]
After separation of variables equation [3.8] becomes
ac/at [ l + p Kd/e] = Dh 32c/ax2 v ac/3x [3.9]
and by defining the retardation factor (R) as
R = 1 + p Kd/0 [3.10]
substitution of equation [3.10] into [3.9] results in the
incorporation of the retardation factor (R) into the mass
transport equation for solute transport under saturated
steady flow conditions:
r ac/at = Dh a2c/3x2 -v ac/ax [3.ii]
Analysis of equation [3.10] indicates that the value of
R is largely dependent on Kd for a homogeneous aquifer
system or laboratory column. Determination of R from soil


143
septa. Based on this loss, the decrease in DO in treatments
2G and 2H was not attributed solely to microbial activity.
The diffusion of oxygen across the teflon septa may also
account for the increased degradation of the solutes in this
study. In general, two parts of oxygen are required to
remove one part of hydrocarbon. Using these calculations,
the microcosms should have been oxygen limited. The absence
of oxygen limitation, particularly in treatments with no
added source of oxygen, was likely the result of oxygen
diffusion into the microcosms. This suggests that in future
studies, a more suitable microcosm should be employed.
5.10.6 Discussion of Batch Biodegradation Data
The rates of biodegradation (k values and half-lives)
were highest in both biodegradation experiments with air
augmentation (1A and 2A) or with the addition of oxygen
(2G). Almost complete degradation (to below detection limit
or less than 2 ug/L) was shown in each case. These data
indicated that the limiting substance was oxygen. Analysis
of water quality data supports this hypothesis. Total
phosphate in the groundwater averages 0.6 mg/L and nitrate
averages 0.25 mg/L.
Addition of NH^Cl to the microcosms may have spurred
the process of nitrification. This would account for the
reduction in dissolved oxygen values without the concomitant
loss of hydrocarbons. This effect was seen in treatment 2B.
In this case, the DO dropped from 7.5 to 2.5 mg/L with no
loss in hydrocarbon concentration. The presence of nitrate


92
sorption. This results from nonlinearity of the sorption
isotherm, which governs the position of the breakthrough
curve.
The BTC data in this study were obtained for a single
flow velocity and at only one range of concentrations.
However, the importance of increased flow velocity and high
concentration on the transport of contaminants may be
significant at the Lake Alfred field site. Killan (1987)
reported seepage velocities of 1 to 18 feet per day in the
Lake Alfred aquifer. This high flow velocity, combined with
the high levels of hydrocarbon contamination and oxygen
limitation in certain areas at the Lake Alfred site suggests
that movement of solutes may be more rapid than these column
experiments would predict. The sorption isotherms
calculated in this study were based on linear isotherms, for
concentrations which were present in the well water.
However, it is possible that residual gasoline in the
aquifer may provide higher concentrations in selected areas,
leading to more rapid leaching of aromatic solutes owing to
higher concentrations (eg., the sorption isotherms may be
nonlinear, and R may be concentration dependent).


o
o
V:
O
O
LOO WATER SOLUBILITY
OC
Figure 5-9. Log K
(from column data) vs. log WS for study compounds
r ^


M + 1B o 1C
Figure 5-16. Concentration vs. time for dissolved oxygen in biodegradation
treatments 1A, IB and 1C.
124


78
Table 5-8. Regression parameters for the analysis of
average values of equilibrium batch
desorption data with the Freundlich model.
Compound
Na
c b
(ug/^L)
log
Kf ,
log
stdc
d
n ,
t t e
std
2
r
Benzene
5
950
-0.635,
0.168
1.02,
0.079
0.982
Toluene
8
4200
-0.478,
0.039
0.992,
0.019
0.998
m,p-Xylene
9
4300
-0.561,
0.096
0.963,
0.043
0.986
o-Xylene
9
2500
-0.159,
0.263
0.774,
0.099
0.891
3 or 4 ETf
9
935
-0.692,
0.068
1.029,
0.030
0.994
1,3,5-TMB9
8
460
-0.569,
0.051
0.956,
0.025
0.996
2-ETh
7
373
-0.657,
0.079
0.983,
0.046
0.989
1,2,4-TMB1
10
1600
-0.658,
0.122
0.997,
0.056
0.981
1,2,3 TMB-1
9
558
-0.624,
0.092
0.988,
0.038
0.990
anumber of data points
b
maximum concentration
clog standard deviation of values
uFreundlich exponent
0 t
standard deviation of Freundlich exponent
^3 or 4 Ethyltoluene
gl,3,5-Trimethylbenzene
2-Ethyltoluene
1l,2,4-Trimethylbenzene
-*1,2,3-Trimethylbenzene


Table 5-5.
71
Ratio of sorbed concentrations calculated
from Freundlich and linear equilibrium models
Solute
concentrations
(ug/L)
1
50
100
500
1000
Benzene
2.01a
1.73
1.27
1.09
1.01
Toluene
3.23
1.97
1.81
1.48
1.36
m,p-Xylene
1.81
1.30
1.23
1.08
1.01
o-Xylene
1.35
1.18
1.16
1.09
1.07
3 or 4 ETb
2.14
1.48
1.38
1.18
1.10
1,3,5-TMBC
1.70
1.25
1.18
1.04
0.99
2-ETd
1.04
1.01
1.00
0.99
0.98
1,2,4TMBS
1.69
1.34
1.28
1.15
1.10
1,2,3TMBf
1.88
1.35
1.27
1.12
1.05
athe ratio of the amount sorbed as calculated from the
Freundlich model to the amount sorbed predicted from the
linear model with suppressed intercept, at the same
solution concentration.
u3 or 4 Ethyltoluene
c
1,3,5-Trimethylbenzene
2-Ethyltoluene
el,2,4-Trimethylbenzene
^1,2,3-Trimethylbenzene


I certify that
opinion it conforms
presentation and is
a dissertation for
I certify that
opinion it conforms
presentation and is
a dissertation for
I certify that
opinion it conforms
presentation and is
a dissertation for
I certify that
opinion it conforms
presentation and is
a dissertation for
I have read this study and that in my
to acceptable standards of scholarly
fully adequate/ in scope and quality/ as
the degree of Doctor of Philosophy.
'I l L
Wesley Lamar Miller/ Chairman
Professor of Environmental
Engineering Sciences
I have read this study and that in my
to acceptable standards of scholarly
fully adequate/ in scope and quality/ as
the degree of Doctor of Philosophy.
Joseph J. Del fino/ Cochairman
Professor of Environmental
Engineering Sciences
I have read this study and that in my
to acceptable standards of scholarly
fully adequate/ in scope and quality/ as
the degree of Doctor of Philosophy.
of
Geology
I
ha
ve
re
ad this st
udy an
d
th
at in my
to
a
cc
ept
able stand
ards o
f
sc
holarly
fu
11
y
ade
quate in
scope
an
d
quality/
the
d
eg
ree
of Doctor
of Ph
il
os
ophy.
Paul A. Chadik
Assistant Professor of
Environmental Engineering Sciences


109
availability of non-biological catalysts in the aqueous
phase. Water from wells OHM-4 (with aromatic solutes) and
RAP-2 (no aromatic solutes) were titrated with hydrogen
peroxide solutions of 240 and 2400 mg/L with no apparent
increase in dissolved oxygen, indicating an the absence of a
active catalyst in both these water samples.
The response of non-filtered water from well OHM-4 to
the addition of 50% hydrogen peroxide is shown in Figure 5-
13. The pH of the water in the reaction flask was 6.5 and
this value remained constant throughout the course of the
experiment. The redox potential increased from 59 milli
volts (mv) to 338 mv immediately following the addition of
500 ul of 50% H(e<3uivalent to 2000 mg/L H2O2). This
addition of was sufficient to maintain an increase of 1
mg/L over the ambient DO in the reaction flask. The
addition of sterile aquifer material from the Lake Alfred
site increased the DO of the reaction flask immediately
after introduction. This indicated the catalytic ability of
the Lake Alfred aquifer and was most likely associated with
the presence of iron salts (Britton 1985) although iron
concentrations were not determined for the Lake Alfred
aquifer material. This small scale study helped to
determine the reactivity of the hydrogen peroxide in the
Lake Alfred aquifer system, and provided ranges for use of
hydrogen peroxide in the biological experiments. Gas
chromatographic analyses of aromatic compounds during the
course of this experiment showed that there were no


1,3,5-Trimethylbenzene Desorption Data
amount
Cs (ug/L) Cw (ug/L) sorbed
avg
std
avg
std
(ug/L)
198
32.7
4 59.7
28 .31
261.7
12
3.38
45.97
a
33.97
2.2
0.36
9
2.11
6.8
143
4.06
32 6
46
183
64
4.02
175
30
111
14
0 71
44
1
30
2.5
0.08
12
3
9.5
1 .6
0.22
4
a
2.4
n= 1
a
amount
sorbed
(ng/g)
90.3
11.7
2.3
63.1
38.3
10.4
3.3
0.8
log log
amount solution
sorbed concentration
1.96 2.66
1.07 1.66
0.37 0.95
1.80 2.51
1.58 2.24
1.01 1.64
0.52 1.08
-0.08 0.60
203


45
zero/ and the log normalized (Freundlich) models (Miller and
Weber, 1984).
4.8 Column Sorption Studies
4.8.1 Experimental Procedures
Leaching column experiments were performed with a 25 x
250 mm glass preparative chromatography column (Altex cat.
no. 252-18) with a Teflon coated adjustable plunger (Nkedi-
Kizza et al./ 1987). Aquifer material was dry packed into
the column which was then autoclaved at 120 C for 1 hour.
The solutes were pumped from 2.6 L Teflon gas sampling bags
(Alltech Associates/ Deerfield/ IL) with a Gilson model 302
HPLC pump fitted with a model 5s pump head (Gilson Medical
Electronics/ Middleton-/ WI). The flow range of this system
was 0.005 5.00 mL per minute. All transfer lines and
connections were Teflon or stainless steel to minimize
interaction of solutes with reactive surfaces. Column
length was adjusted to 5.0 cm. Flow rates through the
column were set at 1 ml/min (0.204 cm/min) for sorption
studies. Column effluent breakthrough curves (BTCs) were
measured under steady saturated water flow conditions with
continuous application of solute containing water.
Effluents from the sorption columns were collected
manually in 1 ml crimp seal vials. These column effluents
were either analyzed immediately or stored at 4 C in 1 mL


WELL O
ERIE
DAYS
BE
TX
EIHBZ
M,P-XYL
O-XYL
02-01-86
0
7060
19055
10280
4395
02-27-86
26
706
1643
2023
814
03-07-86
34
4625
13885
7256
2900
03-20-86
47
6437
42663
237
9394
4080
03-27-86
54
5009
15352
10667
4802
04-25-86
82
1951
1819
3372
1903
06-25-86
144
2473
13381
1651
6765
3124
07-18-86
167
3887
18366
5663
7916
3789
08-28-86
208
1553
14938
1699
7238
3998
09-19-86
229
4010
34621
2409
11187
5810
10-22-86
262
2419
35679
4155
13566
7363
10-25-86
265
1231
14909
1529
5859
3083
10-28-86
268
2804
24028
2281
8526
4275
11-04-86
275
1294
15491
1988
6580
3467
11-07-86
278
1316
14691
1813
6239
3566
11-19-87
290
747
11600
1540
5481
3007
11-23-86
294
2004
29434
3469
11809
6154
12-10-86
311
.1211
12325
150
6618
3342
01-27-87
359
559
11561
1557
6873
3342
02-20-87
383
3794
20930
4031
12903
6194
03-17-87
408
1618
17725
494
10332
5303
04-29-87
451
3399
36695
1711
14302
6994
06-23-87
506
381
23151
2504
9868
4637
H M 3
[SPBZ
n-FBZ
3,4ET
135TM3
2ET
124TMB
123TM3
3176
1147
990
3980
1310
552
243
190
795
197
2906
887
788
3212
680
2650
877
818
3231
758
4167
1300
1064
4935
1162
1143
542
1005
926
473
2345
643
657
2573
630
2208
759
2151
2507
690
3600
4575
3320
1755
1395
4460
2196
142
482
3025
1829
1156
3686
886
71
286
1734
769
748
2215
905
77
250
2213
1150
851
2815
837
248
1844
956
938
2361
809
76
221
1675
1232
936
2177
880
71
185
1567
495
446
1746
529
121
352
2929
781
1185
3103
1482
13
8
1219
405
399
1537
490
58
140
1297
448
334
1634
559
1305
1169
3580
1601
13a
3177
1444
55
65
2223
749
574
2421
970
57
68
2062
702
580
2691
859
67
148
1403
457
402
1816
584
294


20
Log K = 0.53 X + 0.54
oc
[3.15]
This relationship is based on literature values of K from
oc
laboratory experiments with 72 compounds covering a broad
range of polarities and classes/ and a variety of sorbent
systems. The correlation coefficient is 0.976 which
explains 95.2% of the variance.
3.4.4 Desorption
In most cases sorption is considered to be completely
reversible/ that is/ the adsorption-desorption isotherms are
reversible and single valued. However/ several
investigators report desorptions which display hysteresis in
batch studies (Bailey and White/ 1970/ Boucher and Lee,
1972/ Carringer et al./ 1975/ DiToro and Horzempa/ 1982).
Van Genuchten
et al. (1974)
found that
the
exponent for
desorption
is
concentration
dependent,
and
described the
hysteretic
behavior by using
separate
isoth
erm equations
sorption and
desorption:
S =
s
IU C nS
ds s
[3
Sd =
k ,, c, nd
dd d
[3
where subscripts s and d indicate sorption and desorption
respectively. Hysteresis in column studies was noted by
Schwarzenbach and Westall (1981)/ although the reaction was
termed reversible/ since all the solute was eventually
eluted from the column.


125
benzene, toluene, 1,3,5-trimethylbenzene, 2-ethyltoluene,
and 1,2,3-trimethylbenzene. Both m,p-xylene (half life = 3
days) and 1,2,4-trimethylbenzene (half life = 2.96 days)
were less affected and were each degraded to 1.7 ug/L. At
the end of 31 days, 31% of 1,2,3-trimethylbenzene remained
but 1,3,5-trimethylbenzene, 2-ethyltoluene and 1,2,4-
trimethylbenzene although not completely degraded were well
removed.
5.9.5 Treatment IE
Graphical representation of this treatment is shown in
Appendix E. These vials are treated with 18 mg/L NH^Cl and
17 mg/L This combination of treatments caused an
increase in the 1/2 lives for the C^-Cg compounds, but the
removal rates
of
the CgH-j-2 co
mpounds
were
improved relative
to
treatment
with
ammonium ch
loride
alone .
Ultimate removal
of
compounds
was
good except
for the
more
recalcitrant o-
xylene, 1,2,3-trimethylbenzene, 3,4-ET and 1,3,5-
trimethylbenzene. The lag in degradation of the aromatic
solutes was reflected in the reduced consumption of DO in
the microcosms (Figure 5-17).
5.9.6 Treatment IF
Treatment with 68 mg/L 8^0^ and 18 mg/L NH^Cl is shown
in Appendix E and average data are shown in Table 5-16.
There was an obvious lag in the DO profile (Figure 5-17),
and the half life for dissolved oxygen was increased from
1.8 days in treatment 1A to 9.4 days in this treatment.
This was also reflected in the concentrations of benzene, o-


171
in this study. This was likely the result of the use of low
concentrations (less than 2% of the water solubility).
Sorption mechanisms were evaluated by comparison of Kqc
data from column studies in this study with partitioning and
molecular topology models. Regression analysis of Kqc data
versus literature values for K demonstrated that
ow
partitioning alone did not adequately describe the sorption
2
process (r = 0.857). Regression analysis of Kqc data with
first order molecular connectivity indices indicated that
sorption may be partially described as a surface area
2
dependent phenomena (r = 0.839). Both models gave
equivalent fit to the Kqc data, and this suggested that
sorption was the result of several processes.
6.1.3 Biodegradation Studies
Rate constants for the biodegradation of selected
aromatic hydrocarbons were determined from batch and column
studies. Column studies yielded higher rate constants than
the batch studies indicating more rapid removal of solutes.
Half lives for columns run at 0.01 cm/min were between 0.120
days for benzene to 0.041 days for m,p-xylene. Rate
constants derived from columns with velocities of 0.680
cm/min were higher, indicating increased removal of
hydrocarbons. These half lives ranged from 0.940 hours for
benzene to 0.086 hours for n-propylbenzene. The increased
removal at the higher flow rate was the result of improved
transport of oxygen and nutrients to the microbes. The 1
mL/min flow rate (0.680 cm/min) was equivalent to seepage


18
16
14
12
10
8
6
4
2
0
500 uL 507. HP added
a.
0
Time, hours
5-13. Reaction of OHM-4 well water to the addition of 50% hydrogen
peroxide and aquifer material.
110


30
activation or transfer of plasmids (Litchfield, 1986). This
ability of microorganisms to adapt to the presence of
contaminants forms the basis of in-situ biodegradation.
Several researchers have reported the biodegradation of
aromatic compounds in groundwater. One shortcoming of most
of this research is the lack of degradation rate coefficient
data, required for use in groundwater transport models, and
insufficient data on solute concentrations.
Jamison et al. (1976) reported the use of benzene as a
sole carbon source. No rate coefficient data were given.
McKenna and Heath (1976) noted the slow oxidation of benzene
by P. putida. Delfino and Miles (1985) showed the
degradation of benzene in 16 days under aerobic conditions
in Floridan groundwater with an eight day lag phase.
Ethylbenzene was degraded as a sole carbon source (Gibson
and Yeh, 1973), but no rate data were given. Schwarzenbach
et al. (1983) found toluene rapidly degrades within several
meters in a study of
river
water i
nfiltration
to
groundwater
but rate and initial
concentration
data were
not
specified.
Kappeler and Wuhrmann
(1978b)
in a study
of
gas oil
degradation reported
that
nitrogen
and oxygen
were the .
limiting factors in hydrocarbon degradation. Addition of
NH^Cl resulted in further microbial degradation, and cell
densities were on the order of 10 /mL Lag times of 5-6
days were noted in the batch experiments. Kappeler and
Wuhrmann (1978a) showed that microbes from uncontaminated
groundwater can attack gas oil components. Lag times of 1


311
Karickhoff, S.W., D.S. Brown, and T.A. Scott. (1979). Sorption
of Hydrophobic Pollutants on Natural Sediments. Water
Research 13: 241-248.
Kenaga, E.E., and C.A. Goring. (1980). Relationship between
Water Solubility, Soil Sorption, Octanol-Water
Partitioning and Bioconcentration of Chemicals in Biota.
In Aquatic Toxicology. J.G. Eaton, P.R. Parish, and
A.C. Hendricks (eds): New York: American Soc. of Testing
Materials, pp. 78-115.
Killan, G.A. (1987) Hydrogeologic Characterization of
Hydrocarbon Pollutant Transport in a Sandy, Unconfined
Aquifer. M.S. Thesis, University of Florida.
Klein, D.A., T.C. Loh, and R.A. Goulding. (1971). A Rapid
Procedure to Evaluate the Dehydrogenase Activity of Soils
Low in Organic Matter. Soil Bio. Biochem. 3: 385-387.
Kuhn, E.P., P.J. Colberg, J.L. Schnoor, 0. Wanner, A.J.B.
Zehnder, and R.P. Schwarzenbach. (1985). Microbial
Transformations of Substituted Benzenes during
Infiltration of River Water to Groundwater: Laboratory
Column Studies. Environ. Sci. Technol. 19,10: 981-968.
Lapidus, L., and N.R. Amundson. (1952). Mathematics of
Adsorption in Beds. VI. The Effect of Longitudinal
Diffusion in Ion Exchange and Chromatographic Columns. J
Phys. Chem. 56: 984-988.
Lee, M.D., and D.H. Ward. (1984). Reclamation of Contaminated
Aquifers: Biological Techniques. Proceedings of Hazardous
Material Spills Conference April 1984, Nashville, TN.
Worthington, OH: National Well Water Association, pp.
98-103.
Leo, A., C. Hansch, and D. Elkins. (1971). Partition
Coefficients and Their Uses. Chemical Reviews 71: 525-
616.
Levenspiel, 0. (1972). Chemical Reaction Engineering. New
York: John Wiley and Sons, pp. 41-86.


WELL RAP-7
DAIE
CATS
BE
TCL
EthBZ
m,p-XYL
O-XYL
iso-PEZ
n-PBZ
3,4ET
13511
2ET
12411
123HB
10-22-86
262
0.3
0.5
0.5
1.3
0.6
0.5
0.6
11-23-86
294
12-10-86
311
0.1
0.15
1.4
1
01-27-87
359
1
02-20-87
383
1
1
03-17-87
408
04-29-87
451
0.2
0.24
0.18
0.1
1.5
0.43
05-29-87
481
0.02
0.16
0.04
0.25
2.1
0.5
0.3
9.7
06-23-87
506
0
0
1
0
0
0
0
0
1
0
302


48
equilibrated at room temperature (20 + 2 C) in the sealed
flask. Hydrogen peroxide (50%) was added undiluted in
microliter quantities and at various dilutions. Aquifer
material was then added to assess the ability of the
material to catalyze the reaction. The 50% hydrogen
peroxide stock was titrated with 0.01N potassium
permanganate (Dupont, 1984) to check the strength of the
stock solution. The standardized stock was then used to
make the appropriate dilutions without further calibration.
4.10 Batch Biodegradation Studies
4.10.1 Experimental Procedure
Batch biodegradation experiments were performed in 40
mL VOA vials as described for the batch sorption
experiments.
Well water from OHM-4 was used as the source of both
dissolved aromatic hydrocarbons and bacteria in these
studies. The water was not filtered prior to use. This
experiment was designed to evaluate the ability of adapted
groundwater bacteria to degrade mixtures of dissolved
aromatic solutes at field scale concentrations. The
experimental design for batch biodegradation experiment
number 1 is shown in Table 4-1. Seven treatments were set
up, with 15 replicate vials per treatment. Water from Well
OHM-4 was added (350 mL) to a 500 mL erlenmeyer flask, and
then amended with hydrogen peroxide (50%), ammonium chloride




70
water on the day samples were collected for this study. The
linearity of these isotherms was confirmed by the values of
the regression coefficients and the Freundlich exponents
(n)/ both of which were close to unity. As n approaches
unity the models should converge since the linear model is
in effect a special case of the Freundlich model.
A comparison of the Freundlich and linear models is
presented in Table 5-5. The deviation between predicted
amounts of sorption for the linear model with suppressed
intercept and Freundlich models are expressed as ratios
between the calculated sorbed concentrations. This method
was used to evaluate the predictive equivalence of both
models over the concentration ranges encountered in this
study. This method was chosen, since direct comparison of
and values may be misleading owing to the log
transformation of the data in the Freundlich isotherm model.
The largest deviations occurred for toluene at 1 ug/L. In
general the ratios approached unity as the concentrations
increased, but diverged in the range between 1 to 50 ug/L.
This comparison indicates that the models, were essentially
similar, as is predicted from the values of the Freundlich
exponent (n). As n approaches unity, the Freundlich
isotherm approaches the linear isotherm. The convergence of
these models is confirmed by an examination of 2-
ethyltoluene in Table 5-5. This compound has the highest
Freundlich constant (n = 0.993) and the ratios of predicted


185
will be tightly packed to reduce headspace in
the sample container. Samples are
transported on ice and stored at 4 C in the
dar k.
6.4.2Biological Analysis
Soil samples for biological analysis will be
collected with sterilized (100 ppm chlorine
solution) stainless steel auger. Samples will
be placed in a one quart mason jar, cleaned
in the same manner as the described in
section 6.1.1. Samples will be stored at 4 C
in the dark.
6.5 Measurement of field parameters.
6.5.1 Temperature.
Temperature will be measured in the wells
using a thermometer, calibrated against an
NBS standard thermometer.
6.5.2 pH.
The pH of the well water will be measured
using a portable pH meter (Orion Research
model 401) connected to a Fisher AccupHast
microprobe combination electrode.
6.5.3 Dissolved Oxygen.
DO will be measured using a portable
dissolved oxygen meter (YSI 54A ) with a YSI
5739 oxygen probe.


LOO .¡MOUNT SORBED
LOO SOLUTION CONCENTRATION
SORPTION o DESORPTION
Figure 5-3. Freundlich sorption isotherm for toluene at equilibrium.


217
Column Sorption Data as C/Co
PV
BNZ
TOL
Ethyl Bz
m,p-XYL
o-XYL
0.253
0.001
0.002
0.001
0.001
0.001
0.537
0.001
0.001
0.001
0.001
0.001
0.677
0.010
0.006
0.002
0.002
0.003
0.820
0.101
0.062
0.023
0.021
0.037
0.963
0.280
0.201
0.108
0.101
0.150
1.106
0.429
0.322
0.226
0.181
0.269
1.250
0.584
0.469
0.370
0.305
0.414
1.392
0.620
0.525
0.455
0.380
0.500
1.536
0.703
0.590
0.520
0.439
0.560
1.823
0.816
0.713
0.677
0.577
0.697
1.967
0.859
0.756
0.735
0.621
0.744
2.111
0.849
0.763
0.755
0.648
0.761
2.254
0.912
0.830
0.810
0.690
0.822
2.398
0.930
0.846
0.848
0.723
0.855
2.542
0.966
0.855
0.897
0.763
0.903
2.685
1.037
0.962
0.980
0.830
0.974
2.829
0.953
0.925
0.985
0.854
0.980
2.973
0.995
0.964
1.033
0.887
1.017
3.116
1.025
0.979
1.030
0.890
1.018
3.260
0.952
0.944
1.041
0.892
1.033
3.404
0.971
0.929
0.985
0.848
0.992
3.547
1.021
1.024
1.150
0.994
1.122
3.835
1.148
1.166
1.304
1.133
1.304
3.978
1.089
1.091
1.198
1.046
1.210
4.122
1.171
1.171
1.305
1.130
1.300
4.411
1.125
1.109
1.210
1.057
1.238
4.555
1.094
1.084
1.185
1.031
1.197


29
microflora to adapt to the added substance. Adaption is a
phenomenon rather than a mechanism or process, and the term
refers to an increase in the rate of biotransformation of a
substance resulting from exposure to that substance (Wilson
et al. 1983b). Low solute concentrations may result in the
occurrence of a threshold limit, below which the microflora
are unable to utilize the solute with out a cosolute (Wilson
and McNabb, 1983). Jensen et al. (1985) demonstrated the
degradation of aromatic molecules to less than 1 ug/L,
implying that there was a very low threshold limit for the
aromatic hydrocarbons. The relationship between
concentration and biodegradation was reviewed by Alexander
(1985). He stressed the importance of studying contaminant
levels that exist in the environment.
3.5.2 Aromatic Biodegradation Values From the Literature
McKee et al. (1972) reported the oxidation of gasoline
by Pseudomonas and Arthrobacter under aerobic but not
anaerobic conditions. Degradation of gasoline by
Pseudomonas was reported by Williams and Wilder (1971), and
Litchfield and Clark (1973) showed significant numbers (104
cells/mL) of hydrocarbon degrading bacteria in groundwater
contaminated with petroleum hydrocarbons from twelve sites.
Bacterial populations appeared to be related to the
concentrations of hydrocarbons. These data indicate the
adaptation of microbial communities to the changing nutrient
source (i.e., gasoline). The two major mechanisms of
adaptation are induction of metabolic pathways, or the


Table 5-14. Comparison of relationships to predict K
from K values,
ow
oc
log
K
ow
log K values from
3 oc
Range
Compound
Karickoff
a ,, b
Means
ChiouC
iz d
Kenaga
Briggs
p ig
K
oc
Benzene (min.)
1.56
1.35
1.24
0.62
2.22
1.45
0.62-2.61
(max.)
2.28
2.07
1.96
1.27
2.61
1.83
Toluene (min.)
2.11
1.90
1.79
1.12
2.52
1.74
1.12-2.85
(max.)
2.73
2.52
2.41
1.68
2.85
2.06
Ethylbenzene
3.15
2.94
2.83
2.06
3.08
2.28
2.06-3.08
m,p-Xylene
3.18
2.97
2.86
2.08
3.10
2.29
2.08-3.10
o-Xylene (min.)
2.77
2.56-
2.45
1.71
2.88
2.08
1.71-3.07
(max.)
3.13
2.92
2.81
2.04
3.07
2.27
Isopropylbenzene
3.66
3.45
3.34
2.51
3.36
2.54
2.51-3.45
n-Propylbenzene (min.)
3.57
3.36
3.25
2.43
3.31
2.50
2.43-3.37
(max.)
3.68
3.47
3.36
2.53
3.37
2.55
1,3,5-Trimethylbenzene
(min.)
3.42
3.21
3.10
2.30
3.23
2.51
2.30-3.39
(max.)
3.60
3.39
3.28
2.46
3.32
2.51
1,2,3-Trimethylbenzene
3.60
3.39
3.28
2.46
3.32
2.51
2.46-3.39
aKarickoff et al., 1979:
log K = 1.00 *
^ oc
log K
^ ow
- 0.21
Means et al., 1982:
log
k = :
oc
1.00 log
K 0 .
ow
32
CChiou et al., 1983:
log
K = 0.90 log
oc ^
K 0.
ow
78
dKenaga and Goring, 1980:
log K = 0.54 *
^ oc
log K
3 ow
+ 1.38
eBriggs, 1981: Log Kqc
=
0.52 log K +
^ ow
0.64


316
Trevors, J.T. (1982). Effect of Pentachlorophenol on Electron
Transport System Activity in Soil. Bull. Environ. Contam.
Toxicol. 29: 727-730.
Trevors, J.T., C.I. Mayfield, and W.E. Inniss. (1982).
Measurement of Electron Transport System (ETS) Activity
in Soil. Microb. Ecology 8: 163-168.
TRI (1982). Enhancing the Microbial Degradation of Underground
Gasoline by Increasing the Available Oxygen. Austin, TX.:
Texas Research Institute.
USPHS (1981). Second Annual Report on Carcinogens. Research
Triangle Park, NC: United States Public Health Service.
Van Genuchten, M.T., and J.C. Parker. (1984). Boundary
Conditions for Displacement Experiments through Short
Laboratory Soil Columns. Soil Sci. Soc. Am. J. 48: 703-
708.
Voice, T.C., and W.J. Weber. (1983). Sorption of Hydrophobic
Compounds by Sediments, Soils and Suspended Solids I:
Theory and Background. Water Research 17: 1433-1441.
Waksman, S.A. (1916). Bacterial Numbers in Soil at Different
Depths and in Different Seasons of the Year. Soil Science
1: 316-330.
Weber, W.J., T.C. Voice, M. Pirbazari, G.E. Hunt, and D.M.
Ulanoff. (1983) Sorption of Hydrophobic Compounds by
Sediments, Soils and Suspended Solids II: Sorbent
Evaluation Studies. Water Research 17(10): 1443-1452.
Webster, J.J., G.J. Hampton, J.T. Wilson, W.C. Ghiorse, and
F.R. Leach. (1985). Determination of Microbial Cell
Numbers in Subsurface Samples. Ground Water 23,1: 17-25.
Williams, D.E., and D.G. Wilder. (1971). Gasoline Pollution of
a Groundwater Reservoir A Case History. In Proceedings
of the National Groundwater Quality Symposium.
Worthington, OH: National Well Water Association.


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
AN EVALUATION OF THE ATTENUATION MECHANISMS
FOR DISSOLVED AROMATIC HYDROCARBONS FROM GASOLINE
SOURCES IN A SANDY SURFICIAL FLORIDA AQUIFER
by
JOSEPH TIMOTHY ANGLEY
December 1987
Chairman: Wesley Lamar Miller
Cochairman: Joseph J. Delfino
Major Department: Environmental Engineering Sciences
Gasoline is a significant source of groundwater
contamination in Florida. This results from the large
numbers of gasoline storage tanks, high rainfall, reliance
on groundwater-based potable water supplies and the
hydrogeology of Florida. Sorption, biodegradation and
hydrolysis of dissolved aromatic hydrocarbons (all isomers
of C6H6~CgH1?) were determined in multicomponent experiments
with natural aquifer materials under saturated conditions.
Hydrogen peroxide, air, oxygen gas and ammonium chloride
treatments were evaluated as methods to enhance microbial
degradation of aromatic hydrocarbons. The solutes and
sorbents were from a gasoline contaminated aquifer in
central Florida. This site was typical of sandy surficial
xiii


100
is notable that Kqc from this study falls in the upper range
of the predicted Kqc values, given the paucity of organic
carbon in the Lake Alfred aquifer material. A comparison of
predicted Kqc values calculated from water solubility
relationships of several authors and that of equation [5.3]
also show that the experimental K values from this study
oc 1
are generally in the upper range of these predicted values
as well.
The relatively high values of K oredicted from
oc L
equations [5.2] and [5.3] may be the result of several
factors: 1) error in the measurement of organic carbon, 2)
increased hydrophobicity of the organic matter at Lake
Alfred compared to the referenced studies, 3) sorption to
the mineral surface, or 4) any combination of the above
(Curtis et al., 1986). It is unlikely that the organic
matter in this study is more hydrophobic than that used by
other researchers. This is confirmed by analysis of the
slopes of the regression lines in the relationships between
K
oc
and K
ow
The slope of a plot of K vs. K may be
rs v.7
oc
ow
viewed as a measure of the hydrophobicity of the organic
phase in the partitioning model (Leo et al., 1971). In the
experimental data presented here the slope of equation [5.2]
was less than that observed in previous studies where
partitioning is thought to predominate. This is presented
graphically in Figure 5-10. Therefore, increased
hydrophobicity of the organic matter at Lake Alfred was
ruled out.


WELL OHM-1
EME
CAYS BENZENE
TCLUENE
EIHBZ
M,P-XYL
O-XYL
isoFBZ
n-P5Z
3,4ET
13511
2ET
124HB
123TM3
02-01-86
0
3318
77110
2929
11841
4681
3699
970
852
4433
995
02-27-86
26
379
14642
1144
12661
5038
3970
1104
1054
4935
1143
03-07-86
34
305
13514
1353
12963
51%
4029
1173
1084
4758
1094
03-20-86
47
286
13284
921
12215
5313
4236
1330
1143
4580
1123
03-27-86
54
321
9518
265
11061
4986
4551
1478
1202
5063
1399
04-25-86
82
9363
1409
14446
5839
4728
1330
1330
5053
1340
05-23-86
111
214
8259
1404
12423
4998
4262
1448
1099
4610
1179
06-25-83
144
161
9923
22%
%92
4034
3578
911
911
3698
1032
07-18-86
167
224
5201
114
9291
3623
2876
622
3198
541
08-28-86
208
637
4996
1188
7865
3725
2990
1390
3700
09-19-86
229
307
4921
1393
7126
3346
2665
1285
3450
10-22-86
262
108
4291
2059
7595
3607
154
294
2301
966
890
2835
154
11-23-86
294
179
4231
1271
6419
3435
62
120
2124
663
656
2139
783
12-10-86
311
179
2704
82
10270
4490
20
15
2102
6%
615
2566
847
02-20-87
383
411
3799
1472
8787
4109
343
463
1934
1005
808
2716
1211
03-17-87
408
147
2491
715
7494
3548
51
46
1686
582
466
2149
736
04-29-87
451
0.1
0.2
0.1
0.2
0.1
0.1
0.2
0.8
05-29-87
481
118
2129
1420
6865
2934
79
159
1589
551
442
2001
685
06-23-87
506
96
1553
588
5018
2145
37
59
1267
453
356
1564
530
292


159
the hydraulic gradient. Conversely, solutes which are more
highly sorbed move more quickly towards the pumping wells
as a result of increased convective flow of the mobile phase
(ie., groundwater). With these caveats in mind,
interpretation of the field data becomes very complex.
The distribution of benzene at the field site is
highest toward the swamp (well UF-3W) as is shown in Figure
5-28. The major concentrations of benzene seem to have
migrated substantially faster than the other compounds.
This is expected from the relatively low retardation factor
demonstrated in the laboratory studies, and also from the
inefficient biodegradation of benzene at high flow, as
determined in the biodegradation column run at 0.680 cm/min.
In this column, only 10% of the benzene was removed, whereas
the branched aromatics were more easily degraded.
Hydrocarbon data from each monitoring well are
presented in Appendix G. Examination of these data
demonstrate that the areal distribution of other aromatic
solutes are less distinct than benzene. Analyses of these
data do not yield a sequential distribution of compounds
suggested by retardation factors found in laboratory
experiments. This results from the increased susceptibility
to microbial attack, and the probability of multiple spill
sites.
Ortho-xylene (Figure 5-29) has a measured retardation
factor of 1.6, which is 20% larger than that of benzene.
However, the areal distribution of o-xylene is much


WELL RAP-2
CATE
DMS
BSE
TCL
EIHBZ
M,P-XYL
O-XYL
isoPBZ
n-PBZ
3,4ET
135TM3
2ET
124TMB
123TMB
06-25-83
144
07-18-86
167
08-28-86
208
09-19-86
229
8
1
6
4
0.3
0.2
0.1
2
10-22-86
262
11-23-86
294
12-10-86
311
01-27-87
359
2
1
1
1
02-20-87
383
03-17-87
408
1
1
04-29-87
451
0.19
0.1
0.08
0.11
0.73
0.04
05-29-87
481
0.25
0.1
0.45
0.2
0.04
0.04
0.44
0.36
0.4
0.3
0.1
06-23-87
506
0
3
0
1
1
0
0
0
0
0
299


37
Figure 4-2. Extent of the hydrocarbon plume at the
field research site as of October, 1986


Table 3-3. Sorption coefficients of selected aromatic
hydrocarbons on low organic carbon soil.
Compound
Kd
average standard deviation
Toluene
0.37
0.12
p-Xylene
0.50
0.10
1,3,5-Trimethylbenzene
1.00
0.16
1,2,3-Trimethylbenzene
0.95
0.11
Source: Schwarzenbach and Westall, 1981.


LOO AMOUNT SORBED
LOO SOLUTION CONCENTRATION
SORPTION o DESORPTION
Freundlich sorption-desorption isotherm for 2-Ethyltoluene
at equilibrium.
207


64
marked by an initial rapid sorption/ and equilibrium
conditions are established within several (4 to 8) hours.
These data are in agreement with Weber et al. (1983) who
stated that sorption reactions with natural sorbents were
generally rapid and not rate limited. Based on these data
an equilibration time of 18 hours was chosen. Eighteen
hours was chosen to maximize the time for sorption yet
minimize the time for losses from the system (ie./ via
diffusion of solutes through the Teflon septum). This was
equivalent to time scales used in previous studies (Chiou et
al. / 1979, 1983; Schwarzenbach and Westall, 1981). Longer
equilibration times were not possible using this
experimental technique since losses in non-soil blanks after
3 days made it difficult to differentiate between sorption
and loss from the system. The equilibration time used in
this study did not guarantee that the sorption process was
complete, but that it was complete to the extent that it
could be accurately measured.
5.4.2 Batch Sorption Isotherm Data
Data for the equilibrium batch sorption isotherms are
presented in Appendix C. Solution concentrations are in
ug/L, and sorbed concentrations are in ng/g. Three models
were fitted to these data using the method of least squares
regression analysis. These models were the linear, linear
with suppressed fit (forced through the origin), and the
Freundlich (log-log transformed). The results of these
analyses for the linear models are presented in Table 5-2


Treatment 1C
Day
Benzene
Toluene
ra,p-xyl
o-Xyl
3,4 ET
0
664
1971
3962
2369
701
623
1605
3266
1934
623
615
1631
3417
2030
653
avg
634
1735
3548
2111
659
std
22
167
299
187
32
%var
3
10
8
9
5
3
339
853
790
2003
398
355
avg
509
1070
std
200
690
%var
39
64
7
0
8
466
397
51
52
336
314
avg
213
193
std
194
166
%var
61
58
1595
983
243
3815
2385
609
60
1843
108
1823
1737
320
1542
577
212
85
33
66
4
142
8
62
1567
82
8
853
23
140
1213
72
53
944
46
55
527
31
77
24
44
,3,5
TMB
2 ET
1,2,4
TMB
1,2,3 DO
TMB mg/L
289
253
1447
604 10.4
261
232
1027
468
258
239
892
408
269
241
1122
493
14
9
237
82
5
4
21
17
102
96
361
145
3.2
262
236
903
403
3.0
203
204
5
325
2.9
189
179
423
291
3.0
66
60
369
108
0.1
35
33
87
37
4.1
25
45
2
78
168
190
9
319
2.5
200
194
5
414
3.0
121
155
14
273
2.4
128
146
8
271
2.6
66
60
4
123
0.3
20
10
39
17
10.0
234


TREATMENT #2G
treatment #2G
day 0
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
237
460
2006
1303
230
397
80
1367
1017
193
386
123
1348
1044
avg
220
414
102
1574
1121
std
19
33
21
306
129
%variance
9
8
21
19
11
treatment #2G
day 3
BNZ
TOL
ETH BZ
m,p-XYL
O-XYL
0
2
0
1
2
0
2
0
13
69
0
2
0
1
2
avg
0
2
0
5
24
std
0
0
0
6
32
%variance
ERR
10
ERR
113
132
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
432
181
170
773
333
20.00
433
161
198
583
363
523
181
231
617
396
463
174
200
658
364
20.00
43
9
25
83
26
0.00
9
5
12
13
7
n/a
3,4ET
135TMB
2ET
1
47
26
12
51
46
3
7
49
25
5
2
18
79
4
71
124TMB
123TMB
[DO]
1
33
4.50
3
85
4.40
0
2
1
40
4.45
1
34
0.05
106
86
1.12
263


278
Column Biodegradation Data
C/Co
ISPBZ
C/Co
NPBZ
C/Co
3,4ET
C/Co
135TMB
C/Co
2ET
C/Co
124TMB
C/Co
123TMB
0.001
0.002
0.005
0.002
0.002
0.002
0.005
0.000
0.001
0.002
0.001
0.001
0.001
0.003
0.000
0.001
0.001
0.001
0.003
0.001
0.001
0.004
0.001
0.003
0.000
0.001
0.001
0.001
0.002
0.002
0.004
0.003
0.006
0.003
0.005
0.014
0.006
0.012
0.009
0.023
0.011
0.025
0.045
0.019
0.035
0.031
0.060
0.039
0.073
0.109
0.052
0.088
0.078
0.131
0.095
0.149
0.172
0.092
0.144
0.128
0.196
0.148
0.216
0.237
0.141
0.199
0.185
0.258
0.202
0.280
0.320
0.227
0.314
0.273
0.336
0.292
0.361
0.368
0.288
0.334
0.327
0.381
0.340
0.399
0.373
0.300
0.345
0.340
0.391
0.357
0.419
0.401
0.325
0.371
0.363
0.414
0.374
0.434
0.420
0.355
0.397
0.388
0.433
0.404
0.451
0.435
0.361
0.407
0.395
0.442
0.408
0.458
0.470
0.415
0.452
0.439
0.480
0.455
0.503
0.414
0.360
0.395
0.387
0.427
0.402
0.447
0.422
0.367
0.402
0.390
0.430
0.394
0.448
0.445
0.392
0.421
0.416
0.454
0.429
0.469
0.441
0.393
0.399
0.413
0.452
0.420
0.469
0.391
0.340
0.383
0.375
0.416
0.389
0.444
0.436
0.382
0.449
0.407
0.448
0.405
0.473
0.469
0.424
0.456
0.446
0.485
0.462
0.502
0.345
0.282
0.340
0.328
0.371
0.305
0.393
0.486
0.428
0.479
0.457
0.498
0.471
0.508
0.469
0.418
0.456
0.437
0.475
0.495
0.488
0.483
0.433
0.477
0.452
0.490
0.465
0.501
0.513
0.463
0.493
0.481
0.519
0.488
0.531


O o / o
CHLORIDE
PORE
+
VOLUMES
123T RJK fET f/LBENZE NE


ug ¡NT / gram dry v/Blght soil
D AV S
TRT 2A + TRT 2B o TRT 2C
Figure 5-22 Electron transport activity in biodegradation treatments
2A, 2B and 2C.
145


ACKNOWLEDGEMENTS
My sincere thanks are extended to my commitee chairman,
Dr. Lamar Miller, for his insight and support during this
research. Special thanks are also extended to my co-
chairman, Dr. Joseph J. Delfino, for his guidance and
thoughtful criticism. I would also like to thank Dr. Paul
Chadik, Dr. Peter Nkedi-Kizza and Dr. Daniel Spangler for
their generous assistance in the design and interpretation
of these experiments. My thanks also go to Dr. Suresh Rao
for his probing questions and criticisms and for the kind
use of his laboratory.
The work presented in this dissertation could not have
been accomplished without the support and assistance of many
of my colleagues. My sincere thanks are extended to Mr.
Norman Cabrera for his valuable assistance with several
laboratory experiments, and to Mr. Gene Killan, Ms. Vicki
Card and Mr. Ben Horenstein for their help in the collection
of field samples and maintenance of the field site. I would
also like to thank Ms. Robin Mitchell for her work on the
microbial analyses, Mr. Jimmy Yeh for his work on GC
analyses, Ms. Linda Lee for her help in setting up the
column studies, and Mr. Bill Davis for his expert assistance
with gas chromatography and quality assurance procedures.
iii


or nitrogen limited. Hydrogen peroxide increased dissolved
oxyge
lab s
condi
shown
hydro
n/ but did not lead to increased hydrocarbon removal in
tudies. Ammonium chloride produced nitrifying
tions. Oxygen augmentation with air and oxygen gas was
to enhance biological removal of aromatic
carbons.
xv


aquifers in Florida with a low organic carbon content
(0.015%). The aquifer was composed primarily of fine to
medium grained sands.
Hydrolysis was not a significant removal mechanism for
the selected aromatic solutes. Equilibrium batch isotherms
and column studies determined sorption coefficients for
aromatic solutes ranging between 0.045 and 0.1 with
retardation values between 1.36 and 2.40. Column
breakthrough curves exhibited minimal effects of adsorption
non-equilibrium. Sorption isotherms were linear through the
concentration range tested and no significant hysteresis was
noted. Partitioning and surface dependent adsorption were
evaluated by regression of column K data with literature
values of K water solubility and first order connectivity
indices. No single model fully described the sorption
process, and the sorption mechanism appeared to be a
combination of several processes. Competitive solute
interactions were not shown to be significant.
Column biodegradation experiments with acclimated
microorganisms were performed at flow velocities close to
those from the contaminated aquifer. Half lives ranged from
0.940 hr for benzene to 0.086 hr for n-propylbenzene at
0.680 cm/min. Branched aromatic solutes were more easily
degraded in column studies.
Batch studies demonstrated the ability of field
microbes to degrade aromatic hydrocarbons to less than 0.5
ug/L given sufficient oxygen. Microbes were not phosphorus
xiv


Treatment IF
1,3,5 1,2,4 1,2,3 [DO]
Day
Benzene Toluene m,p-Xyl o-
-Xyl
3,4 ET
TMB
2 ET
TMB
TMB
mg/L
15
594
274
39
1405
55
110
144
12
216
4.0
463
176
21
1081
41
76
106
8
148
4.5
619
246
30
1570
61
125
161
12
221
5.4
218
68
11
864
34
68
101
4
152
7.8
avg
474
191
25
1230
48
95
128
9
184
5.4
std
159
79
10
275
11
24
25
3
34
1.5
%var
34
42
41
22
23
25
20
37
19
26.9
31
205
75
14
702
8
48
56
3
108
7.2
1
1
4
298
7
62
68
2
141
5.1
349
92
9
873
11
58
81
2
143
7.4
avg
185
56
9
624
9
56
68
2
131
6.6
std
143
40
4
241
2
6
10
0
16
1.0
%var
77
71
45
39
20
11
15
20
12
15.8


treatment #2A
DAY 21
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
170
148
3
952
522
79
132
1
742
463
186
425
1396
830
avg
145
235
2
1030
605
std
47
135
1
273
161
%variance
32
57
49
26
27
Treatment #2A
DAY 34
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
94
104
8
601
355
80
87
9
336
181
45
52
9
325
189
avg
73
81
8
421
242
std
21
22
1
128
80
%variance
28
27
8
30
33
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
204
94
77
250
128
2.30
174
85
72
170
124
2.20
331
138
117
345
192
4.00
236
106
89
255
148
2.83
68
23
20
72
31
0.83
29
22
23
28
21
29.15
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
155
77
66
158
111
2.10
94
45
39
93
56
1.90
81
40
37
81
60
1.80
110
54
47
111
76
1.93
32
16
13
34
25
0.12
29
30
28
31
33
6.45
246


1,2,4-Trimethylbenzene Sorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
685
70
1072
140
245
7
531
62
64
4
107
0
8
9
13
6
962 .2
28.4
1565.2
93.24
57.9
57.9
156.5
a
10.8
0.14
31.4
a
4.9
0.5
15.7
a
2.4
0.35
6.26
a
1.3
0.28
3.13
a
amount
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentration
387
133.5
2.13
3.03
286
98.7
1.99
2.73
43
14.8
1.17
2.03
5
1.7
0.24
1.11
603
208.0
2.32
3.19
98.6
34.0
1.53
2.19
20.6
7.1
0.85
1.50
10.8
3.7
0.57
1.20
3.86
1.3
0.12
0.80
1.83
0.6
-0.20
0.50
a
n = 1
208


TREATMENT #2D
treatment #2D
day 0
BNZ
TOL
ETH BZ
m,p-XYL
O-XYL
1238
7083
227
6498
3185
1826
10286
330
9320
4225
1350
7355
226
6903
3353
1155
6310
91
6246
3048
avg
1392
7759
219
7242
3453
std
260
1509
85
1223
459
%variance
19
19
39
17
13
treatment #2D
day 2
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
748
3946
191
3479
1937
761
4083
76
3660
1909
743
3871
71
3205
1699
avg
751
3967
113
3448
1848
std
8
88
56
187
106
%variance
1
2
49
5
6
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
1443
509
415
1899
689
7.50
2153
769
624
2805
1036 '
1576
569
462
2031
765
1432
527
428
1941
758
1651
594
482
2169
812
7.50
295
104
84
370
133
0.00
18
17
17
17
16
0.00
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
1026
332
370
1085
550
8.80
732
295
246
1016
11
8.80
550
205
192
757
315
8.00
769
277
269
953
292
8.53
196
53
75
141
221
0.38
25
19
28
15
76
4.42
253


318
Windholz, M. (1976). The Merck Index, 9th Edition. Rahway, NJ:
Merck Co.
Woodburn, K. (1985). Thermodynamics and Mechansims of Sorption
for Hydrophobic Organic Compounds on Natural and
Artificial Sorbent Materials. Ph.D. Dissertation,
University of Florida.


1J
0
o
\
(j
1 -
0.9 -
OA -
0.7 -
6
Breakthrough curve for 2-ethyltoluene in column biodegradation
experiment performed at a flow rate of 1 mL/min.
288


3
sandy clay and sandy clay loams, all of which are noted for
their relatively high permeabilities (Fernald and Patton,
1984). The sandy deposits of the Pliocene and Pleistocene
ages common to Florida are also marked by low organic carbon
and clay content (Fetter, 1980), resulting in high
permeability and low sorptive capacity.
Given the magnitude of this problem, the transport and
environmental reactions of dissolved gasoline components in
shallow sandy aquifers is an important area of study. This
is particularly true of the aromatic constituents of
gasoline, owing to their toxicity, concentrations in
gasoline and their high aqueous solubility. Gasoline
products which are released into the vadose zone travel
downward under the influence of capillary and gravitational
forces. When the sorptive capacity of the soil is exceeded,
gasoline moves onto the groundwater table, where it spreads
laterally across the top of the saturated zone. This is a
3
result of the density of gasoline (0.7-0.75 g/cm ).
Gasoline components partition into the water to the extent
of their water solubility, and move in the direction of the
water table gradient.
Physical, chemical and biological factors must all be
considered in the determination of the fate and transport of
dissolved gasoline hydrocarbons in groundwater. The
interaction of these factors may be conveniently examined in
the context of a generalized mass transport equation. A
one-dimensional form of this equation is


65
Table 5-2. Regression parameters for the analysis of
average values
sorption data
of equilibrium
with the linear
batch
model
isotherm
Compound
ii
ii
ii
ii
ii
(0 11
2 II
II
II
C b
(uS?)
===v==
stdC y-
mt ,
std
2
r
Benzene
14
950
0.066,
0.005
1.5,
4.28
0.914
Toluene
14
4200
0.049,
0.010
10.9
, 65.6
0.694
m/p-Xylene
16
4300
0.095,
0.005
3.4,
28.7
0.961
o-Xylene
16
2500
0.097,
0.004
3.1,
10.8
0.979
3 or 4 ETe
11
935
0.087,
0.012
3.8,
12.6
0.861
1,3,5TMBf
11
460
0.142,
0.008
1.6,
3.92
0.973
2-ET9
11
373
0.106,
0.011
0.81
, 4.66
0.910
1,2,4-TMB
10
1600
0.131,
0.006
4.6,
10.6
0.981
1,2,3TMB1
10
558
0.124,
0.010
1.7,
6.10
0.951
3number of data points
^maximum concentration
c
standard deviation
dy-intercept
e3 or 4 Ethyltoluene
^1,3,5-Trimethylbenzene
92-Ethyltoluene
bl,2,4-Trimethylbenzene
1l,2,3-Trimethylbenzene


89
Nkedi-Kizza et al. (1987) presented a method to assess
the asymmetry in a BTC by measuring the difference in the R
values calculated by the pore volume method (R }, from
pv
those calculated from the area above the BTC (R ). An
cl
empirical index for sorption nonequilibrium (ISNE) was
defined as:
ISNE = [(R R ) / R ] [5.2]
a pv aJ .
where R is the retardation factor calculated from the area
a
above the BTC and R is the retardation factor calculated
pv
by evaluation of the number of pore volumes required for the
column effluent to equal 0.5 of the influent concentration.
For ISNE equal to zero, R is equal to R and for ISNE
^ a pv
equal to 1 R is much less than R The calculated
a pv
values of ISNE for all 12 compounds in this study are
presented in Table 5-12. Based on these data, the solutes
in this study do not show an appreciable amount of sorption
non-equilibrium. These solutes are not strongly sorbed, and
thus are not expected to exhibit a large degree of non
equilibrium. Regression of R^ values with ISNE values
2
yielded a model with a r value of 0.57. Statistical
analysis of this regression model indicated that the model
was useful for predicting ISNE from R values at the 0.01
cl
significance level.
The cause of nonequilibrium may be the result of
several physical or chemical phenomena which limit the rate


Finally, this work would not have been possible without
the love, support and friendship provided by ray wife Beth.
I also thank my family for their financial support during my
many years of schooling.
This research was funded through a research grant from
the Institute for Food and Agricultural Sciences.
IV


o
O
\
o
75
7.2
U
7
0.9
05
0.7
O.Q
05
0A
05
0J2
0J
0

f
HB~&SH
f
/
A~
Â¥
r
Jf
,Â¥
/
/ f
i i
i /
t /
i£+-Lr
T
2
PORE VOLUMES
a CHLORIDE + M.P-XVLENE
T~
4
220


54
from the 1 mL/min columns were collected and analyzed as
described in section 4.8. Breakthrough curves for a non
retained solute were obtained with tritiated water (0.01 uci
3
H for 0.90 ml/hr columns) or CaCl2 (1 ml/min columns).
3
Analyses of H^O effluents were performed on a Delta 300
model 6890 Liquid Scintillation Counter (Cearle Analytical)
using Scintiverse II scintillation cocktail (Fisher
Scientific). Columns operated for biodegradation
experiments were set up in the same manner as the sorption
columns. Solute containing water was filtered through 0.45
um membrane filters (Gelman Metricel) to remove
particulates. A standing microbial population was developed
in the columns operated at 1 ml/min by inoculation with
water from well OHM-4.
4.11.2 Calculation of Rate Constants
Rate constants for the biological degradation of
aromatic solutes from column breakthrough curves were
determined by application of the first order rate equation
to the breakthrough curve data at steady state. Microbial
degradation processes are often assumed to be first order
(Bossert and Bartha, 1984). Substitution of equation [3.18]
into equation [3.11] incorporates the degradation term into
the one dimensional mass transport equation:
= D, 92C/ 3x2 v 3C/ 3x k C
h
R 3C/ 3t
[4.2]


Table 3-2. Summary of adsorption data for aromatic hydrocarbons.
Percent Benzene Toluene o-Xylene
Organic
Soil Content 1/n K 1/n K 1/n K
Silty Clay
16.2
1.272
3.23
1.008
3.52
0.947
11.03
Sandy Loam
10.8
1.298
0.583
1.002
2.69
0.707
4.77
Silty Clay
1.7
1.366
0.003
Silt Loam
1.0
1.51
0.028
0.996
0.931
1.098
0.62
Silty Clay Loam
2.6
0.89
2.4
Silty Clay Loam
1.8
0.94
1.8
Al saturated
MontmorilIonite
0
1.08
30.9
Cu saturated
Montmorillonite
0
0.99
4.4
Adapted from Brookman et al.,
1985.


138
5.10.3 Treatments 2D and 2E
These data assessed the effect of addition on the
microbial community. These were essentially repeats of
treatments 1C and IF. The addition of 58 mg/L
(treatment 2D) produced a 2 day lag phase for benzene,
toluene, m,p-xylene and 2-ethyltoluene relative to no H
treatment (Figure 5-19). The extent of treatment was
comparable to treatment 2A (air addition). The DO profiles
are shown in Figure 5-20. The lag in bioactivity was
paralleled by a lag in consumption of DO for the same 2 day
period. The addition of NH^Cl in treatment 2E produced a
toxic effect, and the hydrocarbon data were equivalent to
the sterile control losses. However, the DO profile (Figure
5-20) showed consumption of dissolved oxygen, and this
implied some microbial activity. The INT data also
demonstrated increased bioactivity (Figure 5-21) following a
lag of at least two days. Microbial activity decreased after
14 days. This decreased INT reduction was not noted for
treatment 2D. Again, there was microbial activity and O^
consumption without substantial reduction in hydrocarbon
concentrations.
5.10.4 Treatments 2G, 2H, 21.
These treatments showed the effect of the addition of
oxygen gas to the microcosms. One consequence of the oxygen
sparging was to reduce the initial concentrations of
hydrocarbons from a total of 26,000 ug/L to 5000 ug/L.
Benzene and toluene are preferentially removed, owing to


165
Table 5-27. Microbial populations from samples
collected during installation of
monitoring wells RAP-5 and RAP-6,
September, 1986.
CFU/gdw x 106
Depth, RAP-4 RAP-5
feet avg. std. dev. avg. std. dev. Comments
2.0
a
ns
ns
4.9
0.34
3.0
8.9
0.96
3.2
0.25
4.0
4.1
0.22
3.1
0.82
5.0
ns
ns
8.4
0.31
6.0
4.2
0.11
2.0
0.85
Saturated
zone
a
no
sample


116
Table 5-17. Biodegradation rate constants, half-lives and
correlation coefficients for the fit of
biodegradation experiment #1 data to a
first order rate equation.
Treatment
Benzene
Toluene
m,p-Xylene
o-Xylene
3,
, 4-ET
1A
k
0.233
0.219
0.295
0.282
0.
. 235
2.97
3.17
2.35
2.46
2,
. 95
2
r
0.779
0.844
0.993
0.995
0 ,
.989
IB
k
0.233
0.262
0.190
0.208
0,
.135
th
2.97
2.65
3.65
3.33
4.
.47
2
r
0.887
0.901
0.909
0.876
0.
.928
1C
k
0.242
0.261
0.271
0.284
0,
.227
th
2.86
2.66
2.56
2.44
3.
. 05
2
r
0.970
0.994
0.913
0.975
0.
.967
ID
k
0.212
0.254
0.216
0.183
0.
. 157
th
3.27
2.73
3.21
2.79
4.
. 42
2
r
0.942
0.920
0.753
.868
0.
.921
IE
k
0.154
0.200
0.200
0.076
0.
. 171
th
4.50
3.47
3.47
9.17
4 .
.05
2
r
0.992
0.952
0.753
0.969
0.
,936
IF
k
0.038
0.107
0.185
0.036
0.
. 134
th
18.3
6.48
3.75
19.47
5.
,17
2
r
0.885
0.945
0.706
0.917
0.
.897
1G
k
0.010
0.013
0.020
0.017
0.
, 030
th
69.31
51.7
35.55
40.29
23.
, 42
2
r
0.370
0.401
0.625
0.584
0.
, 724


112
ammonium chloride on the biodegradation of the aromatic
compounds in the Lake Alfred aquifer, and to assess the
degradation of these compounds in the presence of dissolved
oxygen. The average concentrations of aromatic hydrocarbons
in the microcosms of experiment #1 over the time course of
the experiment (31 days) are shown in Table 5-16. A
detailed presentation and statistical analysis of these data
are presented in Appendix E. These data were fit to several
rate equations. Zero order, first order, an empirically
based first order rate equation (Thomas-slope method),
second order, and a mixed order (zero to first order) rate
equations were fit to the biodegradation data. Only the
first order rate equations gave adequate fit to the data,
based on an analysis of the coefficients of determination
for the various models (Global F-test, 0.05 significance
level). The results of linear regression analysis of the
data to the first order models are shown in Table 5-17
(first order) and Table 5-18 (Thomas-slope). In both tables
the rate constants, calculated half lives and the
coefficients of determination for each solute under each
treatment condition are presented.
Regression analyses and rate data for both types of
first order rate equations are presented, since neither
method yields coefficients of determination which
consistently provide superior fit to the data. First order
and Thomas slope rate equations each provide adequate fit to
2
the data as evidenced by the r values. In the sections


13
balance considerations. For a flux type inlet boundary
condition (flowing concentrations), Brenner's solution was
applicable provided the column Peclet number was not much
less than five The solution of Lapidus and Amundson (1952)
was recommended to evaluate flux averaged concentrations in
finite laboratory columns or semi infinite field profiles.
3.4 Sorption of Aromatic Compounds
Sorption is a major mechanism in the attenuation of
organic solutes in the saturated zone. Solutes
differentially sorb onto aquifer materials and thus are
retarded in their movement through the subsurface, resulting
in a chromatographic like separation of the soluble
constituents of a plume, with groundwater as the mobile
phase.
Sorption describes the transfer of solutes from a
liquid phase to a solid phase (Miller and Weber, 1984). In
this literature review the liquid phase is assumed to be
water, containing solubilized organic solutes and the solid
phase is the aquifer material under saturated, steady flow
conditions. Sorption is influenced by the physical and
chemical characteristics of the aquifer (ie., soil type,
fraction of organic carbon), and the solute (ie ,
solubility, volatility, density).
Although sorption is a major component in the
attenuation of solutes in the subsurface, the fundamental


treatment #2D
day 21
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
19
11
11
248
905
8
383
1027
327
691
16
12
728
avg
288
538
12
135
589
std
40
377
4
175
426
%variance
14
70
34
129
72
treatment #2D
day 35
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
108
405
5
932
533
254
391
6
41
160
avg
181
398
6
487
347
std
73
7
0
446
187
%variance
40
2
9
92
54
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
5
7
12
5
17
4.80
106
129
119
52
256
2.40
27
81
87
2
146
2.60
46
72
73
20
140
3.27
43
50
45
23
98
1.09
94
69
62
116
70
33.28
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
170
87
71
213
138
1.60
16
7
27
6
35
2.10
93
47
49
110
87
1.85
77
40
22
104
52
0.25
83
85
45
95
60
13.51
255


33
This technique is recommended as an index of g
microbial activity of soil microorganisms (Kle
1971).
Reduction of INT to INT-formazan is a sen
for dehydrogenase activity. The INT-formazan
extracted from sediments and soils by methanol
formazan complex is stable. Trevors et al. (1
high correlation between electron transport sy
and oxygen consumption. Klein et al. (1971) p
rapid and simple procedure for the deterrninat
dehydrogenase activity using INT in soils with
carbon .
3.6 Summary
This literature review has presented some
principles required as a basis for the discuss
experimental work reported in this dissertatio
highlighted some of the important findings rel
dispersion, sorption and biodegradation of aro
compounds in groundwater systems.
eneral
in et al.,
sitive assay
is easily
, and the INT-
982) found a
stem activity
resented a
ion of
low organic
of the basic
ion of the
n and has
ative to the
mat ic


156
biodegradation in the field, where oxygen limitation reduces
the biological removal of hydrocarbons.
The rapid biodegradation of solutes in the batch and
column biodegradation studies supports the hypothesis that
the microbial community in the Lake Alfred aquifer is well
adapted to remove aromatic hydrocarbons from gasoline
sources. In instances where adaptation has occurred,
biotransformations may be so rapid that they are considered
instantaneous relative to the rate of groundwater flow.
This shifts the quantitative prediction of biological
activity from a consideration of biological kinetics to a
consideration of the extent of utilization (Wilson et al.,
1983b). Thus geochemical constraints become the controlling
factors in the biodegradation process. This is the
situation at the Lake Alfred site, where oxygen is the
limiting substance.
5.12 Field Data
It is beyond the scope
describe all the field data
months. Rather, the major
will be correlated with sel
These topics include analys
field-scale solute transpor
microbial populations.
of this work to thoroughly
collected during the past 18
findings of this dissertation
ected aspects of the field data,
is of field-scale dispersion,
t and the enumeration of


117
Table 5-17. Continued.
Treatment l,3,5-TMBb 2-ET 1,2,4-TMBC
l,2,3-TMBe D0f
1A
k
th
0.223
3.11
0.207
3.35
0.249
2.78
0.230
3.01
2
r
0.935
0.982
0.989
0.986
0.013
IB
k
th
0.145
4.78
0.102
6.80
0.193
3.59
0.126
5.50
2
r
0.936
0.937
0.939
0.933
0.093
1C
k
th
0.097
7.17
0.146
4.75
0.214
3.24
0.133
5.21
2
r
0.927
0.994
0.777
0.990
0.111
ID
k
th
0.034
20.21
0.052
13.30
0.172
4.03
0.033
21.00
2
r
0.775
0.982
0.632
0.875
0.0
IE
k
th
0.053
13.05
0.065
10.75
0.164
4.23
0.052
13.46
2
r
0.946
0.946
0.591
0.931
0.005
IF
k
th
0.043
16.16
0.036
19.42
0.183
3.79
0.032
21.66
2
r
0.820
0.868
0.673
0.799
0.042
1G
k
th
0.030
23.50
0.026
26.36
0.030
23.11
0.023
30.27
2
r
0.725
0.683
0.728
0.655
0.429
a3,4-Ethyltoluene
1,3,5-Trimethylbenzene
C2-Ethyltoluene
dl,2,4-Trimethylbenzene
0
1,2,3-Tnmethylbenzene
^Dissolved oxygen


WELL P 5
EME
DMS
EENZ
TCL
ethBz
m,p-XÂ¥L
oXYL
02-01-86
0
9322
2414
1095
02-27-86
26
591
6753
1855
12360
5301
03-07-86
34
113
6159
1883
14826
6219
03-20-86
47
133
8214
1478
9630
4002
03-27-86
54
282
10505
2603
16645
7041
04-25-86
82
16360
2497
20573
8633
05-23-86
111
19037
3074
19134
8246
06-25-86
144
174
11110
4080
99%
4498
07-18-86
167
5154
2101
12240
4519
08-28-86
208
1823
09-19-86
229
677
1455
1063
3874
1767
10-22-86
262
39
2695
2904
10256
4994
10-25-86
265
33
1063
1169
4760
2315
10-28-86
268
97
2000
2079
7754
3931
11-04-86
275
84
1668
2000
7553
3589
11-07-86
278
9
306
626
5092
2866
11-19-86
290
24
822
1013
4544
2152
11-23-86
294
26
660
767
3602
1762
12-10-86
311
33
931
1294
6646
2%9
01-27-87
359
1281
1857
1827
8130
3179
02-20-87
383
19
17
2057
1962
03-17-87
408
4
55
42
1187
541
04-29-87
451
0.2
0.1
05-29-87
481
14
9
41
23
06-23-87
506
10
13
228
113
LsEBZ
n-PBZ
3,4ET
135TMB
2ET
124TM3
1231M3
7341
2629
2474
8562
2601
6215
15%
1685
7033
1980
7033
1%0
2020
7900
2019
3635
1044
1044
3950
1113
7427
2141
2003
8234
2279
6994
1970
1724
7397
1881
5869
17%
1555
6379
1474
5883
1648
1622
5923
1836
6348
1277
1668
7119
1231
2580
2825
1650
1145
3565
1880
176
563
3720
1587
1344
4677
1474
81
257
1999
908
733
2510
791
162
470
3471
1517
1159
4146
1307
161
516
3840
1587
1339
4645
1477
104
133
3412
1490
1300
4166
1564
83
164
2145
998
974
2449
824
68
139
2201
687
607
1920
692
73
156
2219
741
592
2568
834
171
408
2935
1066
979
4276
1277
1.36
1402
662
416
1595
653
5
4
343
121
86
417
136
0.1
0.8
0.1
1
4
36
9
12
25
52
1
3
92
38
35
94
52
296


C / C o
PORE VOLUMES
CHLORIDE + 2-ETtr/LEOLUENE
225


CHAPTER III
LITERATURE REVIEW
3.1 Introduction
This chapter presents a review of the pertinent
literature for the reactions of gasoline derived aromatic
hydrocarbons in groundwater. The major areas of discussion
are the environmental effects of gasoline contamination, the
use of advection-dispersion transport models, the sorption
of aromatic compounds to aquifer materials, and the
biodegradation of aromatic compounds in groundwater systems.
3.2 Environmental Effects of Gasoline Contamination
Gasoline is a complex mixture of many hydrocarbon
compounds. A typical gasoline contains between 150-250
identifiable hydrocarbon components (Sanders and Maynard,
1968) consisting of alkane, alkene, aromatic and napthene
hydrocarbons. Automobile gasolines are comprised of C^-C^
hydrocarbons with boiling points in the range 32-210 C. Un
leaded gasolines contain greater.concentrations of aromatic
hydrocarbons to provide for anti-knock protection and
branched hydrocarbons to increase octane ratings (Moore and
Moore, 1976).
/


5-21 Biodegradation rate constants, half lives and
correlation coefficients for the fit of
biodegradation experiment #2 data to the
Thomas-slope rate equation 135
5-22 First order biological rate constants and
half-lives of aromatic hydrocarbons for the
biodegradation column with flow at 0.90 mL/hr.. 149
5-23 First order biological rate constants and
half-lives of aromatic hydrocarbons for the
biodegradation column with flow at lmL/min 151
5-24 Microbial populations in a soil core taken
south of the paint shop (bldg 54), June, 1986.. 163
5-25 Microbial populations in a soil core taken
in the spray field June, 1986 163
5-26 Microbial populations in a soil core taken
south of the pump house (bldg 12) july, 1986... 164
5-27 Microbial populations from samples collected
during instasllation of monitoring wells
RAP-5 amd RAP-6, September, 1986 165
5-28 Water chemistry parameters from selected
monitoring wells at Lake Alfred CREC, 1986 166
ix


Toluene Sorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
6.1
0.24
9.9
1.5
28.9
2.3
49.3
a
67
17.2
99
a
166.3
18.9
261
a
2886
504
4000
a
3813
79
4069
140
209
16
407
14
52
a
81
3
26
a
41
1.2
10
1.2
16
0.56
1.3
0.26
8
0.18
4049
155
4566
565
3118
6.8
457
a
4.7
1.2
47
a
amoun t
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentrat ion
3.8
1.3
0.13
0.99
20.5
7.1
0.85
1.69
31.5
10 .9
1.04
1.99
95.1
32.8
1.52
2.42
1114
384
2.58
3.6
257
88.5
1.95
3.61
198
68.3
1.83
2.61
29.5
10.2
1
1.91
14.7
5.1
0.71
1.6
6.4
2.2
0.34
1.21
1.7
0.6
-0.22
0.9
517
178
2.25
3.66
138
48
1.68
2.66
4
1.4
0.14
1.66
a
n = 1
19 0


132
first order model are shown in Table 5-20 and via the Thomas
slope method in Table 5-21. Examination of correlation
coefficients from the fit of the Thomas slope model to the
data in this experiment suggest that rate constants from
this model selectively give an adequate estimate of the
biological degradation constant.
5.10.1 Treatment 2A
This is a repeat of treatment 1A. The general trends
were the same and the rate constants were equivalent. Again
m,p-xylene and 1,2,4-trimethylbenzene showed rapid loss as
noted in treatment 1A. The extent of degradation was not as
complete as in treatment 1A. This may be the result of the
increased concentration of toluene (7759 ug/L vs 2171 ug/L)
and the concentration of m/p-xylene (7241 ug/L vs 4823 ug/L
in 1A). There was a rapid loss in DO over the first two
days, indicating microbial activity.
5.10.2 Treatment 2B
This is a repeat of treatment ID. The half lives were
generally higher, reflecting a decrease in hydrocarbon
removal. There was a pronounced lag phase of 8 days for
benzene (Figure 5-18). The lag in degradation for toluene,
o-xylene, m,p-xylene and 2-ethyltoluene was two days. The
DO profile in this treatment was consistent with that of 2A
indicating 0^ removal during the first several days.
However, microbial activity was increased over treatment 2A.
This microbial activity did not result in significant
degradation of hydrocarbons.


307
Bedient, P.B., R.C. Borden, and D.I. Leib. (1985) Basic
Concepts for Ground Water Transport Modeling. In Ground
Water Quality. C.H. Ward, W. Giger,. and P.L. McCarty
(eds): New York: John Wiley & Sons, Inc., pp. 512-530.
Biggar, J.W., and D.R. Nielsen. (1962) Some Comments on
Molecular Diffusion and Hydrodynamic Dispersion in Porous
Media. Journal of Geophysical Research 67(9): 3636-3637.
Black, C.A. (1965). Methods of Soil Analysis. Monograph 9.
Madison, Wisconsin: Amer. Soc. Agron.
Blumer, M., J.M. Hunt, J. Atena, and L. Stein. (1973).
Interaction between Marine Organisms and Oil Pollution.
Springfield, VA: National Technical Information Service,
EPA R3-73-042.
Bossert, I., and R. Bartha. (1984). The Fate of Petroleum in
Soil Ecosystems. In Petroleum Microbiology. R.M. Atlas
(ed): New York: Macmillan Pub. Co., pp. 435-473.
Boucher, F.R., and G.F. Lee. (1972). Adsorption of Lindane and
Dieldrin Pesticides on Unconsolidated Aquifer Sands.
Environ. Sci. Technol. 6(6): 538-543.
Bouwer, E.J., and P.L. McCarty. (1984). Modeling of Trace
Organics Biotransformation in the Subsurface. Ground
Water 22(4): 433-440.
Brenner, H. (1962). The Diffusion Model for Longitudinal
Mixing in Beds of Finite Length: Numerical Values.
Chemical Engineering Science 17: 229-243.
Briggs, G.G. (1981). Theoretical and Experimental
Relationships Between Soil Adsorption and Octanol-Water-
Partition Coefficients. J. Agrie. Food Chem. 29: 1050-
1059.
Britton, L. (1985). Feasibility Studies on the Use of Hydrogen
Peroxide to Enhance Microbial Degradation of GasolineT
Washington, D.C.: American Petroleum Institute
Publication No.4389.


Treatment 1A
Day
Benzene
Toluene
m/P~xyl
o-Xyl
3,4 ET
15
0
14
19
25
17
0
14
62
72
12
avg
0
14
41
48
15
std
0
0
21
24
2
%var
1
52
49
16
31
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
avg
0
0
0
0
0
std
0
0
0
0
0
%var
0
0
0
0
0
1,3,5 1,2,4 1,2,3 DO
TMB 2 ET TMB TMB mg/L
8
35
12
11
2.7
0
32
18
15
2.7
4
33
15
13
2.7
4
1
3
2
0.0
100
4
23
14
0.0
0
0
0
0
4.6
0
0
0
0
4.5
0
0
0
0
3.2
0
0
0
0
4.1
0
0
0
0
0.6
0
0
0
0
15.6
231


Ill
measurable changes in the concentrations of these solutes
resulting from the addition of hydrogen peroxide. The
absence of aromatic hydrocarbon removal in this experiment
should not imply that is an ineffective method of
oxygen augmentation. The dissolved oxygen levels did
increase in this experiment. However, removal of
hydrocarbons, abiotically, via oxidation of the aromatic
molecules appeared not to be significant. This experiment
was not designed to measure the microbial removal of
hydrocarbons. The time scale of this experiment was too
short to observe a microbial effect. Batch biodegradation
experiments (sections 5.8 and 5.9) demonstrated that several
days were required for microbial adaptation to hydrogen
peroxide.
The data from this experiment simply confirm that there
are sufficient catalysts available to mediate the conversion
of to C>2 Application of H 2 2 t0 t*ie La^e Alfrec^
aquifer is underway. Preliminary data indicate that
dissolved oxygen levels were increased, and that
hydrocarbons concentrations were reduced following an
adaptation period.
5.9 Batch Biodegradation Experiment #1
Two separate batch biodegradation experiments were
pertormed. The first experiment was designed to investigate
the effect of various combinations of hydrogen peroxide and


a
Figure 5-20. Concentration vs. time for dissolved oxygen in biodegradation
treatments 2A, 2B and 2C.
140


41
mass range
Temp 1
Temp 2
Rate
Hold time
Cryofocus time
Pre-cool
45-450 amu
30 C
280 C
5 C/min
10 minutes
5 minutes
2 minutes
4.5.2 GC Analyses
Hydrocarbon analyses were performed on a Perkin Elmer
model 8410 gas chromatograph with a flame ionization
detector and microprocessor data system. Samples were
concentrated by purge and trap with a Tekmar LSC/ALS system
employing a modified version of EPA method 602. Analytical
separation was achieved with a 0.53 mm i.d., 30 meter long,
fused silica Megabore DB-1 (100% methylpolysiloxane) column
(J & W Scientific) with a 3 urn film thickness.
Benzene, toluene, ethylbenzene, o-xylene and m,p-xylene
were quantified using the internal standard method (1,4
dichlorobenzene) during August and September 1986 for
monthly analysis of field samples and for day = 0 hydrolysis
ampules. After this date, eight isomers of C^H^,, were
identified and confirmed by analysis of individual standards
and were quantified in all chromatograms along with BTEX
(benzene + toluene + ethylbenzene + m,p,o-xylene) compounds.
The internal standard was changed from 1,4-dichlorobenzene
to chlorobenzene to avoid co-elution problems. A complete
description of this analytical method and a summary of the
quality control parameters for this method are in Appendix
A.


33
~\ 1 1 1 r 1 r i i 1 i i i 1 i
2J 23 2J5 2.7 23 3J 33 33 3.7
LOO Kow
Figure 5-10. Regression equations for several models describing the
relationship between K0c and Kow: (a) Curtis et al., 1985,
(b) Schwarzenbach and Westall, 1981, (c) this study, (d) Briggs,
1981 and (e) Chiou et al., 1983.
o


from 0.49 for toluene to 0.142 for 1,3,5-trimethylbenzene .
It was concluded that the sorption process was reversible in
these studies with no significant hysteresis.
Column sorption experiments were performed under
saturated steady flow conditions. Sorption coefficients
from batch isotherm studies and column sorption studies were
closely matched. The average dispersion in these columns
2
was 0.044 cm /min with a standard deviation of 0.029
2
cm /minute. Retardation factors were determined for all C^-
C_ aromatic compounds from the multicomponent system of
dissolved aromatic hydrocarbons in well water. Retardation
factors ranged from 1.36 for benzene to 2.40 for n-
propylbenzene. These data demonstrated the relatively low
retardation of aromatic solutes by the aquifer materials.
The flow velocity used in the column experiments (0.680
cm/min) was close to seepage velocities measured at the
field site (0.02-0.38 cm/min). The column breakthrough
curves (BTC) exhibited some non-equilibria as a result of
slow sorption kinetics, and this process may also affect the
transport of solutes in the field.
The influence of competing solutes was investigated by
comparing retardation values for benzene in a single solute
system with the breakthrough curve for benzene in the
multicomponent system. The retardation factors for benzene
in both column systems were similar (1.36 vs. 1.40). Solute
competition for sorbing sites was not a significant factor


108
competitive sorption effect is operating in the mixed solute
sample, then benzene as a single solute should show
increased sorption. Lack of sorption increase indicates
that competitive sorption between solutes was not important
in this experimental system although this may not be the
case in portions of the aquifer with residual concentrations
of gasoline.
5.8 Evaluation of Hydrogen Peroxide Reactivity
Hydrogen peroxide is known to be a viable method of
increasing the dissolved oxygen in aquifer systems (Britton,
1985, TRI Report, 1982). The purpose of this experiment was
to evaluate the reaction kinetics and the extent of
conversion of hydrogen peroxide to 0^ in the Lake Alfred
aquifer system.
Initial experiments with distilled deionized water and
known additions of dilute hydrogen peroxide showed no
increases in dissolved oxygen. Even after addition of 5 mL
of 50% hydrogen peroxide to the reaction flask, no increase
in dissolved oxygen was noted over a 45 minute interval.
The titer of the 50% stock solution (49.7%) was confirmed by
titration with potassium permanganate. These data indicated
the stability of hydrogen peroxide in the absence of a
catalyst.
The reaction of hydrogen peroxide in filter sterilized
Lake Alfred water was investigated to assess the


CHAPTER II
OBJECTIVES
The main objectives of this study were:
(1) To evaluate the sorption coefficients for 12
selected aromatic hydrocarbons found in water at the Lake
Alfred research site, employing batch isotherms and soil
columns;
(2) To determine the rates of hydrolysis of the 12
selected aromatic hydrocarbons;
(3) To determine the rates of biodegradation of the 12
selected aromatic hydrocarbons under simulated field
conditions, and after treatment with hydrogen peroxide,
oxygen gas and ammonium chloride;
(4) To determine the most appropriate predictive model
for sorption of the 12 selected aromatic hydrocarbons in a
sandy surficial aquifer in Florida;
(5) To correlate molecular properties of the selected
aromatic hydrocarbons with sorptive and biological
parameters;
(6) To evaluate field data based on the laboratory
measurements of sorption and biodegradation and
(7) To extrapolate the laboratory data for application
of aquifer remediation practices.
6


44
concentration owing to sorption, and to more closely
simulate natural aquifer conditions.
Vials used in sorption experiments were equilibrated at
room temperature (20 + 2 C) on a rotary tumbler at
approximately 20 rpm for 18 hours, and then centrifuged at
800 G for 30 minutes. Samples were analyzed by purge and
trap/gas chromatography. Vials used in the batch sorption
kinetic rate study were sampled at 1, 2, 4, 8, 16, 24, 36
and 48 hours.
4.7.2 Desorption experiments
Desorption experiments were conducted subsequent to a
sorption experiment. Following centrifugation and sampling
for sorption losses, approximately 10 mL of supernatant were
removed and replaced with hydrocarbon free water (Well RAP-
2). The vials were re-equilibrated for 24 hours on the
rotary tumbler, centrifuged and sampled. Each vial was only
desorbed one time. These experiments were not designed to
calculate desorption isotherms or test isotherm
nonsingularity.
4.7.3 Calculation of Sorption Coefficients
The amount of solute sorbed to the aquifer material (ng
solute/gram soil) was calculated by determining the
difference between the solution concentration of the non
soil blanks and the soil containing vials. The amount of
solute lost was divided by the solution to soil ratio to
normalize the data to a ng/gram basis. Sorption
coefficients were calculated by fitting isotherm data to
three models; linear, linear with intercept forced through


CHAPTER I
INTRODUCTION
Groundwater contamination is a topic of great
scientific interest and public concern. Groundwater
provides approximately 100 million people with potable water
in the United States (Hoag and Marley, 1986) and nearly
every state contains some number of contaminated wells
(Barbash and Roberts, 1986). The sources of groundwater
contamination are numerous. These include seepage from
lagoons and impoundments, landfills, agricultural and
silvicultural practices, accidental spills and leaking
storage tanks and transfer equipment.
Gasoline and petroleum products are some of the most
common groundwater pollutants. The potential magnitude of
this problem is evident from the volume of petroleum used in
the United States. Approximately 110 billion gallons of
motor fuels are stored underground each year, in an
estimated 1.4 million underground storage tanks, 85% of
which are unprotected steel tanks with finite lifetimes
(Hoag and Marley, 1986). It is expected that 10 to 30% of
these tanks may leak (Dowd, 1984).
Gasoline contamination of groundwater in Florida is a
particularly serious problem. This results from the
confluence of three factors: the large number of petroleum
storage tanks in the state, the reliance on groundwater
1


APPENDIX G
HYDROCARBON CONCENTRATIONS IN MONITORING WELLS AT
THE LAKE ALFRED CITRUS RESEARCH AND EDUCATION CENTER
All concentration values are in units of ug/L. Blank
spaces within the body of each table indicate that the
concentration was below the limit of detection (o.5 ug/L)
of the analytical system. Figure 4-1 shows the location
of each well.
291


62
Table 5-1. Selected physical and chemical Properties
of the Lake Alfred aquifer material.
Parameter
Value
PH
7.4 (0.01M CaCl2)
Particle Density
2.6 g/mL
Water Content (by weight)
24%
Organic Carbon
0.015%
Bulk Density
1.4 g/mL
Particle Size Analysis
clay
1.8%
silt
1.7%
very fine sand
3.0%
fine sand
38.2%
medium sand
47.0%
coarse sand
8.2%
very coarse sand
0.2%


3,4-Ethyltoluene Desorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
305
7.87
812
133
122
10.61
301
17
26
2.77
81
2
5.44
0.12
18
4
4.59
0.93
9
0
145
27.49
935
517.4
21
11.67
93.5
a
5.6
1.39
18.7
a
3
0.07
9.35
a
amount
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentration
507
174.9
2 .24
2.91
179
61.8
1.79
2.48
55
19.0
1.28
1.91
12.56
4.3
0.64
1.26
4.41
1.5
0.18
0.95
790
272.6
2.44
2.97
72.5
25.0
1.40
1.97
13.1
4.5
0.66
1.27
6.35
2.2
0.34
0.97
a
n = l
200


TREATMENT #21
treatment #21
day 0
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
237
460
2006
1303
230
397
80
1367
1017
193
386
123
1348
1044
avg
220
414
102
1574
1121
std
19
33
22
306
129
%variance
9
8
21
19
11
treatment #21
day 2
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
154
250
11
827
661
142
238
9
822
650
avg
148
244
10
825
656
std
6
6
1
2
5
%variance
4
2
10
0
1
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
432
181
170
773
333
20.00
433
161
198
583
363
523
181
231
617
396
463
174
200
658
364
20.00
43
9
25
83
26
0.00
9
5
12
13
7
n/a
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
149
58
68
255
152
9.60
139
59
67
259
152
9.60
144
59
68
257
152
9.60
5
0
0
2
0
0.00
3
1
1
1
0
0.00
269


o
O
\
O
PORE VOLUMES
CHLORIDE + ETHYLBENZENE
219


WELL P 7
EME
IMS
ESSE
TCL
EIHENZ
M,P-XYL
O-XYL
isoffiZ
n-PEZ
3,4ET
135TM3
2ET
1241MB
1231M3
02-01-86
0
99
2183
1719
15783
6139
6708
1655
1497
7457
1665
02-27-86
26
79
3265
1745
15440
6320
6510
1660
1595
7260
1725
03-07-86
34
84
3529
1786
16400
7059
7040
2066
1852
8206
1991
03-20-86
47
128
2623
865
9420
5091
6412
2344
1921
6856
1990
03-27-86
54
143
1731
1088
9001
5130
5319
2020
1793
6019
2177
04-25-86
82
2600
1534
13558
6307
7558
2456
2174
8556
2384
05-23-86
111
3844
1366
13066
6461
7801
2359
2090
9032
2064
06-25-86
144
60
7918
3510
9281
4480
5038
1407
1367
5414
804
07-18-86
167
3197
5572
1181
10616
4304
8165
1697
19%
8417
2163
08-28-86
208
694
5562
2651
1873
3125
1640
3835
09-19-86
229
601
1066
5058
2905
4160
1810
165
5435
2326
10-22-86
262
376
1157
6216
3607
155
421
3854
1730
1580
4970
1659
10-25-86
265
533
902
6152
3342
119
269
3993
1548
1423
5120
1758
10-28-86
268
135
783
585
7333
4195
288
685
6801
2920
3135
8561
2898
11-04-86
275
91
551
538
7090
4128
92
85
4463
1912
1787
5436
2156
11-07-86
278
85
1992
1979
74%
3694
121
379
3001
1289
1078
3494
1086
11-19-86
290
233
288
37%
2058
%
74
2773
32
1202
3307
1210
11-23-86
294
354
651
5448
2903
118
189
4408
1269
1304
4629
1700
12-10-86
311
22
125
4763
2549
17
2993
824
1126
3346
1315
01-27-87
359
205
405
1047
5977
2920
136
365
3780
1478
1003
4531
1556
02-20-87
383
163
499
2182
1617
80
129
1117
689
1929
03-17-87
408
102
314
186
2634
1516
123
139
2805
1204
711
2549
1116
04-29-87
451
1.5
1.5
0.5
1.2
0.4
0.6
0.5
0.6
0.2
05-29-87
481
17
10
150
84
6
6
98
59
45
84
62
06-23-87
506
4
26
15
0.6
1
31
18
16
13.4
25
298


PORE VOLUMES
Breakthrough curve for benzene in column biodegradation
experiment performed at a flow rate of 1 mL/min.
279


105
coefficients are also comparable: 0.916 for this study vs
0.976 for Sabljic (1987). Sabljic (1987) demonstrated that
first order molecular connectivity was a quantitative
measure of the area occupied by the projection of the non
hydrogen skeleton of a molecule. The goodness of fit
between "*"X and Kqc data in this study supports the
hypothesis that sorption depends, at least in part, on some
type of surface interaction.
However, comparison of correlation coefficients between
the three models (K WS and ^X) indicates that neither of
o w
these models completely describe the sorption process (see
Tables 5-13 and 5-15). This suggests that the sorption
mechanism is in reality a combination of processes,
interacting to yield an overall sorption effect. The lack
of any dominant mechanism may be more pronounced in this
study resulting from the low organic carbon content of the
Lake Alfred aquifer material. This serves to reduce the
partitioning effect, by eliminating the sorption substrate
(organic carbon). In addition, Schwarzenbach and Westall
(1981) demonstrated that organic poor sorbents with high
specific surface areas may still exhibit small values,
indicating that surface interactions alone did not
completely account for sorption. These data support the
observation of Voice and Weber (1983) that, given the
heterogeneous nature of natural sorbent materials, sorption
mechanisms of organic solutes in the environment probably
involve many types of interactions. The importance of a


ra/P_Xylene Sorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
3.4
0.2
5.1
a
13.5
1.2
25.7
a
35.8
6.3
51.3
a
80.7
9.2
103
a
943
456
1026
a
4.2
0.2
8.6
a
6.7
0.7
17.1
a
17.2
0.5
42.9
a
37.5
0.3
83.7
1.3
176
12
429
18.4
3028
102
4290
184
3214
107
4232
609
1110
37.9
1893
80
300
9.2
423
a
110
19.5
137
a
34.7
2.1
48
1
amount
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentration
1.8
0.61
0.21
0.71
12.2
4.2
0.62
1.41
15.6
5.4
0.73
1.68
21.9
7.6
0.88
1.71
82 .9
28 .6
1.5
2.63
4.4
1.5
0.18
0.93
10.5
3.6
0.56
1.23
25.7
8.9
0.95
1.92
42.3
16
1 2
2.14
253
87.3
1.94
3.01
1259
434
2 .64
3.63
1081
351
2.54
3.63
783
270
2.43
3.28
123
42.5
1.63
2.63
27 .5
9.5
0.98
2.01
13.3
4.6
0.66
1.63
a
n = 1
193


Table 5-16. Total average hydrocarbon values (ug/L) in the microcosms of batch
biodegradation experiment #1.
Treatment
Compound
Day
1A
IB
1C
ID
IE
IF
1G
Benzene
0
828.35
633.93
663.87
870.85
692.00
692.00
611.33
3
107.85
668.83
508.87
588.83
666.00
476.33
393.00
7
55.00
681.00
213.09
274.20
259.33
499.00
547.00
15
0.00
222.95
8.93
168.27
93.33
473.50
464.33
31
0.00
0.00
0.00
1.15
7.00
185.00
384.67
Toluene
0
2170.91
1735.47
1803.10
2141.95
1691.67
1691.67
1422.00
3
53.45
1348.13
1070.47
1091.70
1509.33
1053.67
780.67
7
39.33
1416.30
192.68
144.45
151.00
388.00
1079.00
15
13.65
414.50
35.53
224.20
74.00
191.00
907.00
31
0.00
0.00
0.00
0.55
3.67
56.00
753.00
m,p-Xylene
0
4823.27
3548.30
3898.10
4664.55
3068.33
3068.33
3528.67
3
1623.15
1608.97
1823.30
652.13
2013.67
2311.67
1984.33
7
924.83
1826.93
53.35
18.20
33.00
40.00
2342.67
15
40.65
935.95
57.30
83.13
29.00
25.25
1966.33
31
0.00
8.07
0.00
1.73
5.00
9.00
1565.00
o-Xylene
0
2755.48
2111.07
2272.20
2770.90
2215.67
2215.67
2237.67
3
1652.45
1714.50
1737.33
1744.60
1884.67
1428.67
1313.00
7
742.00
2110.50
943.53
1675.25
1468.00
1387.33
1723.67
15
48.25
856.45
123.93
1294.70
1063.00
1230.00
1317.33
31
0.00
3.67
0.45
8.45
211.00
624.33
1104.33
113


86
(1962) are shown in Table 5-10. Breakthrough curve data are
compiled in Appendix D.
Retardation factors for these solute breakthrough
curves were also evaluated by estimating the area above the
curve using Simpson's method. This method of calculation
yielded R values which were slightly greater than the fitted
values (Table 5-11)/ but which exhibited the same relative
elution order. The R values calculated from the area above
the BTC were within 0.1 of the values calculated by curve
fitting. Retardation factors were also calculated by
determination of the number of pore volumes required to
reach C/C value of 0.5. All three methods of calculation
o
are compared in Table 5-11. The breakthrough curves for the
solutes in this study were slightly asymmetrical whereas the
curves for the unretained solute were sigmoidal and
symmetrical. This asymmetry was attributed to sorption
nonequilibrium during transport through the column and not
to dispersion. The shape of the measured BTC is determined
by the kinetics of the sorption-desorption process.
Symmetrical BTC are obtained when the sorption process is
instantaneous and equilibrium conditions exist between
sorbed and aqueous concentrations. Under non-equilibrium
conditions during flow, asymmetrical BTC are obtained (Rao
and Davidson, 1979). This type of response has been
reported by several investigators for pesticide breakthrough
(Nkedi-Kizza et al., 1987).


Treatment IB
Day
Benzene Toluene
ra/P-xyl
o-Xyl
3,4 ET
15
64
177
230
299
58
382
652
1642
1414
308
avg
223
415
936
856
183
std
159
237
706
557
125
%var
71
57
75
65
68
31
0
0
8
6
3
0
0
0
0
0
0
0
16
5
11
avg
0
0
8
4
5
std
0
0
7
3
5
%var
0
0
82
73
96
.,3,5
TMB
2 ET
12,4
TMB
1,2,3
TMB
DO
mg/L
14
59
39
73
2.4
154
142
324
266
2.3
84
101
181
170
2.4
70
42
143
96
0.0
84
41
79
57
2.1
3
9
4
17
2.0
0
0
0
0
2.9
7
23
2
12
2.3
3
11
2
10
2.4
3
10
2
7
0.4
88
89
82
74
15.6
233


APPENDIX E
BATCH BIODEGRADATION DATA
This appendix presents data from batch biodegradation
experiments one and two. All hydrocarbon concentration
values are in units of ug/L. Zero values indicate that the
concentration of hydrocarbons was below 0.5 ug/L. Dissolved
oxygem values are in units of mg/L.
229


14
processes of solute-soil interaction and the thermodynamics
of this process are not completely characterized. Therefore/
sorption is used in this study as a generic term to describe
solute retention (ie. uptake of solute)/ regardless of
whether the process is one of adsorption/ absorption or
partitioning (Woodburn/ 1985). Desorption is used here to
describe solute removal from the solid phase.
3.4.1 Sorption Processes
The attractive forces acting to effect sorption of
hydrophobic compounds onto natural sorbents were reviewed by
Voice and Weber (1983). The major theory is discussed
below.
Bonding forces in sorption may be both physical and
chemical/ though both are basically electrostatic in nature.
Physical sorption results from Van der Waals forces. The
strength of these interactions is generally on the order of
1-2 Kcal/mole. These energies may be augmented by a
thermodynamic gradient driving hydrophobic molecules out of
solution. This is based on entropic considerations
(solvophobic theory).
Chemical sorption is the interaction between specific
sites of the sorbent and individual solute molecules. This
approximates a true chemical bond with heats of adsorption
between 15-50 Kcal/mole. Voice and Weber (1983) point out
that it is difficult to assess the importance of each type
of bonding. The heterogeneous nature of natural sorbent
materials is largely unknown, and sorption processes
probably involve all types of interactions.


75
5.4.3 Batch Desorption Experiments
Desorption data are also presented in Figures 5-2 and
5-3, fit with the Freundlich type model. Visual inspection
of the desorption data suggests some degree of
irreversibility or some difference in desorption kinetics
based on the upward displacement of the desorption
regression lines. However, the calculated values of the
partition coefficient for desorption with the linear type
model (Table 5-6) and for the linear type model with
suppressed intercept (Table 5-7) were not significantly
different from sorption values (Kd) at the 0.05 probability
level. Desorption coefficients from the Freundlich type
model (K£^) were also not significantly different from
values at the 0.05 level (Table 5-8). Statistical analyses
of the models used to evaluate the desorption coefficients
indicated that all three models gave excellent fit to the
data, as evidenced by the high coefficients of
determination.
These data suggested the reversibility of the sorption
process, and demonstrated that the hysteretical behavior of
the desorption data were not significant. This was
consistent with a majority of the published literature on
sorption of organic compounds to natural sorbents (Miller
and Weber, 1984).
For purposes of discussion, the Kd values from the
linear model with suppressed intercept are used in the
following sections. As discussed earlier, these data were


10
hydrocarbons (Shehata, 1985). Dermal absorption of volatile
organic contaminants from gasoline may also be a significant
exposure (Brown et al., 1984).
Fire and explosion hazards are also a risk factor in
the release of gasoline to the environment. Volatilization
and subsequent gas phase transport of hydrocarbons in the
unsaturated zone have destroyed buildings (Hoag and Marley,
1986 ) .
3.3 Convective-Dispersive Models
The cogent evaluation of contaminant plumes, remedial
action alternatives, and risk assessment for organic
compounds in groundwater requires a thorough understanding
of the behavior of these contaminants in groundwater
systems. This includes an assessment and quantification of
the relevant processes which influence their fate and
transport (Miller and Weber, 1984).
The interaction of these processes may be examined in
the context of convective-dispersive models. These models
have been reviewed (Anderson, 1979, Freeze and Cherry,
1979) and are marked by their computational simplicity,
reasonable data requirements and sufficiently accurate
output (Roberts et al., 1985). Although the adequacy of
convective-dispersive models for describing solute transport
has been questioned (Anderson, 1979, Smith and Schwartz,
1980), particularly with regard to dispersivity


CHAPTER IV
MATERIALS AND METHODS
4.1 Introduction
This chapter discusses the materials and experimental
methods employed during this study. The field site/ and the
solutes and sorbents are described followed by a description
of the chromatographic systems. Laboratory experiments for
the determination of hydrolysis/ sorption and biodegradation
parameters are discussed. Finally/ the field procedures and
experiments are discussed.
4.2 Site Description
The field research site used for a portion of this
study was located at the Citrus Research and Education
Center (CREC) at Lake Alfred, FI. The site was located in
the Trail-Ridge Lake Wales Ridge system of hills containing
deep internally drained lake basins. Unconsolidated
deposits in the area consisted of sand and sandy clays up to
150 ft thick above the limestone bedrock. The geology was
marked by many sinkholes formed through subsidence of the
unconsolidated deposits into solution cavities in the
limestone (Spangler, 1984).
34


309
Davidson, J.M., P.S.C. Rao, and P. Nkedi-Kizza. (1983).
Physical Processes Influencing Water and Solute Transport
in Soils. In Chemical Mobility and Reactivity in Soil
Systems. Madison, Wisconsin: Soil Science Society of
America, pp. 35-47.
Delfino, J.J., and C.J. Miles. (1985). Aerobic and Anaerobic
Degradation of Organic Contaminants in Florida
Groundwater. Soil & Crop Sci. Soc. Fla. Proc.44: 9-14.
DiToro, D.M., and L.M. Horzempa. (1982). Reversible and
Resistant Components of PCB Adsorption-Desorption
Isotherms. Environ. Sci. Technol 16(9): 594-602.
Dowd, R.M. (1984). Leaking Undergound Storage Tanks. Environ.
Sci. Technol. 18(10): 27-34.
Dupont (1984). Hydrogen Peroxide Solution Storage and
Handling. Wilmington, DE: E.I. Dupont de Nemours & Co.,
pp. E-69997.
Evans, W.C. (1977). Biochemistry of the Bacterial Catabolism
of Aromatic Compounds in Anaerobic Environments. Nature
270: 17-22.
Fernald, E.A., and D.J. Patton. (1984). Water Resources Atlas
of Florida. Tallahassee, FL.: Institute of Science and
Public Affairs, Florida State University.
Fetter, G.W. (1980). Applied Hydrogeology. Columbus, OH:
Charles E. Merrill Co.
FLDER (1986). Florida Sites List: Petroleum Contamination
Incidents^ Tallahassee, FL: Dept, of Environmental
Regulation.
Freeze, R.A., and J.A. Cherry. (1979). Groundwater. Englewood
Cliffs, NJ: Prentice-Hall, Inc.
Ghiorse, W.C., and D.L. Balkwill. (1983). Enumeration and
Morphological Characterization of Bacteria Indigenous to
Subsurface Environments. Dev. Ind. Microb. 24: 213-224.


PORE VOLUMES
Breakthrough curve for 1,3,5-trimethylbenzene in column
biodegradation experiment performed at a flow rate of 1 mL/min.
287


53
calculate the amount of solute lost to sorption in each
batch vial. The extent of the sorption loss correction
varied with the concentration of the analyte and the
sorption parameters and n. This correction factor added
as much as 20% to the measured concentration values. These
predicted losses resulting from sorption were added to the
aqueous concentration for each analyte in each vial to
calculate the total concentration of each solute in the vial
(C ) These C values were employed to obviate the need for
simultaneous calculation of biodegradation on both sorbed
and aqueous concentrations and any calculation of rates of
sorption-desorption during biodegradation. The C values
were used to model the biological rate coefficients. The
rate data were fitted to zero order, first order, second
order and mixed order rate equations (Levenspiel, 1972), and
to the Thomas slope method (Thomas, 1950).
4.11 Column Biodegradation Studies
4.11.1 Experimental Procedure
Column biological degradation experiments were
performed with the same column system described in section
4.8. Two flow rates were used in these experiments. These
were 1 ml/min (0.680 cm/min) and 0.90 ml/hr (0.010 cra/min).
Columns operated at 0.90 ml/hr were fitted with a low dead
volume in-line septa. Effluent was withdrawn with a 50 ul
syringe (Hamilton Co.) and analyzed immediately. Effluents


C / C o
PORE VOLUMES
a BENZENE
Figure 5-12. Breakthrough curve for benzene (single solute) spiked into
RAP-2 well water (C = 4000 ug/L).
10 7


133
Table 5-20. Biodegradation rate constants and correlation
coefficients for the fit of biodegradation
experiment #2 data to a first order rate
equation.
Treatment Benzene Toluene
Ethbza
m,p-Xylene o-Xylene
2A
kb
0.042
r2
0.462
2B
k
0.049
r2
0.887
2C
k
0.003
r2
0.105
2D
k?
0.043
r2
0.621
2E
k
-0.004
r2
0.169
2F
k
-0.001
r2
0.003
2G
k
0.067
r2
0.234
2H
k
0.059
r2
0.640
21
k
-0.002
r2
0.056
0.071
0.486
0.070
0.344
0.089
0.942
0.082
0.919
0.006
0.317
0.013
0.619
0.073
0.877
0.096
0.884
0.006
0.219
0.017
0.138
0.001
0.012
0.024
0.177
0.036
0.057
0.004
0.002
0.072
0.683
0.135
0.469
0.007
0.211
0.049
0.160
0.046
0.618
0.052
0.972
0.114
0.955
0.070
0.894
0.013
0.619
0.007
0.403
0.138
0.986
0.046
0.800
0.017
0.009
0.002
0.038
0.007
0.179
0.002
0.029
0.081
0.266
0.057
0.406
0.095
0.398
0.057
0.500
0.010
0.873
0.004
0.740


treatment #2E
day 0
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
1238
7083
227
6498
3185
1826
10286
330
9320
4225
1350
7355
226
6903
3353
1155
6310
91
6246
3048
avg
1392
7759
219
7242
3453
std
260
1509
85
1223
459
%variance
19
19
39
17
13
treatment
day 2
#2E
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
607
3060
43
2368
1313
692
3539
45
2717
1502
avg
649
3300
44
2543
1408
std
43
240
1
174
95
%variance
7
7
2
7
7
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
1443
509
415
1899
689
7.50
2153
769
624
2805
1036
1576
569
462
2031,
765
1432
527
428
1941
758
1651
594
482
2169
812
7.50
295
104
84
370
133
0.00
18
17
17
17
16
0.00
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
418
149
141
534
229
8.10
457
164
155
565
252
8.05
438
157
148
550
241
8.08
20
8
7
16
12
0.02
4
5
5
3
5
0.31
256


173
microcosms, but did not increase the rates of degradation or
the extent of hydrocarbon removal in batch studies.
Ammonium chloride addition produced conditions favorable to
nitrifying bacteria, which resulted in the depletion of
oxygen without substantial hydrocarbon removal. Treatment
with ammonium chloride resulted in a lag phase, during which
the microbial community adapted to the changed nutrient
conditions. The combination of NH^cl and exhibited a
toxic effect to the microflora from the Lake Alfred aquifer.
This suggests that the use of NH^Cl as a field tracer should
not be followed by application of to increase dissolved
oxygen. Treatment with at concentrations of 17 mg/L
and 68 mg/L produced lag times of up to eight days, with
slightly reduced rate constants.
VOA vials were employed as microcosms for the batch
biodegradation experiments. These vials allowed substantial
abiotic losses of solutes, as determined by control samples,
and were not recommended for use in future experiments.
6.1.4 Microbial Field Data
Oxygen was the limiting substance at the Lake Alfred
Site. Dissolved oxygen concentrations in the main area of
hydrocarbon contamination was only 0.1 to 0.4 mg/L. The
average value for total phosphorus was 0.6 mg/L and the
average value for nitrate was 0.3 mg/L over the study area.
These data indicate that there were sufficient phosphorus
and nitrogen sources to initiate the biological removal of
hydrocarbons, given sufficient oxygen. This hypothesis was


OQ AMOUNT SORBES
Figure 5-2
Freundlich sorption isotherm for benzene at equilibrium
U)


Table 5-9.
Values of dispersion coefficients calculated
from the breakthrough curves of unretained
solutes in laboratory columns.
Tracer
Flow
(mL/min)
Velocity
(cm/min)
Dispersion
(cm/min)
avg
. -,b
std
V
0.015
0.003
0.00053
3H20
0.015
0.003
0.00066
n
3h2o
0.015
0.003
0.00040
0.00053
0.00013
CaC12
o

r{
0.204
0.051
CaCl 2
1.0
0.204
0.013
CaCl
o

i1
0.204
0.069
0.044
0.029
aaverage values of dispersion measurements
standard deviation of dispersion measurements


LIST OF FIGURES
Figure Page
4-1 Site plan of the field research site at
the Citrus Research and Education Center,
Lake Alfred, Fl... 36
4-2 Extent of the hydrocarbon pNlume at the field
research site as of October, 1986 37
5-1 Approach to equilibrium for several aromatic
solutes on Lake Alfred aquifer material 63
5-2 Freundlich sorption isotherm
for benzene at equilibrium 73
5-3 Freundlich sorption isotherm for
toluene at equilibrium 74
5-4 Breakthrough curve for chloride for a 5 cm
sorption column 80
5-5 Breakthrough curve for benzene from
Lake Alfred water (C = 4700 ug/L) 83
5-6 Breakthrough curve for toluene from
Lake Alfred water (C = 2600 ug/L)..... 84
o
5-7 Breakthrough curve for n-propylbenzene from
Lake Alfred water (C = 1000 ug/L) 85
5-8 Log Kqc vs. log Kqw for study compounds 95
5-9 Log K (from column data) vs. log WS
for sSudy compounds 97
5-10 Regression equations for several models
describing the relationship between
K and K : (a) Curtis et al., 1985
(8*7 Schwarzenbach and Westall, 1981 (c) this
study (d) Briggs, 1981 (e) Chiou et al., 1983.. 101
5-11 Log K vs. for aromatic solutes (a) in this
studyand (b) from Sabljic (1987) 103
5-12 Breakthrough curve for benzene (single solute)
spiked into RAP-2 well water (Co = 4000 ug/L).. 107
x


treatment #21
day 7
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
163
282
825
700
186
376
894
734
avg
175
329
ERR
860
717
std
12
47
ERR
35
17
%variance
7
14
ERR
4
2
treatment #21
day 14
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
157
221
4
743
594
159
223
782
615
avg
158
222
4
763
605
std
1
1
0
20
10
%variance
1
0
0
3
2
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
147
58
81
243
159
8.60
141
57
84
265
153
8.60
144
58
83
254
156
8.60
3
0
2
11
3
ERR
2
1
2
4
2
ERR
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
117
51
62
221
132
7.50
122
55
64
245
142
7.20
120
53
63
233
137
7.35
2
2
1
12
5
0.15
2
4
2
5
4
2.04
270


UF-2M
Wetland
Figure 5-29.
Distribution of o-xylene (ug/L) at the
Lake Alfred field site.


26
A review of the techniques for the enumeration and
estimation of microbial biomass were presented by Atlas
(1982) and Webster et al. (1985). Bouwer and McCarty (1884)
noted that the majority of bacterial activity was associated
with bacteria attached to surfaces. This results in the
formation of biofilms, which are favored in low substrate-
high surface area conditions. The biofilm may also present
an active surface with solutes sorbing to the surfaces of
microbial cells. In terms of the advection-dispersion
models, the rates of biological degradation are incorporated
into the model through the sink term which describes the
microbial degradation of solutes from the aqueous phase.
Q. is defined as:
i
Q. = -k 0 C [3.18]
where k is the rate of biological degradation (T ^), 0 is
the volumetric water content (ml/cm^)and C is the solution
phase concentration of a solute (ug/L).
3.5.1 Environmental Factors Affecting Biodegradation
Many factors can affect the transformation of organic
contaminants in the subsurface. McCarty (1984) included low
substrate concentrations, toxic conditions, molecular
structure of the substrate, inaccessibility of the
substrate, and absence of essential arowth farcers
Biological activity is often limited bv certain m^fsho'i^
requirements of the cell, supplied from the environment.
Important geochemical properties include dH redox
potential, nitrogen and phosphorus concentrations and the


17
column studies leads to the evaluation of from equation
[3.10]. Nkedi-Kizza et al. (1987) compared techniques for
the calculation of R from soil column leaching experiments
and from batch isotherm experiments. Values of R calculated
by determining the area above the breakthrough curve were
shown to be equivalent to R values calculated by using
equation [3.10].
3.4.3 Sorption Estimators
Recently, approximation methods based on the assumption
of partitioning as the dominant method of solute interaction
have become common (Karickhoff et al., 1979, Chiou et al.,
1979, Kenaga and Goring, 1980, Chiou et al. 1983). Their
use is largely a result of the time and difficulty in the
accurate measurement of sorption coefficients (K^), and the
general lack of data on hydrocarbon sorption to
environmental sorbents. These authors note a correlation
between the fractional organic carbon content of the sorbent
material (f ) and K.. The K, normalized to f of the
oc d d oc
sorbent is described as K where:
oc
K = K,/f [3.12]
oc d' oc L J
Values
of K is
oc
well correlated
with aqueous
solubility
(ws) (C
hiou
et al
., 1979) and the octanol-wats
sr partition
coeffic
ient
(K )
(Karickhoff et
al., 1979).
These authors
ow
suggest
that
the
solute-sorbent
interaction is a
partiti
oning
proc
ess rather than
an interaction between
solute
and the mi
neral surface.
Evidence for
partitioning
is partially supported by the hydrophobic character of soil


38
shown in Figure 4-1. All experiments were carried out with
subsamples of the same aquifer material. The sample was
collected with a stainless steel auger just below the water
table at a depth of about 4 fe
of Well RAP-1. Care was taken
surface materials by removing
through careful handling of th
was oven dried at 105 C for 24
standard sieve and stored, cov
Prior to use, the aquifer mate
minutes on each of three conse
materials.
Prior to sterilization an
and chemical properties of the
laboratory studies were charac
particle size analysis, percen
density, hydraulic conductivit
standard methods of soil analy
4.4 C hoice
Gasoline contaminated wel
research site was used as the
for the majority of experiment
exception of a single solute c
benzene spiked in to RAP-2 wat
performed with mixtures of dis
et, approximately 10 feet east
to avoid contamination with
one foot of top soil, and
e auger. The aquifer material
hours, sieved through 2 mm
ered, at room temperature,
rial was autoclaved for 90
cutive days to sterilize the
drying
, se
lec
ted
physi
.cal
aquifer
mat
er i
als
used
in the
erized
(pH,
pa
rti c
le density,
organi
c ca
rbo
n b
ulk
, and w
ater
CO
nten
t) using
sis (Black, 1965).
of Solutes
1 water from the Lake Alfred
source of dissolved solutes
s in this study. With the
olumn sorption experiment with
er, all experiments were
solved hydrocarbons at


LOO AMOUNT SORBED
LOO SOLUTION CONCENTRATION
SORPTION o DESORPTION
Freundlich sorption-desorption isotherm for toluene at
equilibrium.
192


C / C o
BNZ
TOL
EBZ
MPX
OX
Figure 5-19. Relative concentrations of Cg-Cg aromatic hydrocarbons
vs. time in biodegradation treatment 2D.
139


Table 5-19. Continued.
Treatment
Compound
Day
2A
2B
2C
2D
2E
2F
2G
2H
21
2-ET
0
482.25
482.25
482.25
482.25
482.25
482.25
199.67
199.67
199.67
3
238.33
200.00
260.67
269.33
148.00
199.33
24.87
85.00
67.50
7
132.67
126.67
176.00
164.67
145.33
147.00
14.57
28.67
82.50
14
100.00
108.00
225.33
64.00
137.33
170.67
18.58
11.00
63.00
21
88.67
104.67
205.67
72.67
202.00
231.00
11.43
16.00
57.50
35
47.33
16.33
165.67
49.00
144.33
157.00
9.47
12.50
51.00
1,2,4-TMB
0
2169.00
2169.00
2169.00
2169.00
2169.00
2169.00
657.67
657.67
657.67
3
260.00
753.00
1042.33
952.67
549.50
818.33
1.33
22.67
257.00
7
369.00
295.00
695.33
439.33
554.33
592.67
7.83
1.77
254.00
14
164.50
114.00
898 00
106.00
510.67
653.67
15.33
3.15
233.00
21
255.00
133.67
801.00
19.67
776.00
896.67
7.93
7.50
231.00
35
110.67
10.00
639.67
109.50
346.00
610.00
1.70
4.00
199.00
1,2,3-TMB
0
812.00
812.00
812.00
812.00
812.00
812.00
364.00
364.00
364.00
3
301.67
337.00
422.33
292.10
240.50
292.00
39.73
195.67
152.00
7
243.67
222.67
301.67
282.33
247.00
262.67
24.27
46.00
156.00
14
164.50
182.50
383.33
129.33
232.67
290.00
22.50
28.00
137.00
21
148.00
192.00
362.00
139.67
332.00
405.67
23.10
49.50
137.50
35
75.67
27.67
278.33
86.50
241.67
267.00
5.60
30.50
120.67
D0a
0
7.50
7.50
7.50
7.50
7.50
7.50
20.00
20.00
20.00
3
2.73
2.43
7.43
8.53
8.08
8.53
4.45
6.40
9.60
7
2.27
2.20
7.53
2.90
4.63
8.23
4.10
5.07
8.60
14
3.53
2.90
7.80
3.73
5.37
7.73
3.23
-
7.35
21
2.83
3.17
7.73
3.27
5.50
7.50
3.13
5.05
7.90
35
1.93
3.33
7.27
1.85
3.27
6.95
3.47
2.95
6.30
a
dissolved oxygen in mg/L
131


Treatment 1A
Day
Benzene
Toluene
ra,p-xyl
o-Xyl
3,4 ET
0
756
2023
4452
2597
858
803
2101
4760
2639
914
926
2389
5258
3031
975
avg
828
2171
4823
2755
916
std
72
157
332
195
48
%var
9
7
7
7
5
3
194
88
2740
2344
499
22
19
506
961
30
avg
108
53
1623
1652
265
std
86
35
1117
692
235
%var
80
65
69
42
89
7
13
19
182
208
42
79
54
1106
867
200
73
45
1487
1151
264
avg
55
39
925
742
168
std
30
15
548
395
93
%var
54
38
59
53
55
,3,5
TMB
2 ET
1,2,4
TMB
1,2,3
TMB
DO
mg/L
385
441
1239
521
7.2
369
438
1317
557
7.3
415
353
1447
604
7.4
390
410
1335
560
7.3
19
41
86
34
0.1
5
10
6
6
1.1
297
255
708
478
1.4
140
81
177
141
1.6
1.5
218
168
443
309
1.5
78
87
266
169
0.1
36
52
60
55
6.7
48
47
47
59
150
149
219
225
1.5
214
199
303
318
2.0
137
132
190
201
1.8
68
64
106
107
0.3
50
48
56
54
14.3
230


PORE VOLUMES
Breakthrough curve for 1,2,4-trimethylbenzene in column
biodegradation experiment performed at a flow rate of 1 mL/min.
289


2-Ethyltoluene Sorption Data
Cs (ug/L) Cw
avg
std
236
21
70
2
22
0
6
6.4
3
1
245.7
3.32
15.5
2.07
3.5
0.14
1 .9
0.5
0.97
0.14
0 52
0.21
amount
(ug/L)
sorbed
avg
std
(ug/L)
306
31
70
143
25
73
24
1
2
8
1
2
4
0
1
373
23.4
127.3
37 .3
a
21.8
7.7
a
4.2
3.7
a
1.8
1.5
a
0.53
0.74
a
0.22
n= 1
a
log
log
amount
amount
solut ion
sorbed
sorbed
concentration
(ng/g)
ii
ii
ii
ii
ii
ii
n
ii
ii
ii
ii
n
n
ii
ii
ii
n
ii
ii
ii
ii
ii
24.2
1.38
2.49
25.2
1.40
2.16
0.7
-0.16
1.38
0.7
-0.16
0.90
0.3
-0.46
0.60
43.9
1.64
2.57
7.5
0.88
1.57
1.4
0.16
0.89
0.6
-0.21
0.57
0.2
-0.74
0.18
0.1
-1.12
-0.13
205


a2
2J5
1 r i [ i i
2 2 2A
i \ r r ~~ i
20 20 3
... r
i r
3-2
LOO /Cow
1 i 1
3A 30
Figure 5-8. Log Kqc vs. log Kqw for study compounds.
30
Ch


PORE VOLUMES
Figure 5-25. Breakthrough curve for toluene in column biodegradation
experiment performed at a flow rate of 1 mL/min.
153


treatment #2G
day 21
BNZ
TOL
ETH BZ
m,p-XYL
O-XYL
3,4ET
135TMB
2ET
124TMB
12 3 TMB
[DO]
0
1
0
39
106
14
21
19
18
44
2.90
0
1
0
4
25
1
10
5
3
2
2.60
0
3
0
5
48
3
9
10
2
24
3.90
avg
0
2
0
16
60
6
13
11
8
23
3.13
std
0
1
0
16
34
6
5
6
7
17
0.56
%variance
ERR
54
ERR
102
57
95
40
52
92
74
17.74
treatment #2G
day 35
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
3,4ET
135TMB
2ET
12 4 TMB
123TMB
[DO]
2
7
0
4
26
3
5
12
3
16
3.20
5
30
0
12
12
2
1
4
3
1
3.60
1
4
0
1
3
0
0
13
0
0
3.60
avg
3
14
0
6
14
2
2
9
2
6
3.47
std
2
12
0
5
10
1
2
4
1
7
0.19
%variance
80
88
ERR
79
70
73
109
43
71
129
5.44
265


TREATMENT #2B
DAY 0
BNZ
TOL
ETH BZ m,p-XYL
O-XYL
1238
7083
227
6498
3185
1826
10286
330
9320
4225
1350
7355
226
6903
3353
1155
6310
91
6246
3048
avg
1392
7759
219
7242
3453
std
260
1509
85
1223
459
%variance
19
19
39
17
13
Treatment #2B
DAY 2
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
892
4486
84
3434
1964
882
4601
79
3339
1891
732
3739
71
2963
1650
avg
835
4275
78
3245
1835
std
73
382
5
203
134
%variance
9
9
7
6
7
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
1443
509
415
1899
689
7.50
2153
769
624
2805
1036
1576
569
462
2031
765
1432
527
428
1941
758
1651
594
482
2169
812
7.50
295
104
84
370
133
0.00
18
17
17
17
16
0.00
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
649
239
221
845
379
2.10
591
214
198
716
334
2.50
524
193
180
699
297
2.70
588
215
200
753
337
2.43
51
19
17
65
34
0.25
9
9
8
9
10
10.25
247


118
Table 5-18. Biodegradation rate constants, half-lives and
correlation coefficients for the fit of
biodegradation experiment #1 data to the
Thomas slope rate equation.
Treatment Benzene Toluene m,p-Xylene o-Xylene 3,4-ET
1A
ka.
t^b
0.224
3.09
0.239
2.91
0.188
3.68
0.139
4.97
0.195
3.56
2
r
0.964
0.958
0.974
0.999
0.967
IB
k
th
-3.406
-0.204
-0.155
-4.46
0.135
5.14
-0.155
-0.107
0.111
6.27
2
r
0.764
0.129
0.838
0.129
0.745
1C
k
th
0.094
7.37
0.153
4.54
0.183
3.79
0.087
7.93
0.195
3.55
2
r
0.899
0.986
0.987
0.947
0.984
ID
k
th
0.118
5.90
0.171
4.06
0.228
3.04
0.096
7.21
0.205
3.38
2
r
0.978
0.975
0.966
0.712
0.972
IE
k
t*s -
-0.027
25.99
0.048
14.30
0.144
4.80
0.045
15.33
0.151
4.60
2
r
0.040
0.199
0.946
0.926
0.982
IF
k
th
0.101
6.88
0.142
4.89
0.116
5.96
0.130
5.31
0.160
4.33
2
r
0.568
0.989
0.822
0.816
0.983
1G
k
th
0.130
5.33
0.177
3.92
0.176
3.93
0.157
4.41
0.173
4.00
2
r
0.488
0.780
0.863
0.761
0.883


76
Table 5-6. Regression parameters for the analysis of
average values of equilibrium batch
desorption data with the linear model.
Compound
N3
c b
(u8?£)
Kdd'
stdC
y-mt
std
2
r
Benzene
5
950
0.248,
0.006
2.2,
4.18
0.998
Toluene
8
4200
0.303,
0.011
4.13,
55.8
0.992
m,p-Xylene
9
4300
0.186,
0.006
13.3,
30.1
0.993
o-Xylene
9
2500
0.152,
0.012
11.0,
31.1
0.955
3 or 4 ETe
9
935
0.250,
0.018
-2.9,
18.4
0.968
1,3,5 TMB f
8
460
0.194,
0.004
1.5,
1.62
0.998
2-ET9
7
373
0.566,
0.010
0.78,
2.64
0.999
1,2,4TMBh
10
1600
0.199,
0.005
3.3,
7.62
0.996
1,2,3TMB1
9
558
0.219,
0.032
1.1,
20.3
0.871
anumber of data points
^maximum concentration
cstandard deviation
^y-intercept
e3 or 4 Ethyltoluene
^1,3,5-Trimethylbenzene
92-Ethyltoluene
bl,2,4-Trimethylbenzene
1l/2/3-Trimethylbenzene


69
appropriate for estimation of sorption. However, analysis
of variance with a global F-test indicated that the model
was useful for predicting sorption at the 0.01 significance
level. Therefore, the linearity of all isotherms was
confirmed. Linear isotherms have been noted by several
authors (Schwarzenbach and Westall, 1981, Chiou et al.,
1979, Karickhoff et al., 1979) and the data presented in
this study are in agreement with these studies.
Curtis et al. (1986) noted that the use of the linear
regression technique was not statistically rigorous since
variance in the dependent variable was not distributed
uniformly across the observed concentration range. These
authors suggested that a least squares fit on the log
transformed data (Freundlich model) gives a better
approximation by providing a more uniform distribution of
variance. The Freundlich model provided a good fit to the
data in this study (Table 5-4) as evidenced by the high
coefficients of determination for the Freundlich model. The
Freundlich isotherm explained between 91.7 to 99.5% of the
variance in the data, and provided a slightly improved fit
2
to the isotherm data relative to the linear models. The r
value for toluene was 0.917, which was much improved over
the coefficient of determination for toluene in the linear
model. The log values for the study compounds are also
presented in Table 5-4. Values for several components
(ethylbenzene, and the propylbenzenes) were not included in
the table owing to their low concentrations in Well OHM-4


Column Biodegradation Data
values as ug/L
CUMM ML
BNZ
TOL
EBZ
MPX
OX
Co
= 1711
7034
10 61
3848
1931
0
0
0
0
0
0
3.897
72.2
59.8
36
0
17
5.553
177.4
163.5
50
0
6.975
316
272
30
33
8.775
433
412
34
49
9.828
437
485
40
64
68
10.8
455
499
43
69
11.7
490
548
54
87
13.05
467
590
43
62
100
14.4
537
731
54
93
33
15.75
491
690
48
92
141
17.1
513
726
52
110
169
18.225
490
751
55
119
177
22.725
385
649
61
133
206
25.425
479
818
85
182
213
28.125
523
853
86
181
205
29.25
658
1092
93
203
249
44.325
599
1085
9 5
192
246
50.85
661
1009
88
195
259
54.45
644
1033
95
227
276
L
v
2.5 cm
0.003 cm/min


39
concentrations occurring in the field. These concentrations
are the result of the solubilization and subsequent
weathering of gasoline hydrocarbons into groundwater. Well
OHM-4 was used as the source of water for these experiments.
This well was chosen based on consistently high levels of
dissolved aromatic hydrocarbons. Hydrocarbon free
groundwater was obtained from a non-contaminated portion of
the aquifer (Well RAP-2). Hydrocarbon concentrations in
these waters were monitored monthly. Well RAP-2 remained
free of aromatic hydrocarbons throughout the course of these
experiments. Concentrations of aromatic hydrocarbons varied
in Well OHM-4 but remained high enough to provide samples
for laboratory experiments.
Water samples were collected with a 5.1 cm (2") id poly
vinyl chloride (PVC) bailer, following removal of five well
volumes to allow collection of a representative sample.
Well volumes were calculated based on the diameter of the
well, and the depth of water in the well. These water
samples were collected in four liter brown glass bottles
transported on ice, and stored at 4 C upon arrival at the
laboratory. The pH of these well waters ranged from 6 to 7.
The conductivity was approximately 300 umhos. Total
phosphate was 0.4 mg/L for RAP-2 and was 0.65 mg/L for well
OHM-4. Nitrate was 0.29 mg/L in well RAP-2 and 0.20 in well
OHM-4.


49
Table 4-1.
Experimental
experiment
design for batch
#1.
biodegradation
Hydrogen
Sodium
Peroxide
NH Cl
Azide
Treatment
(mg/L)
(mg/L)
(mg/L)
1A
none
none
none
IB
17
none
none
1C
68
none
none
ID
none
18
none
IE
17
18
none
IF
68
18
none
1G
none
none
1.25


91
of sorption. Physical limitations to equilibrium include
diffusion controlled adsorption-desorption processes (Rao
and Davidson, 1979) or the presence of physical barriers
limiting the interaction of the sorbent and solute (eg. soil
aggregates, surface films). The kinetics of chemical
reactions between the sorbent and solute may be limiting,
thereby explaining the nonequilibrium in the column
breakthrough curves. Multisite models have been proposed to
account for sorption nonequilibrium (Rao et al., 1979).
However, the physical and chemical processes are
mathematically equivalent when written in non-dimensional
form, thus the identification of the process responsible for
the observed nonequilibria is not possible from breakthrough
curve data.
Sorption nonequilibria are also a function of the flow
velocity. The observed effect of increased flow velocity is
displacement of the elution curve towards a smaller
breakthrough volume, whereas the calculated effect of
increased flow velocity is a broadening of the elution
curve, owing to increased dispersion, without a change in
the position of the position of the BTC. This effect was
demonstrated by Schwarzenbach and Westall (1981) where
retardation factors decreased with increased flow rates,
indicating slow sorption kinetics.
Rao and Davidson (1979) illustrated that the
retardation factor may also be a function of concentration,
with increased concentration of solutes leading to decreased


Treatment ID
1,3,5 1,2,4 1,2,3 DO
Day
Benzene
Toluene
m,p-Xyl
o-Xyl
3,4 ET
TMB
2 ET
TMB
TMB
mg/L
15
305
368
170
1129
62
109
111
6
216
3.0
136
229
49
1446
46
154
163
5
171
4.1
65
76
31
1309
18
134
139
4
271
4.9
avg
168
224
83
1295
42
132
138
5
219
4.0
std
101
119
61
130
18
18
21
0
41
0.8
%var
60
53
74
10
44
14
15
10
19
19.5
31
0
1
3
4
4
96
57
2
163
5.0
2
0
3
21
6
127
84
2
205
5.2
3
1
0
7
5
99
45
2
143
5.7
0
1
1
1
2
77
31
1
112
4.7
avg
1
1
2
8
4
100
54
2
155
5.2
std
1
0
1
8
2
18
19
1
34
0.4
%var
107
71
69
91
40
18
36
43
22
7.1
237


o-Xylene Desorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
814
126.57
1708
74 22
35
11.13
171
a
5
0.85
34
a
6
5.69
17
a
1412
317.35
2316
257.84
528
29.95
1246
a
91
14.57
168
a
16
0.69
61
3.1
14
2.01
27
0.82
amoun t
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentration
894
308.4
2.49
2.91
136
46.9
1.67
1.54
29
10.0
1.00
0.70
11
3.8
0.58
0.78
904
311.9
2.49
3.15
718
247.7
2.39
2.72
77
26.6
1.42
1.96
45
15.5
1.19
1.20
13
4.5
0.65
1.15
a
n = l
197


50
(Reagent grade, Fisher Scientific) and 10% (w/v) aqueous
solution of sodium azide (Fisher Scientific) as outlined in
Table 4-1. Triplicate samples were analyzed for each
treatment at 0, 3, 7, 15, and 31 days. Treatment number 1G
was a sterile control. Hydrogen peroxide was added based on
data from the hydrogen peroxide evaluation experiment and on
data from Britton (1985), who demonstrated that cytotoxicity
was minimal at hydrogen peroxide concentrations less than
100 mg/L. Ammonium chloride was added based on data from
Mitchell (1974) who found that ammonia nitrogen is
assimilated quickly during microbial growth. Ammonia (as
NH^CL) was added to achieve quantities calculated to meet
nitrogen requirements of the bacteria.
Biodegradation experiment number 2 was designed to
evaluate the efficacy of oxygen gas in addition to hydrogen
peroxide (Table 4-2). Sterile controls were maintained in
treatments 2C, 2F and 21. Ammonium chloride and hydrogen
peroxide were added as in biodegradation experiment #1.
Oxygen was added by bubbling O^ gas into a closed 3 liter
flask filled with 1200 mL of contaminated well water. A
valve allowed for pressure relief. Water was released
through a glass tube at the bottom of the flask, fitted with
a teflon stopcock. Vials were filled as described in the
sorption experiments. The vials used in both batch
biodegradation experiments were placed in an incubator (20
1 C) and inverted once every two days to provide mixing.
Samples were taken at 0, 2, 7, 14, 21 and 35 days.


87
Table 5-10 Calculated values of R, K. and K from
analysis of solute breakthrough curves.
Compound
c. a
inf
Rb
KdC
K d
oc
log K
3 oc
Benzene
4700
1.36
0.059
393
2.60
Toluene
2600
1.55
0.091
607
2.78
Ethylbenzene
1800
1.65
0.107
713
2.85
m,p-Xylene
1700
1.85
0.140
933
2.97
o-Xylene
2200
1.60
0.099
660
2.82
Isopropylbenzene
1000
2.00
0.165
1100
3.04
n-Propylbenzene
560
2.40
0.231
1540
3.19
3 or 4 Ethyltoluene
1600
2.25
0.206
1373
3.14
l,3,5-TMBe
530
2.15
0.190
1267
3.10
2-Ethyltoluene
990
1.90
0.148
987
2.99
1,2/4-TMB f
770
2.10
0.181
1207
3.08
1,2,3-TMB9
1223
1.84
0.138
920
2.96
ainfluent concentration
calculated by curve fitting with Brenner (1962)
with P = 8.
e
Q
calculated from the relationship K, = (R-l) q/p where 0=
0.30 and p = 1.82 d
dK = K ./f where f = 0.00015.
oc d oc oc
0
1,3,5-Trimethylbenzene
^1,2,4-Trimethylbenzene
gl,2,3-Trimethylbenzene


REFERENCES
Abdul, A.S., T.C. Gibson, and D.N. Rai. (1986). The Effect of
Organic Carbon on the Adsorption of Fluorene by Aquifer
Materials. Hazardous Waste and Hazardous Materials 3(4):
429-440.
Alexander, M. (1985). Biodegradation of Organic Chemicals.
Environ. Sci. Technol. 19(2): 106-111.
Anderson, M.P. (1979). Using Models to Simulate the Movement
of Contaminants through Groundwater Flow Systems. In CRC
Critical Reviews in Environmental Control. Boca Raton,
FL: CRC Press, pp. y7-156.
Atlas, R.M. (1982). Enumeration and Estimation of Microbial
Biomass. In Experimental Microbial Ecology. R.I. Burns
and H.J. Slater (eds) : Boston, MAT: Blackwell Scientific
Co., pp. 84-102.
Bailey, G.W., and J.L. White. (1970). Factors Influencing the
Adsorption, Desorption, and Movement of Pesticides in
Soil. Residue Review. 32: 29-92.
Barbash, J., and P.V. Roberts. (1986). Volatile Organic
Chemical Contamination of Groundwater Resources in the
U.S. Journal Water Pollution Control Federation 58(5):
343-348.
Barker, J.F., and G.C. Patrick. (1985). Natural Attenuation of
Aromatic Hydrocarbons in a Shallow Sand Aquifer. In
Proceedings of NWWA/API Conference on Petroleum
Hydrocarbons and Organic Chemicals in Ground Water.
Houston, TX: National Water Well Assoc., pp. 160-176.
Bear, J. (1979). Hydraulics of Groundwater. New York: McGraw
Hill Book Co.
306


155
Based on these data, it is evident that a well adapted,
standing microbial population from Lake Alfred is capable of
degrading aromatic hydrocarbons at relatively high loadings
and short contact times. Degradation may be aided by the
development of an efficient biofilm (Bouwer and McCarty,
1984). Benzene was degraded to a lesser extent than the
alkyl aromatics and o-xylene was more resistant to microbial
degradation than the meta and para isomers. Kuhn et al.
(1985) in column studies with all three xylene isomers noted
the same phenomenon. The increased resistance of o-xylene
was also seen in the batch biodegradation data presented in
this study.
In the batch studies, benzene was degraded at higher
rates than most of the branched aromatic compounds. This is
contrary to the column data. This difference in removal
rates may be the result of longer contact time in the batch
studies. This phenomenon has important consequences for the
degradation of hydrocarbons in field studies, where high
flow rates may provide insufficient contact time for
biological removal. Flow rates were seen to significantly
affect the rates of degradation in the experimental column
system. The half life for benzene decreased from 0.120 days
at 0.01 cm/min to 0.039 days at a flow velocity of .680
cm/min. The half life for toluene decreased from 0.063
hours to 0.0097 hours.
However, these rates are derived from non-limiting
conditions and these data may not completely represent


95
maximum solubility level. Therefore/ the fact that the
isotherms are linear in this study does not confirm the
dominance of the partitioning theory.
An improved method to assess the importance of
partitioning in the sorption process at the Lake Alfred site
is to compare K values from this work with octanol-water
oc
partition coefficients (Figure 5-8) and water solubility
(Figure 5-9) from the literature. The regression
coefficients for these correlations are shown in Table 5-13.
These experimentally derived relationships can now be
compared with those from previous studies.
The experimentally derived relationships between K
^ oc
and K and K and WS were determined by regression of
ow oc
literature values of K and water solubility with K data
ow oc
from the sorption BTC data. These relationships are
log
log
K
oc
K
oc
0.31 log Kow + 1.91
-0.272 log WS (umoles/L) + 3.78
[5.2]
[5.3]
Table 5-14 compares the predicted values of K from
oc
the work of several authors (Karickhoff et al., 1979, Means
et al 1982, Chiou et al., 1983, Kenaga and Goring, 1980,
Briggs, 1981). The Kqc data from this study (Table 5-10)
consistently fall within the upper range of the predicted
values shown in Table 5-14. The relationships used to
calculate the values in Table 5-14 were based on a wide
range of organic solutes and natural sorbent materials
It


31
day at 25 C and 5 days at 10 C were reported in column
studies with mixed autochthonous flora from clean
groundwater. The meta and para isomers of xylene and 1,2,4-
trimethylbenzene were degraded more rapidly than o-xylene,
1,2,3-tjrimethy Ibenz ene or 1,3,5-trimethy lbenz ene These
studies by Kappeler and Wuhrmann (1978a,b) make up the bulk
of the work on degradation of alkyl substituted benzenes.
3.5.3 In-situ Biodegradation
Application of in-situ bioremediation technology for
the renovation of hydrocarbon contaminated aquifers is based
primarily on the work of Raymond et al. (1975a,b) and
Raymond et al. (1977) at Suntech. Nutrients and oxygen were
introduced with injection wells, and circulated through the
aquifer with pumping wells. This technique and other bio
remediation methods were reviewed by Wilson et al. (1986).
These authors noted that studies are needed to investigate
the effectiveness of natural biorestoration and to evaluate
whether enhancement of natural processes is possible or
desirable.
Transport of sufficient oxygen to subsurface microbes
is a major technical problem. Oxygen is only slightly
soluble in water and is quickly depleted during aerobic
biodegradation. Oxygen addition by air sparging, oxygen
sparging and the use of hydrogen peroxide are documented in
the literature (Lee and Ward, 1984). The use of hydrogen
peroxide appears particularly advantageous (TRI, 1982).
Hydrogen peroxide is relatively inexpensive, nonpersistent


Treatment
Day
IE
Benzene
Toluene
n>/P-Xyl
o-Xyl
3,4 ET
1,3,5
TMB
2 ET
1,2,4
TMB
1,2,3
TMB
[DO]
mg/L
0
681
1655
3613
2179
663
285
259
985
444
10.5
804
1991
4163
2555
791
322
291
1134
491
9.9
591
1429
1429
1913
572
233
219
821
373
10.2
avg
692
1692
3068
2216
675
280
256
980
436
10.2
std
87
231
1181
263
90
37
29
128
49
0.2
%var
13
14
38
12
13
13
11
13
11
2.4
3
606
1390
2333
1699
402
169
161
488
279
3.0
744
1619
1514
2056
411
204
193
188
345
1.8
648
1519
2194
1899
417
183
173
372
294
1.5
avg
666
1509
2014
1885
410
185
176
349
306
2.1
std
58
94
358
146
6
14
13
124
28
0.6
%var
9
6
18
8
2
8
8
35
9
30.9
7
243
159
36
1455
68
145
159
6
255
5.0
224
99
21
1463
68
136
150
5
242
2.4
311
195
42
1486
71
123
146
5
232
5.0
avg
259
151
33
1468
69
135
152
5
243
4.1
std
37
40
9
13
1
9
5
0
9
1.2
%var
14
26
27
1
2
7
4
9
4
29.7
238


Treatment IF
Day
Benzene Toluene m,p-Xyl o-Xyl
3,4 ET
0
681
1655
3613
2179
663
804
1991
4163
2555
791
591
1429
1429
1913
572
avg
692
1692
3068
2216
675
std
87
231
1181
263
90
%var
13
14
38
12
13
3
521
1123
2707
1549
475
408
884
1737
1143
261
500
1154
2491
1594
414
avg
476
1054
2312
1429
383
std
49
121
416
203
90
%var
10
11
18
14
23
7
507
470
48
1453
71
551
228
9
1360
53
439
466
63
1349
74
avg
499
388
40
1387
66
std
46
113
23
47
9
%var
9
29
57
3
14
-,3,5
TMB
2 ET
1,2,4
TMB
1,2,3
TMB
[DO]
mg/L
285
259
985
444
10.5
322
291
1134
491
9.9
233
219
821
373
10.2
280
256
980
436
10.2
37
29
128
49
0.2
13
11
13
11
2.4
112
169
629
258
9.0
105
106
387
181
9.8
174
160
629
285
10.6
130
145
548
241
9.8
31
28
114
44
0.7
24
19
21
18
6.7
136
163
9
251
2.4
102
134
4
206
3.0
130
146
9
233
3.0
123
148
7
230
2.8
15
12
2
18
0.3
12
8
32
8
10.1
240


Treatment 1G
Day
Benzene Toluene m,p-Xyl o-Xyl
3,4 ET
15
478
934
2036
1326
317
483
978
2116
1396
339
432
809
1747
1230
281
avg
464
907
1966
1317
312
std
23
72
158
68
24
%var
5
8
8
5
8
31
528
1028
2278
1538
326
446
859
1617
1165
217
180
372
800
610
129
avg
385
753
1565
1104
224
std
149
278
605
381
81
%var
39
37
39
35
36
.5
i
2 ET
1,2,4
TMB
1,2,3
TMB
[DO]
mg/L
132
128
434
224
7.5
138
131
440
235
8.4
118
119
370
207
129
126
415
222
8.0
8
5
32
12
0.4
6
4
8
5
5.7
152
143
483
279
7.5
101
100
317
205
8.0
60
60
207
100
7.9
104
101
336
195
7.8
38
34
113
73
0.2
36
34
34
38
2.8
243


93
5.5.3 Comparison of Column and Equilibrium Isotherm Data.
Retardation factors (Table 5-11 ) and sorption
coefficients (Tables 5-10 and 5-7) from the column data and
the equilibrium data isotherm compare favorably. On
average, values from regression analysis of isotherm data
using the linear model overestimate the value of the
sorption coefficients by 40%, and the Freundlich model
underestimates the value of the sorption coefficients by 33%
relative to the column derived sorption coefficients.
Based on this comparison, the column data appear to
fall within a range of values bounded by the batch isotherm
data. In the following discussion, sorption coefficients
from the column data are used to evaluate various sorption
relationships. Column data are used here since they are
equivalent to the isotherm data, and also since the column
data provide values for ethylbenzene and the propylbenzenes
which were not evaluated in the isotherm studies owing to
low concentrations in the well water.
The retardation values of aromatic hydrocarbons in
these experiments are relatively low. The retardation
values from the column studies range between 1.36 and 2.40.
These data indicate that the most retained solute will
continue to move at 42% the rate of water movement. Thus
solutes may be expected to move relatively rapidly through
the site.


equal to the area above the BTC when the effluent
concentration (C) divided by the influent concentration (C )
was plotted vs pore volume as described by equation [4.1]
R = / [1-C/Cq] dpv
[4.1]
where pv is the total number of pore volumes displaced
through the column, and pv is pore volumes (Nkedi-Kizza et
al. 1987). This method assumed a mass balance existed in
the soil columns. The third method set the retardation
factor (R ) to equal the number of pore volumes required
for the effluent concentration of each analyte to reach 0.5
of the influent concentration. The use of this method
assumes that the breakthrough curve is symmetrical and
sigmoidal, and that equilibrium conditions exist between the
solution and sorbed concentrations during leaching through
the column (Nkedi-Kizza et al., 1987). The value of was
calculated from the various R values with equation [3.10].
4.9 Hydrogen Peroxide Evaluation
The reaction rate of hydrogen peroxide in the aquifer
environment was simulated by monitoring the dissolved oxygen
(DO) (YSI model 5739 probe and YSI model 54A DO meter),
redox potential (platinum redox electrode, Fisher
Scientific) and pH (gel membrane electrode, Fisher
Scientific) of well water and aquifer material in a 3 arm
500 mL reaction flask. Contaminated well water was


181
Precision and accuracy data for the analysis of aromatic
hydrocarbons in groundwater by EPA method 602,
(modified).
Compound
Precision
% RSD, sd
Accuracy
% R, sd
Benzene
6.6,
8.7
98.0,
13.4
Toluene
6.2,
9.3
99.3,
18.0
Ethylbenzene
5.1,
7.0
95.2 ,
12.7
m rp-Xylene
4.2,
4.2
95.3,
12.1
o-Xylene
4.8,
4.7
100.8,
15.9
Isopropylbenzene
5.8,
13.2
00
KD

00
11.3
n-Propy1benzene
5.7,
8.3
86.5,
10.7
3,4-Ethyltoluene
4.5,
6.1
90.4,
10.2
1,3,5-Trimethylbenzene
7.3,
16.2
89.6,
12.7
2-Ethyltoluene
4.0,
4.7
83.8,
10.2
1,2,4-Trimethylbenzene
4.4,
3.6
90.0,
15.2
1,2,3-Trimethylbenzene
6.1,
5.5
93.0,
12.2


19
universally significant. These authors cited several
studies where removal of organic carbon from a soil actually
increased the amount of sorption, or had no negative effect
on the sorption values. These authors suggested that
molecular structure of the solute may be a better predictor
of sorption to sediments than water solubility or
octanol/water partition coefficients. This results from the
observation that with a relatively rigid adsorbing surface,
the conformation of the solute molecule will greatly affect
its adsorption (i.e., steric effects), but not its
partitioning between an organic phase and water.
Recently, first order molecular connectivity indexes
(^X) were shown to be well correlated with K values
oc
(Sabljic, 1984, Sabljic, 1987). Molecular connectivity is
described as a quantitative measure of the area occupied by
the projection of the non-hydrogen skeleton of a molecule.
The correlation between K and the first order molecular
oc
connectivity index supports the contention that the process
of soil
sorption may be v
iewed as an
at
tracti
ve int
eracti
between
two planes, with
the magnitude
of
the
inter
action
directly
proportional to
the surface
ar
ea
of
the mo
lecule
This suggests that the so
il sorption
and
part
itioni
ng
process
reflect different
mechanisms
*
An
acc
urate
model
sorption
may include both
part i tionii
ng
and su
r f ace
area
dependen
t affects.
The relationship be
tween K and
oc
is
(Sabij
ic ,
1987):


67
Table 5-3. Regression parameters for the analysis of
average values of equilibrium batch isotherm
sorption data with the linear model
(suppressed intercept).
Compound
Na
c b
(St?L)
V
stdC

y-int
2
r
Benzene
14
950
0.069,
0.005
0
0.904
Toluene
14
4200
0.051,
0.009
0
0.636
m,p-Xylene
16
4300
0.096,
0.004
0
0.960
o-Xylene
16
2500
0.099,
0.003
0
0.978
3 or 4 ETe
11
935
0.093,
0.010
0
0.850
1,3,5TMBf
11
460
0.146,
0.007
0
0.969
2-ET9
11
373
0.108,
0.009
0
0.908
1,2,4TMBh
10
1600
0.135,
0.005
0
0.978
1,2,3TMB1
9
558
0.128,
0.008
0
0.948
anumber of data points
b . .
maximum concentration
c .
standard deviation
d .
y-intercept
e3 or 4 Ethyltoluene
^1,3,5-Trimethylbenzene
g2-Ethyltoluene
bl,2,4-Trimethylbenzene
1l,2,3-Trimethylbenzene


C / C o
PORE VOLUMES
Figure 5-27. Breakthrough curve for field tracer (NH4CI) experiment
measured at RAP-10.
15 8


119
Table 5-18. Continued.
Treatment
1,3,5-TMB
2-ET
1,2,4-TMB
1,2,3-TMB
DO
1A
k
0.140
0.165
0.193
0.140
0,
. 382
tJ*
4.96
4.20
3.59
4.94
1,
.81
2
r
0.988
0.955
0.978
0.984
0,
.990
IB
k
0.032
0.012
0.172
0.078
0.
.259
th
21.66
56.98
4.04
8.85
2,
. 68
2
r
0.139
0.012
0.925
0.526
0 .
. 952
1C
k
0.158
0.129
0.197
0.122
0.
.262
th
4.39
5.38
3.52
5.70
2.
.64
2
r
0.975
0.949
0.986
0.903
0.
.955
ID
k
0.166
0.106
0.235
0.148
0.
,310
th
4.17
6.57
2.96
4.67
2.
.24
2
r
0.969
0.889
0.964
0.933
0.
.939
IE
k
0.127
0.102
0.210
0.110
0.
.324
th
5.45
6.81
3.44
6.30
2 .
. 14
2
r
0.896
0.786
0.985
0.785
0 .
. 940
IF
k
0.176
0.151
0.167
0.169
0 .
. 074
th
3.95
4.60
4.15
4.10
9.
, 37
2
r
0.924
0.850
0.981
0.923
0.
.183
1G
k
0.171
0.176
0.170
0.174
0.
. 176
th
4.05
3.95
4.07
4.00
3.
.94
2
r
0.897
0.890
0.896
0.885
0.
.801
a
day
-1
b
days


135
Table 5-21. Biodegradation rate constants and correlation
coefficients for the fit of biodegradation
experiment #2 data to the Thomas slope rate
equation.
Treatment Benzene Toluene
Ethbz
m,p-Xylene o-Xylene
2 A
ka
0.239
0.248
0.250
0.222
0.096
r2
0.915
0.929
0.948
0.893
0.962
2B
k
0.004
0.081
0.194
0.133
0.028
r2
0.020
0.902
0.921
0.971
0.373
2C
k
0.379
0.139
0.232
0.122
0.139
r2
0.850
0.384
0.920
0.802
0.466
2D
k
0.032
-0.016
0.170
0.124
0.031
r2
0.196
0.026
0.975
0.997
0.249
2E
k
0.597
0.153
0.256
0.201
0.298
r2
0.979
0.832
0.931
0.687
0.388
2F
k
0.228
0.212
0.249
0.237
0.212
r2
0.631
0.730.
0.923
0.740
0.880
2G
0.230
0.232
_
0.227
0.215
r2
0.948
0.935
-
0.938
0.908
2H
k
0.098
0.174
0.174
0.246
0.158
r2
0.883
0.974
0.977
0.937
0.960
21
k

_
0.287
0.123

r2
-
-
0.957
0.651
-


172
velocities at the field site, and suggested that the contact
time was suitable for complete degradation of aromatic
solutes, under non-limiting conditions. This indicated the
need for oxygen augmentation at the field site to increase
the biodegradation rates of aromatic contaminants.
Batch biodegradation experiments were performed to
assess the efficacy of various methods to increase the
%
biological degradation of dissolved aromatic hydrocarbons at
the Lake Alfred field site. Laboratory experiments with
hydrogen peroxide indicated the ability of the microbial
community and the aquifer materials to catalyze the
reduction of hydrogen peroxide to yield oxygen gas. No
hydrocarbon oxidation was apparent as a result of the
hydrogen peroxide decomposition.
The half lives for biolo.gical removal of the selected
aromatic hydrocarbons with the addition of air (7-8 mg/L C^)
in the batch biodegradation studies (Treatment 1A, Thomas
slope rate equation) ranged from 2.91 days for toluene to
4.96 days for 1,3,5-trimethyIbenzene. Benzene, toluene and
1,2,4-trimethylbenzene were degraded most rapidly.
Augmentation of oxygen in the form of air or oxygen gas was
most effective for increasing the biodegradation of aromatic
hydrocarbons. These data indicated that the microbes from
the Lake Alfred site were well adapted to aromatic gasoline
hydrocarbons, and were limited only by the availability of
oxygen. Treatment with hydrogen peroxide (17 mg/L to 68
mg/L) increased the dissolved oxygen levels in the


LOO AMOUNT SORBED
3
Freundlich sorption-desorption isotherm for o-Xylene
at equilibrium.
198


Treatment 2E
treatment #2E
day 0
BNZ
TOL
ETH BZ m,p-XYL
o-XYL
1238
7083
227
6498
3185
1826
10286
330
9320
4225
1350
7355
226
6903
3353
1155
6310
91
6246
3048
avg
1392
7759
219
7242
3453
std
260
1509
85
1223
459
%variance
19
19
39
17
13
treatment #2F
DAY 2
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
799
3996
38
3568
1929
518
2596
23
2203
1221
640
3415
32
3259
1770
avg
652
3336
31
3010
1640
std
115
574
6
584
303
%variance
18
17
20
19
18
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
1443
509
415
1899
689
7.50
2153
769
624
2805
1036
1576
569
462
2031
765
1432
527
428
1941
758
1651
594
482
2169
812
7.50
295
104
84
370
133
0.00
18
17
17
17
16
0.00
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
695
254
239
972
396
9.00
403
146
135
539
227
8.10
664
252
224
944
253
8.50
587
217
199
818
292
8.53
131
50
46
198
74
0.37
22
23
23
24
25
4.31
260


88
Table 5-11. Retardation factors calculated from leaching
column and equilibrium batch isotherm data
Compound
ii
ii
11 73
IIQJ
II (U
II
II
II
II
II
II
R b
: = = £¥ = = = = =
ii
O 11
Hll
CC II
ii
ii
ii
R d
Ben zene
1.45
1.17
1.60
1.36
Toluene
1.73
1.33
1.72
1.55
Ethylbenzene
1.73
1.49
,e
nd
1.65
m,p-Xylene
1.99
1.66
1.76
1.85
o-Xylene
1.68
1.39
1.58
1.60
Isopropylbenzene
2.08
1.82
nd
2.00
n-Propylbenzene
2.49
2.29
nd
2.40
3 or 4 Ethyltoluene
2.32
2.05
1.86
2.25
1,3/5-Trimethylbenzene
2.26
2.02
1.94
2.15
2-Ethyltoluene
2.02
1.74
1.49
1.90
1,2,4-Trimethylbenzene
2.20
1.92
1.99
2.10
1,2/3-Trimethylbenzene
1.93
1.67
2.03
1.84
aR retardation factor
breakthrough curve.
calculated
from the
area of
the
R retardation factor
volumes at C/C = 0.5
o
calculated
from the
number
of pore
c
R. retardation factor
1
calculated
from equilibrium
batch
isotherm data.
Ja
retardation factor calculated from fitting column data
to the solution of Brenner (1962).
0
not determined


61
5.3 Characterization of Aquifer Materials
An analysis of a sub-sample of the aquifer materials
used in the laboratory experiments is presented in Table 5-
1. All experiments with aquifer material were performed
with subsamples of well-mixed aquifer material. Single size
fractions of aquifer material were not used since
extrapolation from one size fraction to another has been
shown to lead to errors in the estimation of sorption values
(Abdul et al./ 1986). Unwashed, natural sorbent material
from the Lake Alfred site was used in this study to more
closely approximate field conditions. The organic carbon
content of this material was low, and particle size analysis
indicated the dominance of fine to medium grained sands.
The pH of the aquifer material was in the range suitable for
biological degradation, and was consistent with the pH
values in the well water.
5.4 Batch Sorption Studies
5.4.1 Sorption Rate Studies
Rate studies were conducted to determine the sorption
kinetics of the selected aromatic solutes with Lake Alfred
aquifer material. These experiments established the
equilibration time for the sorption isotherms. The approach
to equilibrium is shown in Figure 5-1. These curves
are


183
6.0 SAMPLING PROCEDURES
6.1Cleaning Procedures
6.1.1 Volatile Organics.
Bottle type: water: 60 mL glass vial with
teflon lined septum caps.
- soil: 1 quart mason jars.
Soap: Alconox
1) Wash caps, liners and vials in hot soapy
water .
2) Rinse liberally with tap and DI water.
3) Rinse with pesticide grade methanol.
4) Dry caps, septa, and vials in oven at 105
C for no more than 60 minutes.
5) Cool in inverted position, and cap
immediately when bottles are cool enough
to handle.
6.1.2 Labels
1)After cleaning the appropriate label is
attached to each bottle, and the date cleaned
is entered.
6.2Field Documents and Records.
6.2.1 Field sheets.
The field sheet (see attachments) is filled
in with the following information upon
sampling:
1) date
2) time
3) sample type
4) preservation
5) well number (for well samples)
6) well casing and diameter
7) depth of water at time of sampling
8) depth of core (if applicable; soil
samples)
9) note special characteristics of
sample.
10)field number
All field measurements are recorded in the
bound field notebook or on the data sheets.


276
Values are as ug/L
ISPBZ
NPBZ
3,4ET
135TMB
2 ET
124TMB
123TMB
Co = 151
850
2318
836
1479
1145
1786
1.9
1.6
10.5
1.4
2.8
2.2
9.1
0
1.1
5.7
0.9
1.9
1.3
5.3
0
0.6
2.7
0.8
4.2
1.5
1.7
6
0.9
7.3
0
1.6
1.4
1.9
3.1
2
8.4
2.2
9.2
2.9
9.3
21.8
5
27
7.9
34
13
44
68
16
81
26
89
45
130
165
44
204
65
194
109
267
260
78
333
107
290
170
386
359
120
462
155
382
231
501
484
193
727
228
497
335
645
557
245
774
273
563
389
712
564
255
799
284
578
409
748
607
276
860
303
612
428
776
635
302
920
324
641
463
805
658
307
943
330
654
467
819
711
353
1048
367
710
521
899
627
306
915
323
631
460
798
638
312
933
326
636
451
800
673
333
977
348
672
491
837
667
334
926
345
668
481
838
592
289
889
313
616
445
793
659
325
1040
340
663
464
845
709
360
1058
373
718
529
896
522
240
789
274
549
349
702
735
364
1111
382
736
539
908
710
355
1057
365
702
567
871
730
368
1106
378
725
532
895
776
393
1144
402
767
559
948


151
Table 5-23. First order biological rate constants and
half-lives of aromatic hydrocarbons for the
biodegradation column with flpw at 1 mL/min.
Compound
ka
. -1
day
1/2
day
Benzene
17.7
0.040
Toluene
71.1
0.010
Ethylbenzene
125.3
0.006
m,p-Xylene
133.1
0.005
o-Xylene
115.2
0.006
Isopropylbenzene
166.7
0.004
n-Propylbenzene
192.4
0.004
3 or 4 Ethyltoluene
172.4
0.004
1/3,5-Trimethylbenzene
178.1
0.004
2-Ethyltoluene
158.4
0.004
1,2,4-Trimethylbenzene
172.3
0.004
1,2,3-Trimethylbenzene
150.6
0.005
£
calculated with the following data:
length = 5.0 cm
pore water velocity = 0.680 cm/min
particle density = 2.6 g/mL
bulk density = 1.82 g/mL
volumetric water content = 0.30


WELL OHM-2
QM1D CftYS
BENZENE
TOL
EIHBZ
M,P-XYL
O-XYL
isoffiZ
rv-EBZ
3,4ET
1351143
2ET
1241MB
1231MB
02-01-86
0
1.04
0.43
3.36
2.57
5.47
2.97
2.35
7.53
2.96
02-27-86
26
03-07-86
34
695
03-20-86
47
03-27-86
54
04-25-86
82
424
05-23-86
111
06-25-86
144
75
1416
632
839
523
232
224
343
710
465
07-18-86
167
305
180
17
55
18
40
11
5
6
43
08-28-86
208
0
09-19-86
229
33
22
12
20
20
20
444
10-22-86
262
5
2
3
2
2
2
3
3
6
4
11-23-86
294
1
1
1
1
1
6
12-10-86
311
2
14
5
17
8
1
4
8
3
6
7
01-27-87
359
1
4
1
6
3
3
4
3
3
02-20-87
383
1
1
1
2
03-17-87
408
27
77
50
300
56
24
25
70
29
64
305
04-29-87
451
0.6
0.1
0.1
0.1
1.1
0.1
0.6
0.3
0.6
05-29-87
481
1
2
0
1
2
1
1
9
1
1
6
06-23-87
506
5
3
18
8
3
13
14
6
4
14
5
293


Treatment #2C
DAY 21
BNZ
TOL
ETH BZ
m,p-XYL
O-XYL
712
3677
61
3026
1726
822
4227
69
3448
1969
730
3662
59
2960
1688
avg
755
3855
63
3145
1794
std
48
263
4
216
124
%variance
6
7
7
7
7
Treatment #2C
DAY 35
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
922
4052
71
3244
1847
595
2619
41
1828
1087
713
3451
58
2735
1568
avg
743
3374
56
2602
1501
std
135
588
12
586
314
%variance
18
17
22
23
21
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
550
214
197
764
353
8.00
631
247
227
875
391
7.50
546
209
193
764
342
7.70
576
223
206
801
362
7.73
39
17
15
52
21
0.21
7
8
7
7
6
2.66
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
579
226
209
806
348
6.90
294
118
111
427
193
7.30
491
194
177
686
294
7.60
455
179
166
640
278
7.27
119
45
41
158
64
0.29
26
25
25
25
23
3.95
252


Treatment #2C
DAY 6
BNZ
TOL
ETH BZ
m,p-XYL
O-XYL
652
3428
52
2843
1590
740
3812
67
3131
1668
598
3065
45
2473
1409
avg
663
3435
55
2816
1556
std
59
305
9
269
108
%variance
9
9
17
10
7
Treatment #2C
DAY 14
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
893
4426
81
3543
1986
849
4222
74
3333
1870
854
4549
81
3339
2147
avg
865
4399
79
3405
2001
std
20
135
3
98
114
%variance
2
3
4
3
6
3,4ET
135TMB
2ET
124TMB
12 3 TMB
[DO]
533
199
180
712
312
7.40
558
203
185
730
308
7.30
482
176
163
644
285
7.90
524
193
176
695
302
7.53
32
12
9
37
12
0.26
6
6
5
5
4
3.48
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
617
237
219
868
369
8.10
575
217
203
786
341
7.50
735
298
254
1040
440
7.80
642
251
225
898
383
7.80
68
34
21
106
42
0.24
11
14
9
12
11
3.14
251


174
confirmed by the laboratory biodegradation experiments,
where the microbes from the field site were well adapted and
were able to rapidly degrade the aromatic solutes to less
than 0.5 ug/L. Microbial populations at the field site were
5 6
determined to be -in the range of 10 to 10 organisms per
gram dry weight of soil.
6.1.5 Field Scale Solute Transport
The distribution of contaminants at the Lake Alfred
field site was complicated by physical structures, numerous
spills and underground utilities. This made the
interpretation of field data difficult. The major
concentrations of benzene were found at the western boundary
of the field site, down gradient from the spill area. This
distribution of benzene demonstrates that the combination of
low retardation and inefficient biodegradation can result in
increased migration, relative to solutes which were more
retarded and more easily degraded.


104
Table 5-15.
Regression coefficients for the relationship
between log K and -*-X.
r oc
Slope
0.360
Std. error of slope
0.050
Y-intercept
1.509
Std. error of
y-intercept
0.072
r2
0.839
Number of
observations
12
Degrees of freedom
10


TABLE OF CONTENTS
Pa9e
ACKNOWLEDGEMENTS iii
LIST OF TABLES vii
LIST OF FIGURES x
ABSTRACT... xii
CHAPTERS
I INTRODUCTION 1
II OBJECTIVES 6
III LITERATURE REVIEW 7
3.1 Introduction... 7
3.2 Environmental Effects of Gasoline
Contamination 7
3.3 Convective-Dispersive Models.. 10
3.4 Sorption of Aromatic Compounds... 13
3.5 Biodegradation of Aromatic Compounds.... 24
3.6 Summary 33
IV MATERIALS AND METHODS 34
4.1 Introduction 34
4.2 Site Description 34
4.3 Aquifer Material... 35
4.4 Choice of Solutes 38
4.5 Hydrocarbon Analyses 40
4.6 Hydrolysis Studies 42
4.7 Batch Sorption Studies 43
4.8 Column Sorption Studies 45
4.9 Hydrogen Peroxide Evaluation.... 47
4.10 Batch Biodegradation Studies 48
4.11 Column Biodegradation Studies 53
4.12 Field Studies. 56
V RESULTS AND DISCUSSION 59
5.1 Introduction 59
5.2 Hydrolysis of Aromatic Compounds 59
5.3 Characterization of Aquifer Materials... 61
5.4 Batch Sorption Studies 61
v


C / C o
Figure 5-14.
Relative concentration vs. time for five aromatic compounds
in biodegradation treatment 1A.
121


1,2,3-Trimethylbenzene Desorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
252
34.37
558
32.1
18
2.36
55.8
a
3 2
0.63
11.2
a
1.5
0.135
5.6
a
215
4.48
429
82
99
5.77
257
44
22
0.61
434
1
4.2
0.04
15
2
2.77
0.63
6
0
amount
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentrat ion
306
105.6
2.02
2.75
37.8
13.0
1.12
1.75
8
2.8
0.44
1.05
4.1
1.4
0.15
0.75
214
73.8
1.87
2.63
158
54.5
1.74
2.41
412
142.1
2.15
2.64
10.8
3.7
0.57
1.18
3.23
1.1
0.05
0.78
a
n= 1
212


66
and Table 5-3. The Freundlich regression parameters are
presented in Table 5-4.
There is no significant difference (student's t-test,
0.05 level) between sorption coefficients predicted with the
linear model and those predicted with the linear model with
suppressed intercept. The sorption coefficients are
determined form the slope of the linear isotherms. In
addition, statistical determination of the confidence
intervals of the y-intercepts indicate that there is no
significant difference between the predicted value of the y-
intercept in the linear model and zero at the 0.05
significance level, confirming that these two models are
analogous. Equivalence between these two models is expected
since the sorbed concentration should equal zero when no
solute is added to the system. A non zero intercept is an
indication of nonlinearity in the isotherm. In most cases
both linear models fit the data well as evidenced by the
relatively high coefficients of determination (r ). Based
on these analyses, the isotherms for the sorption of
aromatic solutes from Lake Alfred water onto Lake Alfred
aquifer material were concluded to be linear. The
coefficients of determination for toluene in both linear
models were substantially lower than for other compounds in
this study. The linear model with suppressed intercept
accounted for only 63.6% of the total sum of squares
deviations about the means for the 14 values in the toluene
isotherm. This suggested that this model was not


128
teflon septa. The loss of volatile compounds was
exacerbated by storage at 20 C. However, this does not
account for the increased reduction of C H. concentrations
y z
relative to the more volatile C,-Cn. C^-C values would
bo DO
normally exhibit greater volatile losses. The
biodegradation data were not corrected for these losses.
5.10 Batch Biodegradation Experiment #2
were
oxyg
some
expe
bett
expe
acti
of INT to INT-forma
The data from
models as described
consistently good f
to first order) and
the data well as ev
determination.
Average values
shown in Table 5-19
coefficients for th
s experiment were fi
section 5.9. No si
to the data. Mixed
ero order rate equat
need by low coeffici
hydrocarbons in the
Rate constants, and
it of biodegradation
The second series of batch biodegrada
performed to assess the efficacy of s
en addition to the Lake Alfred aquifer
of the previous treatments. In this
riments, additional sterile controls w
er assess the losses exhibited in biod
riment #1 (treatment IF). In addition
vity was measured by quantifying the m
zan.
thi
in
it
z
ide
of
e f
tion experiment
everal methods
, and to repeat
series of
ere added to
egradation
, microbial
icrobial reduct
t to
several ra
ngle
model gave
order
(z ero ord
ions
did not ma
ents
of
microcosms are
regression
#2 data to the
s
of
ion
te
a
er
tch


based potable water supplies, and the hydrogeology of
Florida.
The major sources of petroleum contamination in Florida
are leaking storage tanks and pipes. The high water table
in the state leads to conditions favorable for corrosion.
As of February 1986 there were 455 known storage tank
incidents resulting in 368 cases of groundwater
contamination. The total volume of spilled gasoline exceeds
4.2 million gallons (FLDER, 1986). The remaining 60,000
petroleum storage tanks in the state provide potential
sources for future groundwater pollution.
These sources of contamination are particularly
significant owing to the importance of groundwater in
Florida. Groundwater withdrawal for potable water use is
approximately 1400 Mgal/d, comprising 87% of public water
and 94% of rural water supplies. It is noteworthy that
nearly 2 million residents drink untreated water from
shallow private wells which are particularly prone to
contamination from underground storage tanks (Fernald and
Patton, 1984).
Hydrogeology is the third factor which contributes to
the sensitivity of Florida's water supplies to gasoline
contamination. Most of the potable water aquifers are
surficial or intermediate in depth, and are susceptible to
contamination. In addition, the generally porous nature of
top soil in the state enhances pollutant transport to the
underlying aquifers. Most soils in Florida are sandy loam,


WELL OHM-4
EME
CMS
BENZENE
TOLUENE
EIHBZ
M,P-XYL
O-XYL
isoPBZ
n-PBZ
3,4ET
135TM3
2ET
124TM3
123TM3
02-01-86
0
10171
32229
2956
18866
8228
6375
1887
1962
7653
2116
02-27-86
26
3930
15197
1925
15246
6979
5299
1616
1418
6245
1635
03-07-86
34
7835
21200
2288
15561
6928
54%
1793
1675
6107
1675
03-20-86
47
5683
17373
2229
15062
6718
4984
1773
1517
5733
1576
03-27-86
54
10290
18441
2381
14170
6158
5595
2482
2653
7263
2417
04-25-86
82
8323
22376
3124
21098
9106
6836
1754
1694
7664
1990
05-23-86
111
4824
20232
2530
17039
7187
5145
2073
1608
5789
1429
06-25-86
144
3109
15756
4756
9805
4069
5160
1251
1304
5485
1411
07-18-86
167
4087
12807
2649
13030
5463
4247
966
1119
5121
1181
08-28-86
208
8540
25654
2703
10644
5262
4127
2400
5483
09-19-86
229
7945
29956
2746
11210
5454
3315
1735
1270
4585
2276
10-22-86
262
986
2887
509
1158
648
499
960
510
10-25-86
265
7545
21466
2087
10523
5091
131
291
3019
1227
1081
4019
1201
10-28-86
268
3284
11339
1895
9729
4337
209
476
4006
1734
1455
5110
1512
11-04-86
275
4294
13190
2158
8886
4021
170
370
3085
1336
1102
3491
1164
11-07-86
278
4300
14416
2724
10012
4412
196
538
3434
1471
1411
4119
1581
11-19-86
290
2729
9669
1313
7349
3166
119
215
2993
926
830
3229
1073
11-23-86
294
2512
10217
2180
7848
3499
158
441
2932
894
901
3037
1061
12-10-86
311
2117
10845
1589
9737
4073
138
258
2819
904
777
3440
1110
01-27-87
359
4472
19193
2943
12400
5433
132
284
2460
784
663
2858
1036
02-20-87
383
1260
3853
1559
8429
3706
156
274
2974
1248
894
3711
1334
03-17-87
408
1500
6160
923
8176
3519
76
81
2432
881
704
3027
1099
04-29-87
451
6681
46241
2269
18555
9215
68
55
3276
1181
986
4150
1516
06-23-87
506
1551
16940
1837
7006
3314
54
114
1102
411
336
1462
524
295


3,4-Ethylto 1uene Sorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
758 3
12.34
934.8
517.4
43.9
3.52
93.5
a
9
0
18.7
a
4.1
0.63
9.35
a
1 .97
0 .14
3.74
a
0.72
0.02
1.87
a
532
64
812
133
167
7
301
17
47
4
81
2
14.5
2
18
4
5
1
9
0
amount
sorbed
(ug/L)
amoun t
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentrat ion
176.5
60.9
1.78
2.97
49.6
17.1
1.23
1.97
9.7
3.3
0.52
1.27
5.25
1.8
0.26
0.97
1.77
0.6
-0.21
0.57
1.15
0.4
-0.40
0.27
280
96.6
1.98
2.91
134
46.2
1.66
2.48
34
11.7
1.07
1.91
3.5
1.2
0.08
1.26
4
1.4
0.14
0.95
a
n = l
199


Treatment 1G
Day
Benzene
Toluene m,p-Xyl o-Xyl
3,4 ET
0
565
1484
3375
2013
612
615
1339
3158
2237
694
654
1443
4053
2463
847
avg
611
1422
3529
2238
718
std
36
61
381
184
97
%var
6
4
11
8
14
3
551
1066
2686
1789
453
118
258
545
371
125
510
1018
2722
1779
483
avg
393
781
1984
1313
354
std
195
370
1018
666
162
%var
50
47
51
51
46
7
504
992
1623
1590
368
626
1207
2820
1889
448
511
1038
2585
1692
427
avg
547
1079
2343
1724
414
std
56
92
518
124
34
%var
10
9
22
7
8
.,3,5
TMB
2 ET
1,2,4
TMB
1,2,3
TMB
[DO]
mg/L
270
249
881
409
9.0
303
271
1066
469
8.6
389
336
1192
560
8.3
321
285
1046
479
8.6
50
37
128
62
0.3
16
13
12
13
3.3
215
191
701
346
8.0
53
51
184
93
7.8
228
197
728
353
7.8
165
146
538
264
7.9
80
67
250
121
0.1
48
46
47
46
1.2
166
152
554
275
8.2
206
188
658
341
8.4
196
176
643
316
8.0
189
172
618
311
8.2
17
15
46
27
0.2
9
9
7
9
2.0
242


310
Ghiorse, W.C., and D.L. Balkwill. (1985). Microbiological
Characterization of Subsurface Environments. In
Ground Water Quality. C.H. Ward, W. Giger, and P.L.
McCarty (eds): New York: John Wiley & Sons, Inc., pp.
387-401.
Gibson, D.T., and W.K. Yeh. (1973). Microbial Degradation of
Aromatic Hydrocarbons. In The Microbial Degradation of
Oil Pollutants. D.G. Ahearn and S.P. Meyers (eds):
Baton Rouge: Louisiana State Univ., pp. 33-38.
Hoag, G.E., and M.C. Marley. (1986). Gasoline Residual
Saturation in Unsaturated Uniform Aquifer Materials.
Journal of the Environmental Engineering Division,
ASCE, 112: 586-604.
Houzim, V. (1978). Alterations of the Petroleum Substance in
Rock-Water-Air and Rock-Water Interfaces. In
International Symposium on Groundwater Pollution by Oil
Hydrocarbons. Prague. Worthington, OH: National Well
Water Association.
Jamison, V.W., R.L. Raymond, and J.O. Hudson. (1976).
Biodegradation of High-Octane Gasoline. Proceedings of
Third International Biodegradation Symposium. J.M.
Sharpley, A.M. Kaplan (eds.): London, Great Britian:
Applied Science Publishers, pp. 187-196.
Jensen, B., E. Arvin, and A.T. Gundersen. (1985). The
Degradation of Aromatic Hydrocarbons with Bacteria from
Oil Contaminated Aquifers. In Proceedings of NWWA/API
Conference on Petroleum Hydrocarbons and Organic
Chemicals in Ground Water, Houston, TX Worthington,
OH: National Water Well Association, pp. 421-435.
Kappeler, T., and K. Wuhrmann. (1978a). Microbial
Degradation of the Water-Soluble Fraction of Gas Oil -
I. Water Research 12: 327-333.
Kappeler, T.H., and K. Wuhrmann. (1978b). Microbial
Degradation of the Water Soluble Fraction of Gas Oil -
II. Bioassays with Pure Strains. Water Research 12:
335-342.


52
Following sample removal for GC analysis, dissolved oxygen
was measured in each batch biodegradation vial (batch
experiments 1 and 2) with a YSI model 5739 DO probe and YSI
model 54A DO meter (Yellow Springs Instruments Co.).
Microbial activity was assessed through the measurement
of INT reduction to INT-formazan (Klein et al., 1971). Ten
grams of soil from each vial were placed in sterile 50 mL
Erlenmeyer flasks. Each flask was amended with 1 mL
distilled water and 1.5 mL of 0.4% (w/v) aqueous solution of
filter sterilized (0.2 um Gelman Metricel membrane filters)
INT (Eastman-Kodak Co.). The soil was mixed with a sterile
glass rod, capped with aluminum foil and incubated at 20 C
for 72 hours. Sterile controls were prepared by
autoclaving several flasks for 3 consecutive days for 90
minutes. Approximately 3 grams (dry weight) of soil were
removed from each flask following incubation and placed in a
test tube. Ten mL of methanol were added to each tube and
the contents were mixed on a vortex mixer for 1 minute, then
centrifuged at 800G for 20 minutes. The INT- formazan in
the methanolic extract was measured spectrophotometrically
at 480 nm against a methanol extract of soil containing no
INT. The INT-formazan concentration was derived from a
standard curve of INT-formazan in methanol.
4.10.2 Calculation of Biological Rate Constants
Aqueous concentration data from the batch
biodegradation vials were used with the regression equations
from the Freundlich fit of the batch desorption data to


Treatment #2A
DAY 6 BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
3,4ET
135TMB 2ET
124TMB
123TMB
[DO]
222
602
5
1902
1365
428
200
170
511
303
2.20
188
395
1605
1033
311
142
123
401
219
2.50
59
62
739
832
184
124
105
195
209
2.10
avg
156
353
5
1415
1077
308
155
133
369
244
2.27
std
70
222
0
493
220
100
32
27
131
42
0.17
%variance
45
63
0
35
20
32
21
21
35
17
7.50
treatment #2A
DAY 14
BNZ
TOL
ETH BZ
m,p-XYL
O-XYL
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
82
136
9
777
554
159
72
78
148
185
3.10
195
345
1201
794
241
111
122
181
125
3.70
3.80
avg
139
241
9
989
674
200
92
100
165
155
3.53
std
56
105
0
212
120
41
20
22
17
30
0.31
%variance
41
43
0
21
18
20
21
22
10
19
8.75
245


APPENDICES


C / C O
BNZ + TOL O EBZ A MPX x OX
Figure 5-18. Relative concentrations of C^-Cg aromatic hydrocarbons
vs. time in biodegradation treatment 2B.
137


TREATMENT #2C
DAY 0
BNZ
TOL
ETH BZ m,p-XYL
o-XYL
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
1238
7083
227
6498
3185
1443
509
415
1899
689
7.50
1826
10286
330
9320
4225
2153
769
624
2805
1036
1350
7355
226
6903
3353
1576
569
462
2031
765
1155
6310
91
6246
3048
1432
527
428
1941
758
avg
1392
7759
219
7242
3453
1651
594
482
2169
812
7.50
Std
260
1509
85
1223
459
295
104
84
370
133
0.00
%variance
19
19
39
17
13
18
17
17
17
16
0.00
Treatment #2C
DAY 2
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
992
4924
81
3897
2132
716
261
244
963
389
7.00
913
4703
79
3820
2099
703
265
241
949
395
7.80
1053
5580
100
4743
2547
894
331
297
1215
483
7.50
avg
986
5069
87
4153
2259
771
286
261
1042
422
7.43
std
57
372
10
418
204
87
32
26
122
43
0.33
%variance
6
7
11
10
9
11
11
10
12
10
4.44
250


6.2 Conclusions
1. Hydrolysis was not a significant removal mechanism
for aromatic hydrocarbons.
2. Solute-sorbent equilibrium was established in batch
sorption vials in four to eight hours.
3. Equilibrium batch sorption isotherms were linear.
4. Column breakthrough curves exhibited apparent
nonequilibria .
5. Solute-solute competition for sorbing sites was not
observed.
6. Equilibrium batch sorption isotherm data and
breakthrough curve data yielded similar estimates of solute
retardation and sorption.
7. Partitioning models and the first order molecular
connectivity model gave equivalent fit to the sorption data.
This supports the hypothesis that sorption results from
several processes depending on the sorbent and the solute.
8. Bacteria from the Lake Alfred site are adapted to
aromatic hydrocarbons from gasoline sources.
9. Enzymatic and nonbiological hydrogen peroxide
catalysts are present at the Lake Alfred site.
10.Hydrogen peroxide does not oxidize aromatic
hydrocarbons.


8
Despite the large number of hydrocarbons comprising
gasoline, much of the environmental concern focuses on the
water soluble components of gasoline, particularly the
single ring aromatic compounds. These compounds are of
concern based on their toxicity, aqueous solubility and
concentration in gasoline (Barker and Patrick, 1985). Acute
toxicity is associated with the water soluble fraction of
oils (Blumer et al., 1973) and the major components of the
water soluble fraction are aromatic (Coleman et al., 1984).
Data from the work of Coleman et al. (1984) showed that
although aromatic components made up only 50% of the
unleaded gasoline product in their study, 87-95% of the
components in the water soluble fraction were aromatic.
Thus in a spill situation a significant amount of the
contaminants in the water phase will be aromatic. Selected
physical properties of the compounds used in this study are
listed in Table 3-1.
The health effects from the use of gasoline
contaminated water may be significant. Benzene is a
carcinogen in rats and mice and exposure is linked with
leukemia (USPHS, 1981). The maximum contaminant level for
benzene in community drinking water supplies is 1 ppb in
Florida. Toluene, ethylbenzene and m-xylene affect the
central nervous system (Windholtz, 1976). Unleaded gasoline
induces renal and hepatocellular carcinomas in rats and the
use of petroleum contaminated water can produce elevated
levels of indoor air pollutants allowing chronic exposure to


o
o
\
o
CHLORIDE
PORE VOLUMES
+ I35TRIMETHYLBENZENE
224


215
Column Sorption Data
L = 5 cm
v = 0.204 cm/min
pv = 6.9 mL
Values are as ug/L
mL
BNZ
TOL
ETHBZ
m,p-XYL
O-XYL
1.76
3
4
2
2
2
3.74
2
3
1
2
2
4.71
48
15
3
4
7
5.71
480
158
42
37
83
6.7
1332
514
197
174
335
7.7
2040
825
413
313
598
8.7
2777
1200
677
525
922
9.69
2948
1345
831
655
1115
10.69
3341
1511
951
756
1249
12.69
3877
1826
1238
994
1553
13.69
4081
1935
1343
1070
1658
14.69
4037
1954
1380
1116
1696
15.69
4332
2124
1482
1188
1831
16.69
4420
2165
1551
1246
1905
17.69
4589
2189
1641
1315
2013
18.69
4930
2462
1793
1431
2171
19.69
4531
2368
1801
1472
2183
20.69
4727
2468
1889
1528
2266
21.69
4871
2505
1883
1534
2267
22.69
4523
2415
1904
1537
2301
23.69
4615
2377
1802
1460
2210
24.69
4851
2621
2104
1713
2499
26.69
5454
2985
2385
1952
2905
27.69
5177
2794
2192
1802
2696
28.69
5563
2999
2386
1947
2897
30.7
5345
2838
2213
1822
2759
31.7
5197
2 77 6
216 8
1776
2666


treatment #2F
DAY 21
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
542
2770
24
2229
1298
820
4048
40
3374
1928
1309
6405
66
5357
3008
avg
890
4408
43
3653
2078
std
317
1506
17
1292
706
%variance
36
34
40
35
34
treatment #2F
DAY 35
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
659
3131
31
2542
1473
635
3035
27
2497
1449
avg
647
3083
29
2520
1461
std
12
48
2
22
12
%variance
2
2
6
1
1
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
378
146
138
531
246
7.30
583
228
221
854
403
7.70
920
349
334
1305
568
7.50
627
241
231
897
406
7.50
223
83
80
317
131
0.16
36
35
35
35
32
2.18
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
428
166
157
606
266
6.30
427
170
157
614
268
7.60
428
168
157
610
267
6.95
0
2
0
4
1
0.65
0
1
0
1
0
9.35
262


AN EVALUATION OF THE ATTENUATION MECHANISMS
FOR DISSOLVED AROMATIC HYDROCARBONS FROM GASOLINE
SOURCES IN A SANDY SURFICIAL FLORIDA AQUIFER
By
JOSEPH TIMOTHY ANGLEY
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA


Table 5-19. Continued.
Treatment
Compound
Day
2A
2B
2C
2D
2E
2F
2G
2H
21
m,p-Xylene 0
7241.75
7241.75
7241.75
7241.75
7241.75
7241.75
1573.67
1573.67
1573.67
3
973.67
3245.00
4153.33
3448.00
2542.50
3010.00
5.17
112.93
824.50
7
1415.33
1561.00
2815.67
1905.17
2504.33
2456.67
17.27
7.50
859.50
14
989.00
662.50
3405.00
555.00
2312.67
2872.33
54.15
11.45
762.50
21
1030.00
704.93
3144.67
135.33
3368.00
3653.33
16.10
28.00
756.50
35
420.67
63.33
2602.33
486.5
1626.67
2519.50
5.93
10.00
652.67
o-Xylene
0
3452.75
3452.75
3452.75
3452.75
3452.75
3452.75
1121.33
1121.33
1121.33
3
1629.33
1835.00
2259.33
1848.33
1407.50
1640.00
23.97
754.33
655.50
7
1076.67
1192.00
1555.67
1313.00
1396.00
1346.67
59.70
144.00
717.00
14
674.00
870.00
2001.00
416.00
1326.67
1611.67
70.28
41.25
604.50
21
605.00
810.33
1794.33
588.67
1899.33
2078.00
59.77
24.00
622.50
35
241.67
102.33
1500.67
346.50
1397.33
1461.00
13.57
74.00
532.00
3,4-ET
0
1651.00
1651.00
1651.00
1651.00
1651.00
1651.00
462.67
462.67
462.67
3
299.67
588.00
771.00
769.33
437.50
587.33
6.75
54.67
144.00
7
307.67
327.33
524.33
336.67
412.00
450.00
7.30
5.70
144.00
14
200.00
157.00
642.33
95.67
331.00
483.00
12.55
3.35
119.50
21
236.33
163.67
575.67
46.00
561.00
627.00
5.90
8.00
111.50
35
110.00
18.67
454.67
93.00
295.33
427.50
1.77
6.00
99.67
1,3,5-TMB
0
593.50
593.50
593.50
593.50
593.50
593.50
174.33
174.33
174.33
3
261.00
215.00
285.67
277.33
156.50
217.33
48.75
79.67
58.50
7
155.33
125.33
192.67
160.00
153.67
160.00
3.17
12.90
57.50
14
91.50
100.50
250.67
79.00
143.00
182.33
9.38
6.00
53.00
21
105.67
99.33
223.33
72.33
217.67
241.00
13.47
12.50
52.00
35
54.00
11.00
179.33
47.00
154.33
168.00
1.87
8.50
44.33
130


314
Rao, P.S.C., A.G. Hornsby, D.P. Kilcrease, and P. Nkedi-Kizza.
(1985). Sorption and Transport of Hydrophobic Organic
Chemicals in Aqueous and Mixed Solvent Systems: Model
Development and Preliminary Evaluation. J. Environ. Qual.
14: 376-382.
Rao, P.S.C., and R.E. Jessup. (1983). Sorption and Movement of
Pesticides and Other Toxic Organic Substances in Soils.
In Chemical Mobility and Reactivity in Soil Systems.
Madison, WI": Soil Science Soc. of America, p"I Ch. TJ.
Raymond, R.L., V.W. Jamison, and J.O. Hudson. (1975a).
Beneficial Stimulation of Bacterial Activity in
Groundwaters Containing Petroleum Products. AIChE
Symposium Series 73. pp. 390-404.
Raymond, R.L., V.W. Jamison, and J.O. Hudson. (1975b). Final
Report on Beneficial Stimulation of Bacterial Activity in
Groundwaters Containing Petroleum Products. Washington,
D.C.: American Petroleum Institute, API Project OS21.2,
Raymond, R.L., V.W. Jamison, and J.O. Hudson. (1977).
Bacterial Growth in and Penetration of Consolidated and
Unconsolidated Sands Containing Gasoline. Washington,
D.C.: American Petroleum Institute, API Project 307-76.
Roberts, P.V., M. Reinhard, G.D. Hopkins, and R.S. Summers.
(1985). Advection-Dispersion-Sorption Models for
Simulating the Transport of Organic Contaminants. In
Ground Water Quality. C.H. Ward, W. Giger, and P.L.
McCarty (eds): New York: John Wiley & Sons, Inc., pp.
425-445.
Rodgers, R.D., J.C. McFarlane, and A.J. Cross. (1980).
Adsorption and Desorption of Benzene in Two Soils and
MontmorilIonite Clay. Environ. Sci. Technol. 14: 457-461.
Sabljic, A. (1984). Predictions of the Nature and Strength of
Soil Sorption of Organic Pollutants by Molecular
Topology. J. Agrie. Food Chem. 32(2): 243-246.


46
crimp seal vials with Teflon coated septa for later
analysis. All samples were analyzed within 48 hours.
The breakthrough of an unretained solute was determined
for each column using calcium chloride (1 ml/min columns).
Breakthrough curves were determined by spiking hydrocarbon
free groundwater from Lake Alfred (RAP-2) with chloride (600
mg/L CaCL^). Chloride analyses were performed with a
chloridometer automatic titrator (Buchler-Cotlove).
Chloride ion was not expected to be adsorbed owing to the
low cation exchange capacity of the Lake Alfred soil.
Well water used in the sorption experiments was
filtered through 0.2 um membrane filters (Gelman Metricel)
directly into the Teflon bags. The bags were autoclaved
prior to each use. Columns were saturated with filter
sterilized water from well RAP-2 prior to the input of
solute containing water.
4.8.2 Estimation of Retardation Factor (R) in Columns
Three methods were used to estimate the value of R from
the column data. In method 1, retardation factors (R ) were
calculated by fitting the solution of Brenner (1962) to the
column effluent curves. Peclet numbers used for these
calculations were determined from the breakthrough of the
non-retained solutes having retardation factors equal to
unity. Method 2 was based on the conservation of mass
principle. This method calculated retardation factors (R )
cl
by evaluating the area above the breakthrough curve using
Simpson's Rule (Swokowski, 1975). The R value was assumed
cl


treatment #21
day 21
BNZ
TOL
ETH BZ
m,p-XYL
O-XYL
177
236
bdl
786
639
174
223
bdl
727
606
avg
176
230
0
757
623
std
2
7
0
30
17
%variance
1
3
ERR
4
3
treatment #21
day 35
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
107
151
514
442
156
214
5
707
577
170
221
5
707
577
avg
144
195
5
643
532
std
27
31
0
91
64
%variance
19
16
0
14
12
3,4ET
135TMB
2ET
124 TMB
12 3 TMB
[DO]
116
53
59
239
139
7.90
107
51
56
223
136
7.90
112
52
58
231
138
7.90
5
1
2
8
2
ERR
4
2
3
3
1
ERR
3,4ET
135TMB
2ET
124TMB
123 TMB
[DO]
79
36
41
166
104
6.20
110
49
57
218
131
5.50
110
48
55
213
127
7.20
100
44
51
199
121
6.30
15
6
7
23
12
0.70
15
13
14
12
10
11.07
271


42
The meta and para isomers of xylene were not resolved
on either chromatographic system employed in this research.
The combination of these analytes was reported as m,p-
xylene. Likewise, 3-ethyltoluene and 4-ethyltoluene were
not resolved with the analytical system employed in this
study, and the combined concentrations of these analytes
were reported in this study with the abbreviation 3,4-
ethyltoluene.
4.6 Hydrolysis Studies
Hydrolysis studies were performed in 5 mL glass ampules
(Fisher Scientific). Ampules were rinsed with methanol and
oven dried at 105 C Ten microliters of hydrocarbon
contaminated groundwater were spiked into ampules containing
5 mL of buffer solution. Buffer solutions were prepared
wi
th non
conta
minated w
ell water, and the pH was
adjusted to
pH
= 2.0,
7.0,
9.2, and
12.0 with 0.01 M
phosphat
e
buffers.
Th
e ampul
es we
re sealed
with an ampule s
ealer (Oc
eanographic
In
ternati
onal,
College
Station TX), and
autoclaved
(1 hour
at
120 C)
. On
e set of
ampules was analyzed at ti
me
z ero .
Another s
et of
ampules
was stored in the
dark at
20
, 40 and
60
C and
anal y
zed by ga
s chromatography
(GC) after
60 days.


1J
o
O
\
O
1 -
0.9 -
0 2 4 6
PORE VOLUMES
Breakthrough curve for toluene in column biodegradation
experiments performed at a flow rate of 1 mL/min.
280


Table 5-28. Water chemistry parameters from selected monitoring wells at Lake
Alfred CREC, 1986.
Well
Chloride,
mg/L
Conductivity,
umhos pH
Dissolved
Oxygen,
mg/L
Total
Phosphate,
mg/L
Nitrate,
mg/L
OHM-1
-
270-
302
6.1-6.6
0.2-0.7
0.19
-
OHM-2
793
2100-
2700
6.1-6.9
0.2-0.7
1.40
0.94
OHM-3
18
350-
390
5.9-6.6
0.1-0.3
0.62
0.14
OHM-4
16
290-
333
6.1-6.7
0.2-0.3
0.40
0.20
P-5
19
340-
390
6.1-6.7
0.2-0.6
0.47
0.19
P-6
19
245-
300
6.4-7.2
0.4-0.8
0.33
0.22
P-7
21
278-
410
5.8-7.1
0.3-0.4
0.34
0.24
UF-1E
21
270-
353
5.8-6.6
0.9-3.5
0.47
-
UF-2M
12
315-
382
5.4-6.7
0.7-0.8
0.58
0.14
UF-3W
16
470-
700
6.1-6.7
0.1-0.5
0.82
0.19
RAP-2
22
278-
325
6.1-7.1
0.9-4.1
0.65
0.29
RAP-4
-
300-
319
6.1-6.9
0.5-1.8
0.53
-
RAP-5
-
262-
280
5.8-6.9
0.2-2.2
0.57
0.15
RAP-6
-
290-
317
6.2-7.1
1.4-3.9
0.65
0.41
RAP-7
0
315-
325
6.3-7.1
1.7-4.8
0.67
0.43
166


C / C o
13
13
1J
7
0.9
03
0.7
0.0
OS
0.4
03
03
0.7
0
Figure 5-5. Breakthrough curve for benzene from Lake Alfred water (C = 4700 ug/L)
oo
LO
A
jBqB
A
=uA -A A
V'
f
i /
r r
/
/
/ /
/ /
/
/ ;
~T
2
T
4
PORE VOLUMES
n CHLORIDE + BENZENE


142
their higher vapor pressure (95 torr for benzene and 29 torr
for toluene compared with 6 torr for m-xylene at 25 C). The
half lives for biodegradation under these conditions were in
the same range as those for the higher concentrations (i.e.
treatment 2A). Degradation to the low ug/L level was noted
for all compounds. The most recalcitrant was o-xylene. The
addition of NH^Cl produced the same effect noted in other
treatments. The lag phase seemed to be especially
significant for benzene, o-xylene, 1,3,5-trimethylbenzene,
2-ethyltoluene and 1,2,3-trimethylbenzene. As in previous
experiments, 1,2,4-trimethylbenzene was well degraded under
all non-sterile conditions. The reduced treatment of
solutes in 2H was accompanied by consumption of oxygen and
an apparent increase in microbial activity. The DO profiles
show that the concentration of dissolved oxygen remained
above 4 mg/L throughout the entire study, indicating no
oxygen limitation.
5.10.5 Treatments 2C, 2F, 21 (Sterile Controls)
Sterility in treatments 2C, 2F and 2G was indicated by
the lack of 0^ consumption, low INT reduction and the
persistence of aromatic hydrocarbons. The losses (assumed
to result from diffusion through the teflon septa) were in
the range of 0-25% for G^-Cg hydrocarbons and 20-50% for
C9H12 compounds. Sorption losses were accounted for in
these data by adding the amount lost to sorption to the
aqueous concentration data. The drop in DO in treatment 2G
indicated that oxygen also diffuses through the teflon


167
The opposite appears to be true in data from well P-7.
This well shows significant decreases in some aromatic
hydrocarbons, and the dissolved oxygen levels start to
increase after November, 1986. This may be the result of
the increased recharge of aerated water and change in
pumping conditions established by Killan (1987). Decreases
in hydrocarbon concentrations concomitant with increasing DO
are also noted up gradient of P-7 prior to November 22,
1986. Wells RAP-6 and RAP-5 exhibit rapid removals of
hydrocarbons following the start of increased flushing with
aerated water (22 October, 1986). However, the data are
insufficient to conclude whether this change results from
the increased supply of oxygenated water and subsequent
biodegradation, or if it is caused by the more rapid solute
transport owing to increasing the flow velocity of the
aquifer.


5-13 Reaction of OHM-4 well water to the
addition of 50% hydrogen peroxide and aquifer
material . . 110
5-14 Relative concentration vs. time for five aromatic
compounds in biodegradation treatment 1A 121
5-15 Relative concentration vs. time for four CgH^
compounds in biodegradation treatment 1A....... 122
5-16 Concentration vs. time for dissolved oxygen
in biodegradation treatments 1A, IB and 1C 124
5-17 Concentration vs. time for dissolved oxygen
in biodegradation treatments ID, IE, IF
and 1G 126
5-18 Relative concentrations of C -Cg aromatic
hydrocarbons vs. time in biodegradation
treatment 2B 137
5-19 Relative concentrations of C^-Cg aromatic
hydrocarbons vs. time in biodegradation
treatment 2D 139
5-20 Concentration vs. time for dissolved oxygen
in biodegradation treatments 2D, 2E and 2F 140
5-21 Electron transport activity in biodegradation
treatments 2D, 2E and 2F 141
5-22 Electron transport activity in biodegradation
treatments 2A, 2B and 2C 145
5-23 Breakthrough curves for aromatic compounds in
column biodegradation experiments performed
at a flow rate of 0.90 mL/hr 148
5-24 Breakthrough curve for benzene in column
biodegradation experiment performed at a flow
rate of 1 mL/min 152
5-25 Breakthrough curve for toluene in column
biodegradation experiment performed at a flow
rate of 1 mL/min 153
5-26 Breakthrough curve for 1,2,4-trimethylbenzene
in column biodegradation experiment performed
at a flow rate of 1 mL/min..... 154
xx


LIST OF TABLES
Table Page
3-1 Selected physical properties of study compounds 9
3-2 Summary of adsorption data for aromatic
hydrocarbons 23
3-3 Sorption coefficients of selected aromatic
hydrocarbons on low organic soil 25
4-1 Experimental design for batch biodegradation
experiment #1 49
4-2 Experimental design for batch biodegradation
experiment #2 51
5-1 Selected physical and chemical properties of the
Lake Alfred aquifer material 62
5-2 Regression parameters for the analysis of
average values of equilibrium batch isotherm
sorption data with the linear model 65
5-3 Regression parameters for the analysis of
average values of equilibrium batch isotherm
sorption data with the linear model (supressed
intercept).. 67
5-4 Regression parameters for the analysis of
average values of equilibrium batch isotherm
data with the Freundlich model.... 68
5-5 Ratios of sorbed concentrations calculated from
Freundlich and linear equilibrium models 71
5-6 Regression parameters for the analysis of
average values of equilibrium batch
desorption data with the linear model 76
5-7 Regression parameters for the analysis of
average values of equilibrium batch .
desorption data with the linear model
(supressed intercept) 77
vii


275
L = 5 cm
v = 0.204 cm/min
1 pore volume = 6.94 ML
Values are as ug/L
CUMM ML
BNZ
TOL
EBZ
MPX
O-XYL
Co = 5000
2862
2449
2092
2805
1.78
0.7
2.9
0.9
2.8
3.4
3.78
0.7
6.4
0.9
2.1
1.9
4.78
0.7
9.2
0.8
2.9
2.5
5.8
54.4
12.9
2.3
2.6
4.9
6.8
465.6
122.3
26
23.4
50.4
7.8
1346.1
398.7
122
106
211
8.8
2231
769
331.6
251
484
9.8
3104
1186
608
473
817
10.8
3472
1373
775
610
1008
11.8
3822
1552
922
728
1170
13.8
4206
1740
1082
874
1338
15.8
4360
1851
1173
951
1428
16.8
4401
1846
1170
961
1445
17.8
4631
1948
1240
1007
1516
18.8
4414
1921
1264
1038
1531
19.8
5027
2093
1313
1071
1593
20.8
4774
2106
1373
1145
1633
21.8
4302
1897
1245
1016
1498
22.8
4577
1968
1266
1036
1515
25.8
4668
2056
1342
1097
1607
26.8
4642
203 5
1320
108 7
1578
27.8
4385
1889
1205
986
1487
28.8
4632
2011
1307
1067
1569
29.8
4541
2064
1386
1147
1658
30.8
4378
1809
1080
900
1371
31.8
4730
2149
1437
1193
1710
32.8
4579
2065
1383
1134
1636
33.8
4648
2119
1422
1173
1681
34.8
4914
2241
1513
1237
1780
Pore water velocity
= 0.680
cm/min.
Particle
density = 2
.6 g/mL
.
Bulk density = 1.82 g/mL.
Volumetric water content = 0.30


Toluene Desorption Data
amount
(ug/L)
Cw
(ug/L)
sorbed
avg
std
avg
std
(ug/L)
295
219
4566
653
4271
93
36
1086
a
992
6
2.8
456
a
450
1
0.35
46
a
45
784
214
4069
172
3285
3
2
406
a
403
7
a
41
a
34
n = 1
a
log
log
amount
amount
solution
sorbed
sorbed
concentr
(ng/g)
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
1474
3.17
3.66
342
2.53
3.04
155
2.19
2.66
15.4
1.19
1.66
1133
3.05
3.61
139
2.14
2.61
11.7
1.07
1.61
191


C / C o
u
15
v
1
0.9
05
0.7
O.Q
05
OA
05
05
OJ
0
f
S"
/
t
/
'+

Â¥
;/
/
P /
/ *
B
0 7
CHLORIDE
T"
2
T
3
PORE VOLUMES
+ ISOPROPYLBENZENE
T
4
5
222


77
Table 5-7. Regression parameters for the analysis of
average values of equilibrium batch
desorption data with the linear model
(suppressed intercept).
Compound
Na
c b
Kdd'
stdC
y-int
2
r
Benzene
5
950
0.251,
0.004
0
0.998
Toluene
8
4200
0.304,
0.008
0
0.992
m p-Xylene
9
4300
0.190,
0.005
0
0.992
o-Xylene
9
2500
0.159,
0.010
0
0.951
3 or 4 ET8
9
935
0.256,
0.014
0
0.967
1/3,5 TMB f
8
460
0.1968
0.003
0
0.997
2-ET9
7
373
0.570,
0.007
0
0.999
1,2,4-TMBh
10
1600
0.202,
0.004
0
0.996
1,2,3TMB1
9
558
0.221,
0.022
0
0.870
number of data points
b . .
maximum concentration
Q
standard deviation
d .
y-intercept
e3 or 4 Ethyltoluene
^1,3,5-Trimethylbenzene
g2-Ethyltoluene
nl/2,4-Trimethylbenzene
1l,2,3-Trimethylbenzene


28
Over a six week period only toluene showed substantial
degradation, but after 40 weeks, benzene was reduced by 72%,
toluene by 99%, ethylbenzene by 74% and o-xylene by 78%.
Nutrient addition decreased the rate of hydrocarbon removal.
The metabolic products from the anaerobic degradation of the
aromatic molecules were not investigated. Nitrate
respiration of xylene in a river alluvium was demonstrated
by Kuhn et al. (1985). However, anaerobic
biotransformations occur extremely slowly (months), relative
to aerobic processes which may be completed in a matter of
hours (Wilson, 1985).
Physical properties of the aquifer also play an
important role in determining the extent of microbial
degradation. Porosity and hydraulic conductivity are
significant parameters since the resupply of oxygen,
substrate and nutrients to the microbial cells must come via
the groundwater.
The concentration of the contaminant substrates is an
important factor in the extent of biodegradation. High
concentrations may result in incomplete degradation
resulting from rapid depletion of oxygen and high substrate
concentrations may also lead to increased acclimation times.
Jensen et al. (1985) demonstrated an increase in the time
required for acclimation (lag time) of bacterial cultures
with increasing concentrations of napthelene. Lag times
prior to substantial microbial degradation of a solute
nutrient reflects the time required by the indigenous
or


4
3C/ at = D ( 3C/ 3x2 ) v ( 3C/ 3x ) p/ 0( as/ 3t) Q. [1.1]
where C
S
0
t
x
P
Dh
V
Qi
= solution phase concentration of solute (ug/L)
= adsorbed phase concentration of^solute (ng/g)
= volumetric water content (mL/cm;
= time (min)
= horizontal distanc^ (cm)
= bulk density (g/crn )
= hydrodynamic dispersion coefficient (cm /min)
= average pore water velocity (cm/min)
= degradation rate (min )
The components of this equation are convection,
dispersion, sorption and degradation terms. Convection
describes the movement of a dissolved contaminant with the
groundwater. Dispersion describes the spreading of the
solutes during flow through the aquifer material. Sorption
terms account for the retardation of the dissolved solutes
by interaction with the aquifer matrix, and degradation
terms evaluate the removal or transformation of the
contaminants. Research has shown that sorption and
biological degradation are the major attenuation mechanisms
for organic solutes in soils and groundwater (Woodburn,
1985 ) .
Mathematical models based on such equations are
important tools for the prediction of contaminant movement
(Pinder, 1984). However, the adequacy of these predictions
is directly related to a knowledgeable and accurate
quantification of the processes involved (MacKay et al ,
1985). The remediation of groundwater contamination also


APPENDIX B
FIELD SAMPLING PROCEDURES
The sampling procedures employed during this research
were described in the Lake Alfred Quality Assurance/Quality
Control (QA/QC) plan (Killan, 1987). Section six of the QA/QC
plan is presented in the following pages.
182


163
Table 5-24. Microbial populations in a soil core
taken south of the paint shop (Bldg. 54),
June, 1986.
a 5
CFU/gdw x 10
Depth,
feet avg. std. dev.
4.15
4.00
1.53
4.67
5.28
0.72
5.46
3.07
0.56
aCFU/gdw:
colony forming units per gram dry weight
Table 5-25. Microbial populations in a soil core
taken in the spray field, June, 1986.
CFU/gdwax 105
Depth,
feet avg. std. dev.
LO

O
82.3
5.18
1.0
30.8
0.54
1.5
8.77
0.66
2.0
4.21
0.36
3.0
4.59
2.83
aCFU/gdw:
colony forming units per gram dry weight


144
in the aquifer at the Lake Alfred site and the low dissolved
oxygen levels in the aquifer indicate that there may be
significant levels of nitrifying bacteria which may be
stimulated by the addition of NH Cl. Indirect evidence for
this hypothesis is seen in the results of the INT studies
for treatments 2A and 2B. Treatment 2B showed a seven-fold
increase in electron transport activity although there was
no substantial decrease in hydrocarbon concentration (Figure
5-22).
The microorganisms in this study are able to degrade
aromatic hydrocarbons rapidly down to the 1 ug/L range given
sufficient oxygen. These data confirm the work of Jensen et
al. (1985) who show the degradation of aromatic hydrocarbons
in petroleum contaminated groundwater to 1 ug/L or less.
The rates of biodegradation determined from these batch
biodegradation studies were significantly faster than that
of Kappeler and Wuhrmann (1978b). In that study benzene
required 12 days to degrade completely. Delfino and Miles
(1985) showed an eight day lag phase for benzene dosed to
clean groundwater. In this study, benzene was completely
removed in a minimum of two days, indicating the adaptation
of bacteria from the Lake Alfred site to degrade aromatic
hydrocarbons.
5.10.7 Hydrogen Peroxide
The introduction of hydrogen peroxide into the
microcosms produced a lag phase. The microbial populations
required several days to adapt to the changing environmental


274
Column Biodegradation Data
PV
Values are C/Co
BZ TOL EBZ MPX
OX
0.000
0.000
0.000
0.570
0.042
0.009
0.812
0.104
0.023
1.020
0.185
0.039
1.283
0.253
0.059
1.437
0.255
0.069
1.579
0.266
0.071
1.711
0.286
0.078
1.908
0.273
0.084
2.105
0.314
0.104
2.303
0.287
0.098
2.500
0.300
0.103
2.664
0.286
0.107
3.323
0.225
0.092
3.718
0.280
0.116
4.112
0.306
0.121
4.277
0.385
0.155
6.481
0.350
0.154
7.435
0.386
0.143
7.962
0.376
0.147
L = 2.5 cm
v = 0.003 crn/min
pore water velocity =
bulk density = 1.8
particle density = 2.6
0.000
0.000
0.000
0.034
0.000
0.009
0.047
0.000
0.000
0.008
0.017
0.009
0.025
0.038
0.017
0.035
0.041
0.036
0.051
0.045
0.041
0.016
0.052
0.051
0.024
0.045
0.024
0.073
0.049
0.029
0.088
0.052
0.031
0.092
0.057
0.035
0.107
0.080
0.047
0.110
0.081
0.047
0.106
0.088
0.053
0.129
0.090
0.050
0.127
0.083
0.051
0.134
0.090
0.059
0.143
21290
cm/day
g/ml
g/ml


157
5.12.1 Dispersion
The breakthrough curve for the NH^Cl tracer at the Lake
Alfred site is shown in Figure 5-27. The dispersion
2
coefficient calculated from these data was 0.546 cm /min.
Compared with the dispersion coefficients from the column
experiments performed at 0.680 cm/min (0.01-0.07 cm /min),
the field scale dispersion is an order of magnitude larger
than the column data. The calculated is approximately
25. This value should be useful in the modeling of the Lake
Alfred aquifer.
5.12.2 Solute Transport
An analysis of solute transport at the Lake Alfred
research site is hampered by geologic and man-made
obstacles. The presence of a swale running through the site
and of a dual flow pattern around the pump house (Building
12) have produced preferential flow in the aquifer. Also,
sewer, drainage, steam and telecommunications lines criss
cross contaminated portions of the aquifer, complicating the
flow path of dissolved hydrocarbons. It is also probable
that gasoline storage tanks in between Buildings 10 and 12
and transfer equipment south of the wash rack added unknown
quantities of gasoline to portions of the study area
(Killan, 1987). This skews the distribution of hydrocarbons
in the aquifer and makes determination of solute transport
difficult. Finally, the pumping wells (UF-2M, RAP-1 and
RAP-3) distort the transport of contaminants. Less
retarded solutes appear to be more retained by reversal of


27
availability of an appropriate electron acceptor- Oxygen is
used as the ultimate electron acceptor for aerobic
degradation processes and is often a limiting factor in the
degradation of hydrocarbons. Molecular oxygen is also
essential to the aerobic metabolism of aromatic compounds,
because it is incorporated into the structure of the
metabolic products (Evans, 1977). The biochemistry of the
aerobic metabolism of aromatic compounds is well established
(Dagley, 1975). The first step in this metabolic pathway
is the removal of side chains, followed by the enzyme
(oxygenases) mediated hydroxylation of the aromatic ring.
Assuming 50% conversion of carbon to biomass and incomplete
oxidation of the hydrocarbon molecules, two parts of oxygen
are required for the degradation of each part hydrocarbon
(Wilson et al., 1986). The complete oxidation of
hydrocarbon molecules to CO^ and H2 four parts of oxygen per part hydrocarbon.
There is some evidence for the anaerobic biodegradation
of aromatic compounds in the environment. In the absence of
oxygen, nitrates, sulfates and CC>2 become electron
acceptors. Bouwer and McCarty (1984) presented a review of
these processes. Nitrate respiration (Psuedomonas and
Moraxella sp.) and methanogenic fermentation processes can
reduce the benzene nucleus followed by hydrolysis to yield
aliphatic acids (Evans, 1977). Wilson and Rees (1985)
showed the anaerobic degradation of benzene, toluene,
xylenes and alkylbenzenes under methanogenic conditions.


20. Microbial populations at the Lake Alfred site were
oxygen limited, but not phosphorus or nitrogen limited.
21. Horizontal dispersion at the field site was
2
calculated to be 0.546 cm /min.
22. Low retardation (1.36), high flow velocity (0.680
cm/min) and a degradation rate of 17.65 ug/L/day explain
the distribution of benzene at the field site.


21
3.4.5 Sorption Kinetics
Hysteretical behavior may actually be a manifestation
of sorption-desorption kinetics. Rao and Jessup (1983)
noted that the influence of non-singular isotherms (ie.,
isotherms which display hysteresis) on solute movement may
be less significant than the effects of sorption
nonequilibria. In a study of the transport of pesticides at
high concentrations, Rao and Davidson (1979) noted that the
position of an adsorbed solute in a breakthrough curve was
governed by the nature of the equilibrium adsorption
isotherm equation, whereas the shape of the curve was
defined by the kinetics of the sorption-desorption process.
Sorption reactions between hydrophobic pollutants and
sediments are generally rapid and not rate limited (Weber et
al 1983). Rao and Davidson (1980) concluded that many
sorption reactions are complete within one minute in batch
slurry experiments, although longer times to equilibrium
were noted in several studies (Karickhoff et al., 1979,
Miller and Weber, 1984). Schwarzenbach and Westall (1981),
in a comparison of solute breakthrough at various flow
velocities, concluded that values from column experiments
_3
where velocity was less than 10 cm/second were similar to
values from 18 hour equilibrium batch studies.
3.4.6 Aromatic Sorption Values From The Literature
There are few data in the literature addressing
sorption of dissolved gasoline components in the subsurface.
Much of the research involved aromatic compounds in single


APPENDIX D
BREAKTHROUGH CURVE DATA FOR THE SORPTION OF STUDY
COMPOUNDS TO LAKE ALFRED AQUIFER MATERIAL
This appendix presents the breakthrough data for the
aromatic solutes used in this study. The data is presented
as concentrations (ug/L) and as C/Cq (effluent concentration/
influent concentration). Following these data, plots of C/Cq
vs. pore volumes are presented for those compounds not shown
graphically in the body of the dissertation. The final page
of this appendix presents the data for the single solute
breakthrough of benzene.
214


60
0.05 level) change in concentration of analytes over the pH
range tested (pH 2,7,9,12).
Only one compound, 1,2,3-trimethylbenzene, demonstrated
a significant (student's t-test, 0.01 level) temperature
effect at pH values of 7,9 and 12. This change in
concentration occurs only at 40 C, and the concentration
values at 20 and 60 C are equivalent for all pH values.
These data are not consistent with data from other aromatic
compounds in this study, which showed no change in
concentration with varying temperatures. The apparent loss
of solute seen for 1,2,3-trimethylbenzene was likely the
result of working near the detection limit of the analytical
system, or the result of experimental error.
The absence of concentration differences across a wide
range of pH and temperature for the 60 day ampules implies
that hydrolysis was not a significant mechanism for removal
of aromatic hydrocarbons. This was expected, owing to the
resistance of aromatic structures to nucleophilic attack by
water. This results from the electronegativity associated
with the delocalization of electrons in the pi bonds of the
aromatic nucleous. McCarty (1984) has noted that chemical
hydrolysis may occur, but that for most compounds this
process was slow relative to biological removal rates. In
addition, hydrolysis results in simple changes in the
molecular structure, whereas biological transformations
often result in the mineralization of organic compounds to
carbon dioxide and water.


51
Table 4-2. Experimental design for batch biodegradation
experiment #2.
Treatment #
Oxygen
addition
NH4C1
(mg/L)
Sodium
Azide
(mg/L)
2A
air
none
none
2B
air
18
none
2C
air
none
1.25
2D
60 mg/L ^22
none
none
2 E
60 mg/L H22
18
none
2F
60 mg/L H 02
none
1.25
2G
0^ saturation
none
none
2H
0^ saturation
18
none
21
O2 saturation
none
1.25


57
6, P-7, UF-1E, RAP-4, OHM-4, UF-2M and UF-3W were also
monitored periodically for the following two weeks.
The breakthrough of the tracer was calculated in pore
volumes using the equation
pv = vt/L [4.8]
where pv is pore volumes, t is time (hours), L is the
distance between RAP-9 and RAP-10 (5 ft) and v is the
seepage velocity (ft/hour)from work by Killan (1987).
4.12.2 Water Quality Monitoring
Samples for hydrocarbon analysis were taken from
selected monitoring wells monthly from February 1, 1986 to
June 1987. Sampling procedures are detailed in Appendix B.
Hydrocarbon analyses were as described previously using the
three chromatographic methods as they became available. The
pH, temperature, dissolved oxygen, and conductivity were
measured periodically in selected wells. Sampling
procedures are detailed in Appendix B.
Total phosphorus concentrations were determined in all
monitoring wells (EPA method 365.1). All phosphorus forms
were converted to orthophosphate by autoclaving with
potassium permanganate in an acidic medium. Orthophosphate
was determined spectrophotometrically at 880 nm with a
Perkin Elmer model 552 spectrophotometer.
Chloride was determined colorometrically in each
monitoring well over several months to determine background
levels of chloride via EPA method 325.1. Average background
concentrations were 20+8 mg/L. Nitrate was
measured with


313
Moore, J.W., and E.A. Moore. (1976). Environmental
Chemistry. New York: Academic Press.
Nathawani, J.S., and C.R. Phillips. (1977). Absorption-
Desorption of Selected Hydrocarbons in Crude Oil on
Soils. Chemosphere 6: 157-162.
Nkedi-Kizza, P., P.S.C. Rao, and A.G. Hornsby. (1987). The
Influence of Organic Co-Solvents on Leaching of
Hydrophobic Organic Chemicals through Soils. Environ.
Sci. Technol. 21(11): 1107-1111.
Pinder, G.F. (1984). Groundwater Contaminant Transport
Modeling. Environ. Sci. Technol. 18(4): 108-114.
Rao, P.S.C. (1985). Class Lecture Notes, SOS 6622.
University of FLorida, Soil Science Department.
Rao, P.S.C., and J.M. Davidson. (1979). Adsorption and
Movement of Selected Pesticides at High Concentrations
in Soils. Water Research 13: 375-380.
Rao, P.S.C., and J.M. Davidson. (1980). Estimation of
Pesticide Retention and Transformation Parameters
Required in Non-Point Source Pollution Models. In
Environmental Impact of Non-Point Source Pollution.
M.R. Overcash and J.M. Davidson (eds): Ann Arbor, MI:
Ann Arbor Science Publishing Inc., pp. 23-67.
Rao, P.S.C., J.M. Davidson, R.E. Jessup and H.M. Selim.
(1979). Evaluation of Conceptual Models for Describing
Non Equilibrium Adsorption-Desorption of Pesticides
During Steady Flow in Soils. Soil Sci. Soc. Am. J. 43:
904-912.


Treatment ID
Day
Benzene Toluene
0
706
1816
1035
2468
avg
871
2142
std
164
326
%var
19
15
3
525
1165
727
1376
514
734
avg
589
1092
std
98
267
%var
17
24
7
326
148
223
141
avg
274
144
std
52
3
%var
19
2
Xyl
o-Xyl
3,4 ET
4137
2370
769
5192
3172
948
4665
2771
858
528
401
90
11
14
10
843
1756
255
946
1899
365
168
1579
130
652
1745
250
345
131
96
53
8
38
14
1938
75
22
1412
45
18
1675
60
4
263
15
23
16
25
,3,5
TMB
2 ET
1,2,4
TMB
1,2,3
TMB
DO
mg/L
379
318
1103
519
8.8
317
281
1124
469
9.0
348
300
1114
494
8.9
31
18
10
25
0.1
9
6
1
5
1.1
235
220
133
319
2.9
214
229
130
350
1.7
194
188
7
277
2.2
214
212
90
315
2.3
16
18
58
30
0.5
8
8
65
9
21.7
186
208
4
334
4.3
121
150
6
233
6.0
154
179
5
284
5.2
32
29
1
51
0.8
21
16
16
18
16.5
236


58
an Orion nitrate electrode via standard method 418b (APHA,
1980).
4.12.3 Microbial analyses
Viable microbial cells were enumerated by plate count
technique using dilute soil extract agar (DSEA) media. This
technique was developed based on work by Ghiorse and
Balkwill (1983) and Wilson et al. (1983).
\
DSEA was prepared by autoclaving 100 g of surface soil
in 100 mL of distilled water for one hour at 120 C. The
supernatant was filtered (Whatman glass fiber filters) to
remove particulates and diluted ten fold with distilled
water and amended 1.5% (w/v) with agar (Fisher Scientific).
Ten grams of subsurface material were suspended
aseptically in 100 mL 0.1% sodium pyrophosphate (Fisher
Scientific) then appropriate dilutions were plated in
triplicate on DSEA media. All plates were incubated
aerobically at 27-30 C for ten days.


169
6.1.1 Hydrolysis studies
Hydrolysis did not account for substantial losses of
the aromatic hydrocarbons in this study. These solutes were
resistant to hydrolysis even under extreme (relative to the
environment) conditions of pH (2,9/12) or temperature (60
C) .
6.1.2 Sorption studies
Sorption of C^-Cg aromatic solutes to the aquifer
material employed in this work was relatively rapid. Rate
studies to determine the approach to equilibrium revealed
that there was an initial period of rapid sorption and that
equilibrium conditions were established within four to eight
hours.
Multicomponent sorption experiments of the dissolved
aromatic hydrocarbons in this study were performed in batch
isotherms and in leaching column experiments. Surficial
well water was used as the source of these solutes. Aquifer
material from the Lake Alfred site was used as the sorbent.
Batch sorption employed a 3:1 solids to solution ratio to
approximate aquifer conditions, and to maximize the change
in solution concentration resulting from sorption of the
solutes to the aquifer material. Equilibrium batch isotherm
data was evaluated with the Freundlich model, the linear
model and the linear model with suppressed intercept.
Sorption coefficients (K^) for the two linear models were
equivalent, and the Freundlich model gave similar sorption
coefficients (K^). values from the linear models ranged


146
conditions. This was reflected in the electron transport
activity graphs where H22 treatment reduced INT-formazan
production. This may result from the toxicity of H202 to
the microbial population.
The addition of hydrogen peroxide to the batch
microcosms did increase the DO/ especially in biodegradation
experiment #1. Initial DO levels were increased by 2 to 3
mg/L following addition of H^O^ in treatments IB and 1C.
However/ hydrogen peroxide treatment did not increase the
rates of degradation/ or improve the extent of removal of
aromatic hydrocarbons. Air or oxygen addition was shown to
be more effective methods of oxygen supplementation/ since
they did not require an adaption period.
This conclusion may not be significant under field
conditions/ where an adaption period may not be an important
drawback/ given the economy of ^22 relative to air or
oxygen addition. These studies demonstrate that H does
not limit the extent of biodegradation/ but that there is an
adaption period associated with its use. No column
experiments were performed with hydrogen peroxide. These
experiments would have assessed hydrogen peroxide reactivity
under flowing conditions.
5.11 Column Biodegradation Experiments
Several authors employed flow-through soil columns to
study the degradation of organic contaminants (Kuhn et al.;
1985). Kuhn et al. (1985) noted that if one expects to


147
apply laboratory derived rate constants to field conditions
that input concentrations should be similar to field
concentrations. The columns used in this work were packed
with soil from the Lake Alfred field site, and were supplied
with well water from Lake Alfred so that field and
laboratory conditions were closely matched. Two flow rates
were used to better simulate the varied flow conditions
present in the Lake Alfred aquifer.
The results of the columns run at low flow velocities
(0.01 cm/min) are shown in Figure 5-23. These data were
analyzed to determine rate constants, and these are shown in
Table 5-22. The rate constants were calculated with equation
[4.7]. The rates of degradation were much higher in the
column system than in the batch biodegradation system. The
rate constants of the aromatic compounds in the column
system were one to two orders of magnitude greater than
batch study constants. The increased rate of hydrocarbon
removal was the result of improved transport of carbon
sources, nutrients and oxygen to the microbial community in
the column system. The microcosms in the batch studies were
not continuously mixed so that portions of the microcosm may
have been nutrient or oxygen limited. Removal efficiencies
of 85-95% were seen for all compounds except for benzene,
which was degraded more slowly and showed a 60% percent
removal. The order of degradation was m,p-xylene >
ethylbenzene > o-xylene > toluene > benzene. This order was


11
approximations, these models provide a convenient framework
for understanding the transport of dissolved solutes in
groundwater.
The general form of the solute transport equation under
saturated flow conditions is given by Bear (1979). A one-
dimensional form of this equation for conservative
contaminants under steady flow conditions is
3C/3t = D ( 82C/Sx2)- v ( dC/dx)
[3.1]
where C =
S =
x =
V =
solution phase concentration of solute (ug/L)
sorbed phase concentration of solute (ng/g)
hydrodymanic dispersion coefficient (cm /min)
time (min)
horizontal distance (cm)
average pore water velocity (cm/min)
The major components of this equation are convection (bulk
flow) and dispersion (deviation from bulk flow). A brief
discussion of dispersion follows, with reference to
extrapolation of laboratory data to field scale
applications.
The hydrodynamic dispersion coefficient describes the
spreading of a solute as it moves through porous media.
Hydrodynamic dispersion (D ) is the sum of mechanical
dispersion, caused by differences in water velocity through
sinuous and tortuous pores, and molecular diffusion (Biggar
and Nielsen, 1962). Dispersion values reflect the
heterogeneity of the aquifer material. Dispersion is
usually determined by measuring the breakthrough of a
conservative tracer such as chloride or tritiated water.


10
a
a
7
6
5
4
3
2
1
0
V-
-X-
-x
** -* x> 0
i r i i i i i i i i i 1
20
40
60 80
100
120
+ TOL
o
TIME
EBZ
(HOURS)
A mp-XYL
X
o-XYL
sproach to
ike Alfred
equilibrium for several
aquifer material.
aromatic solutes on


Table 519. Total average hydrocarbon values (ug/L) in the microcosms of batch
biodegradation experiment #2.
Treatment
Compound
Day
2A
2B
2C
2D
2E
2F
2G
2H
21
Benzene
0
1392.25
1392.25
1392.25
1392.25
1392.25
1392.25
220.00
220.00
220.00
3
128.17
835.33
986.00
750.67
649.40
652.33
2.00
170.00
148.00
7
156.33
654.33
663.33
492.93
655.00
571.67
2.00
77.00
174.50
14
138.70
492.00
865.33
141.97
731.33
735.67
2.05
19.50
158.00
21
145.00
487.67
754.67
287.50
884.67
890.33
2.00
34.50
175.50
35
73.00
133.67
743.33
181.00
755.33
647.00
2.50
24.50
144.33
Toluene
0
7758.50
7758.50
7758.50
7758.50
7758.50
7758.50
414.33
414.33
414.33
3
197.33
4275.33
5069.00
3966.67
3299.50
3335.67
1.73
133.67
244.00
7
353.00
2675.00
3435.00
2466.33
3245.67
2871.33
7.87
49.67
329.00
14
240.50
1293.50
4399.00
704.33
3118.00
3537.00
29.48
16.00
222.00
21
235.00
1287.33
3855.33
538.33
4287.33
4407.67
1.60
34.00
229.50
35
81.00
174.67
3374.00
398.00
2637.00
3083.00
13.50
16.00
195.33
Ethbz
0
218.50
218.50
218.50
218.50
218.50
218.50
101.50
101.50
101.50
3
24.77
78.00
86.50
112.57
44.00
31.00
0.00
0.00
10.00
7
5.00
52.37
54.67
38.80
41.67
24.07
0.00
0.90
5.12
14
9.40
28.10
78.67
14.65
35.33
33.33
3.78
0.55
4.00
21
1.95
28.60
63.00
11.95
60.67
43.33
0.00
0.65
0.00
35
8 37
7.13
56.47
5.50
47.33
29.00
0.00
1.00
5.30
129


It is more likely that the increased sorption results
from some affinity of the aromatic solutes in this study for
the mineral surface of the aquifer material. This is
consistent with the findings of Schwarzenbach and Westall
(1981) and Curtis et al., (1986). These authors demonstrate
that the mineral surface area and the nature of the mineral
surface, exert a greater influence on sorption than organic
carbon for sorbents with low amounts of naturally occurring
organic material.
5.6.2 Relationship Between and K
To assess the contribution of the mineral surface in
the sorption of aromatic solutes from the Lake Alfred
aquifer, Kqc values from this study were correlated with
first order molecular connectivity indices (^X). This
relationship is shown in Figure 5-11 and the regression
parameters are shown in Table 5-15. The use of this
correlation was based on the suggestion of Milgelgrin and
Gerstl (1983) that molecular structure or topology may be
more effectively correlated with sorption than Kqw or WS.
Sabljic (1987) suggested the use of first order molecular
connectivity indices (^X) as an estimator of molecular
topology. The regression equation developed by Sabljic
(1987) is also shown in Figure 5-11. This relationship was
based on the regression of calculated ^X versus literature
values of K data,
oc
The slopes of these lines are not significantly
different at the 0.05 significance level. The correlation


treatment #2H
day 21 BNZ
TOL ETH BZ m,p-XYL O-XYL 3,4ET 135TMB 2ET 124TMB 123TMB [DO]
25
43
1
37
109
9
11
14
9
44
5.50
44
25
0
19
139
7
14
18
6
55
4.60
avg
35
34
1
28
124
8
13
16
8
50
5.05
std
10
9
1
9
15
1
2
2
2
5
0.45
%variance
28
26
100
32
12
12
12
12
20
11
8.91
treatment #2H
day 35
BNZ
TOL
ETH BZ
mfp-XYL
o-XYL
3,4ET
135TMB
2ET
124TMB
12 3 TMB
[DO]
4
5
0
5
14
3
1
5
3
7
3.50
45
27
2
15
134
9
16
20
5
54
2.40
avg
25
16
1
10
74
6
9
13
4
31
2.95
std
20
11
1
5
60
3
8
8
1
24
0.55
%variance
84
69
100
50
81
50
88
60
25
77
18.64
268


315
SabljiC/ A. (1987). On the Prediction of Soil Sorption
Coefficients of Organic Pollutants from Molecular
Structure: Application of Molecular Topology Model.
Environ. Sci. Technol. 21(4): 358-366.
Sanders, W.N., and J.B. Maynard. (1968). Capillary Gas
Chromatographic Method for Determining the C3-C
Hydrocarbons in Full Range Motor Gasolines. Anal. Chem.
40(3): 67-72.
Schwarzenbach, R.P., W. Giger, E. Hoehn, and J.K. Schneider.
(1983). Behavior of Organic Compounds During
Infiltration of River Water to Groundwater, Field
Studies. Environ. Sci. Technol. 17: 472-479.
Schwarzenbach, R.P., and J. Westall. (1981). Transport of
Nonpolar Organic Compounds from Surface Water to Ground
Water. Environ. Sci. Technol. 15: 1360-1367
Shehata, A. (1985). A Multi-Route Exposure Assessment to
Chemically Contaminated Drinking Water and Health
Significance with Emphasis on Gasoline. Augusta, ME:
Maine Dept, of Human Services.
Smith, L., and F.W. Schwartz. (1980). Mass Transport: 1. A
Stochastic Analysis of Macroscopic Dispersion. Water
Resour. Res. 16: 303-313.
Spangler, D. (1984). Hydrogeologic Study of University of
Florida Agricultural Research and Education Center,
Lake Alfred, Florida, unpublished report.
Standard Methods for the Examination of Water and Wastewater
15th Edition. (1980). Washington, D.C.: American Public
Health Assoc.
Swokowski, E.A. (1975). Calculus With Analytical Geometry.
Boston: Prindle, Weber and Schmidt, p. 209.
Thomas, H.A. (1950). Graphical Determination of BOD Curve
Constants. Water and Sewage Works 97: 123.


Table 5-2 0.. Continued
Treatment
3,4-ET 1,3,5-TMB 2-ET
1,2,4-TMB 1,2,3-TMB
2A
k
0.046
0.049
0.048
0.049
0.048
r2
0.698
0.867
0.917
0.574
0.923
2B
k
0.105
0.086
0.073
0.130
0.072
r2
0.951
0.889
0.886
0.949
0.8 7,1
2C
k
0.017
0.015
0.013
0.016
0.012
r2
0.653
0.553
0.557
0.572
0.539
2D
k
0.078
0.057
0.053
0.091
0.045
r2
0.691
0.885
0.833
0.586
0.858
2E
k
0.019
0.010
0.008
0.022
0.008
r2
0.360
0.139
0.136
0.404
0.128
2F
k
0.013
0.011
0.009
0.012
0.006
r2
0.333
0.240
0.192
0.256
0.110
2G
k
0.103
0.096
0.058
0.085
0.085
r2
0.531
0.585
0.578
0.255
0.763
2H
k
0.091
0.070
0.067
0.087
0.056
r2
0.421
0.529
0.649
0.297
0.572
21
0.024
0.018
0.021
0.016
0.014

r
0.627
0.560
0.627
0.614
0.651
a
Ethylbenzene


72
sorption from the two models are consistently close to one
over the entire concentration range tested.
Freundlich isotherms for benzene and toluene are shown
in Figures 5-2 and 5-3. Graphs of Freundlich isotherms for
the remaining solutes are presented in Appendix C. Average
values are plotted in Figures 5-2 and 5-3 and error bars
showing one standard deviation in the experimental
determination of the sorbed concentrations are presented to
give an indication of the variance in these data. Standard
deviations for all compounds are shown in Appendix C. The
influence of dissolved organic carbon was not assessed
during this study. However, based on the work of Curtis et
al., (1986) with a sandy aquifer material (0.02% organic
carbon), organic carbon in this study was not expected to
decrease the values of by more than 5%. Water from the
Lake Alfred aquifer was used in these experiments, and the
organic carbon in solution was assumed to be in equilibrium
with the organic carbon on the aquifer material. Therefore,
dissolution of additional organic carbon into solution
should have been minimal, and should not be greatly
affected. This hypothesis was confirmed by evaluation of
the partitioning model as a predictive technique for
sorption of aromatic solutes to the Lake Alfred aquifer
material in section 5.6. The interaction between organic
carbon and the solutes was shown to be low.


98
Table 5-13. Regression coefficients for plots of log
K vs. log K and log K vs. log WS.
oc ^ ow ^ oc ^
Log K vs. Log K
oc ^ ow
Log Kqc vs. Log WSa
Slope
0. 310
Std. error
of slope
0.052
Y-intercept
1.909
Std. error of
y-intercept
0.073
2
r
0.857
Number of
observations
8
Degrees of
freedom
6
Slope
-0.272
Std. error
of slope
0.039
Y-intercept
3.785
Std. error of
y-intercept
0.074
2
r
0.828
Number of
observations
12
Degrees of
freedom
10
aumoles/L


Copyright 1987
by
Joseph T. Angley


o
O
\
O
15
12 -
1J -
1 -
0.9
0.8
0.7
0.6
05 -\
0.4
05
02 -|
OJ
O

B-
f
J2r~0-q0&Q-- 0
A
/
/
,-K
. k
,4K \
Â¥
Â¥
:/
Â¥
/
4-^:;
,y
T"
2
T"
4
chloride:
PORE VOLUMES
+ N-PROPVLBENZENE
Figure 5-7 Breakthrough curve for n-propylbenzene from Lake Alfred
water (C = 1000 ug/L).
03
Un


treatment #2E
day 21
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
693
3401
48
2689
1526
1160
5580
78
4406
2455
801
3881
56
3009
1717
avg
885
4287
61
3368
1899
std
200
935
13
746
401
%variance
23
22
21
22
21
treatment #2E
day 35
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
830
3654
51
2489
1397
704
3134
46
2197
1387
732
1123
45
194
1408
avg
755
2637
47
1627
1397
std
54
1091
3
1020
9
%variance
7
41
6
63
1
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
448
173
164
634
264
5.00
735
285
261
1012
428
6.10
500
195
181
682
304
5.40
561
218
202
776
332
5.50
125
48
42
168
70
0.45
22
22
21
22
21
8.27
3,4ET
135TMB
2ET
427
167
144
343
134
136
116
162
153
295
154
144
131
15
7
44
9
5
124TMB
12 3 TMB
[DO]
494
260
3.30
468
226
3.90
76
239
2.60
346
242
3.27
191
14
0.53
55
6
16.26
258


35
The research site was located on the rim of an ancient
sinkhole. The surficial aquifer was composed of sand and
clayey sands. An continuous clayey confining layer of
uneven depth was present between 7 to 12 ft below land
surface. This layer supported a saturated zone between 3 to
6 ft in thickness. Local relief was from 156 ft (above mean
sea level) at the top of the hill at the eastern boundary of
the site, to 131 ft in the wetland area at the west edge of
the site. A site map is shown in Figure 4-1. The surficial
aquifer was comprised of medium angular grained sands and
fill material. The hydrology of the site was discussed by
Killan (1987).
The surficial aquifer was contaminated during the
spring of 1983 by the loss of 7500-8000 gallons of leaded
gasoline from a storage tank. Free floating gasoline was
removed by surface skimming as of May 1985. The outline of
the contaminated area as of October, 1986 is shown in Figure
4-2. The plume was defined by determination of explosive
gas concentrations in bore holes throughout the site. These
data were confirmed by GC analysis of soil cores and the use
of ground penetrating radar. These techniques were described
in detail by Killan (1987).
4.3 Aquifer Material
Aquifer materials used in this research were obtained
from the field research site at the IFAS-Citrus Research and
Education Center at Lake Alfred Florida. A site map is



PAGE 1

$1 (9$/8$7,21 2) 7+( $77(18$7,21 0(&+$1,606 )25 ',662/9(' $520$7,& +<'52&$5%216 )520 *$62/,1( 6285&(6 ,1 $ 6$1'< 685),&,$/ )/25,'$ $48,)(5 %\ -26(3+ 7,027+< $1*/(< $ ',66(57$7,21 35(6(17(' 72 7+( *5$'8$7( 6&+22/ 2) 7+( 81,9(56,7< 2) )/25,'$ ,1 3$57,$/ )8/),//0(17 2) 7+( 5(48,5(0(176 )25 7+( '(*5(( 2) '2&725 2) 3+,/2623+< 81,9(56,7< 2) )/25,'$

PAGE 2

&RS\ULJKW E\ -RVHSK 7 $QJOH\

PAGE 3

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
PAGE 4

)LQDOO\ WKLV ZRUN ZRXOG QRW KDYH EHHQ SRVVLEOH ZLWKRXW WKH ORYH VXSSRUW DQG IULHQGVKLS SURYLGHG E\ UD\ ZLIH %HWK DOVR WKDQN P\ IDPLO\ IRU WKHLU ILQDQFLDO VXSSRUW GXULQJ P\ PDQ\ \HDUV RI VFKRROLQJ 7KLV UHVHDUFK ZDV IXQGHG WKURXJK D UHVHDUFK JUDQW IURP WKH ,QVWLWXWH IRU )RRG DQG $JULFXOWXUDO 6FLHQFHV ,9

PAGE 5

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

PAGE 6

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

PAGE 7

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f 5HJUHVVLRQ SDUDPHWHUV IRU WKH DQDO\VLV RI DYHUDJH YDOXHV RI HTXLOLEULXP EDWFK LVRWKHUP GDWD ZLWK WKH )UHXQGOLFK PRGHO 5DWLRV RI VRUEHG FRQFHQWUDWLRQV FDOFXODWHG IURP )UHXQGOLFK DQG OLQHDU HTXLOLEULXP PRGHOV 5HJUHVVLRQ SDUDPHWHUV IRU WKH DQDO\VLV RI DYHUDJH YDOXHV RI HTXLOLEULXP EDWFK GHVRUSWLRQ GDWD ZLWK WKH OLQHDU PRGHO 5HJUHVVLRQ SDUDPHWHUV IRU WKH DQDO\VLV RI DYHUDJH YDOXHV RI HTXLOLEULXP EDWFK GHVRUSWLRQ GDWD ZLWK WKH OLQHDU PRGHO VXSUHVVHG LQWHUFHSWf YLL

PAGE 8

5HJUHVVLRQ SDUDPHWHUV IRU WKH DQDO\VLV RI DYHUDJH YDOXHV RI HTXLOLEULXP EDWFK GHVRUSWLRQ GDWD ZLWK WKH )UHXQGOLFK PRGHO 9DOXHV RI 'LVSHUVLRQ FDOFXODWHG IURP WKH EUHDNWKURXJK FXUYHV RI XQUHWDLQHG VROXWHV LQ ODERUDWRU\ FROXPQV &DOFXODWHG YDOXHV RI 5 DQG IURP DQDO\VLV RI VROXWH EUHDNWKURXJK FXUYHV 5HWDUGDWLRQ IDFWRUV FDOFXODWHG IURP OHDFKLQJ FROXPQ DQG HTXLOLEULXP EDWFK LVRWKHUP GDWD $Q HPSLULFDO LQGH[ RI VRUSWLRQ QRQHTXLOLEULXP ,61(f IRU VHOHFWHG DURPDWLF VROXWHV OHDFKLQJ WKURXJK /DNH $OIUHG DTXLIHU PDWHULDO 5HJUHVVLRQ FRHIILFLHQWV IRU SORWV RI ORJ .RF YV ORJ .RZ DQG ORJ .RF YV ORJ :6 &RPSDULVRQ RI UHODWLRQVKLSV WR SUHGLFW .RF IURP .RZ YDOXHV 5HJUHVVLRQ FRHIILFLHQWV IRU WKH UHODWLRQVKLS EHWZHHQ ORJ .RF DQG ; 7RWDO DYHUDJH K\GURFDUERQ YDOXHV XJ/f LQ WKH PLFURFRVPV RI EDWFK ELRGHJUDGDWLRQ H[SHULPHQW %LRGHJUDGDWLRQ UDWH FRQVWDQWV KDOI OLYHV DQG FRUUHODWLRQ FRHIILFLHQWV IRU WKH ILW RI ELRGHJUDGDWLRQ H[SHULPHQW GDWD WR D ILUVW RUGHU UDWH HTXDWLRQ %LRGHJUDGDWLRQ UDWH FRQVWDQWV KDOI OLYHV DQG FRUUHODWLRQ FRHIILFLHQWV IRU WKH ILW RI ELRGHJUDGDWLRQ H[SHULPHQW GDWD WR WKH 7KRPDVVORSH UDWH HTXDWLRQ 7RWDO DYHUDJH K\GURFDUERQ YDOXHV XJ/f LQ WKH PLFURFRVPV RI EDWFK ELRGHJUDGDWLRQ H[SHULPHQW %LRGHJUDGDWLRQ UDWH FRQVWDQWV KDOI OLYHV DQG FRUUHODWLRQ FRHIILFLHQWV IRU WKH ILW RI ELRGHJUDGDWLRQ H[SHULPHQW GDWD WR D ILUVW RUGHU UDWH HTXDWLRQ YLLL

PAGE 9

%LRGHJUDGDWLRQ UDWH FRQVWDQWV KDOI OLYHV DQG FRUUHODWLRQ FRHIILFLHQWV IRU WKH ILW RI ELRGHJUDGDWLRQ H[SHULPHQW GDWD WR WKH 7KRPDVVORSH UDWH HTXDWLRQ )LUVW RUGHU ELRORJLFDO UDWH FRQVWDQWV DQG KDOIOLYHV RI DURPDWLF K\GURFDUERQV IRU WKH ELRGHJUDGDWLRQ FROXPQ ZLWK IORZ DW P/KU )LUVW RUGHU ELRORJLFDO UDWH FRQVWDQWV DQG KDOIOLYHV RI DURPDWLF K\GURFDUERQV IRU WKH ELRGHJUDGDWLRQ FROXPQ ZLWK IORZ DW OP/PLQ 0LFURELDO SRSXODWLRQV LQ D VRLO FRUH WDNHQ VRXWK RI WKH SDLQW VKRS EOGJ f -XQH 0LFURELDO SRSXODWLRQV LQ D VRLO FRUH WDNHQ LQ WKH VSUD\ ILHOG -XQH 0LFURELDO SRSXODWLRQV LQ D VRLO FRUH WDNHQ VRXWK RI WKH SXPS KRXVH EOGJ f MXO\ 0LFURELDO SRSXODWLRQV IURP VDPSOHV FROOHFWHG GXULQJ LQVWDVOODWLRQ RI PRQLWRULQJ ZHOOV 5$3 DPG 5$3 6HSWHPEHU :DWHU FKHPLVWU\ SDUDPHWHUV IURP VHOHFWHG PRQLWRULQJ ZHOOV DW /DNH $OIUHG &5(& L[

PAGE 10

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f %UHDNWKURXJK FXUYH IRU WROXHQH IURP /DNH $OIUHG ZDWHU & XJ/f R %UHDNWKURXJK FXUYH IRU QSURS\OEHQ]HQH IURP /DNH $OIUHG ZDWHU & XJ/f /RJ .TF YV ORJ .TZ IRU VWXG\ FRPSRXQGV /RJ IURP FROXPQ GDWDf YV ORJ :6 IRU V6XG\ FRPSRXQGV 5HJUHVVLRQ HTXDWLRQV IRU VHYHUDO PRGHOV GHVFULELQJ WKH UHODWLRQVKLS EHWZHHQ DQG Df &XUWLV HW DO r 6FKZDU]HQEDFK DQG :HVWDOO Ff WKLV VWXG\ Gf %ULJJV Hf &KLRX HW DO /RJ YV IRU DURPDWLF VROXWHV Df LQ WKLV VWXG\rDQG Ef IURP 6DEOMLF f %UHDNWKURXJK FXUYH IRU EHQ]HQH VLQJOH VROXWHf VSLNHG LQWR 5$3 ZHOO ZDWHU &R XJ/f [

PAGE 11

5HDFWLRQ RI 2+0 ZHOO ZDWHU WR WKH DGGLWLRQ RI b K\GURJHQ SHUR[LGH DQG DTXLIHU PDWHULDO 5HODWLYH FRQFHQWUDWLRQ YV WLPH IRU ILYH DURPDWLF FRPSRXQGV LQ ELRGHJUDGDWLRQ WUHDWPHQW $ 5HODWLYH FRQFHQWUDWLRQ YV WLPH IRU IRXU &J+A FRPSRXQGV LQ ELRGHJUDGDWLRQ WUHDWPHQW $ &RQFHQWUDWLRQ YV WLPH IRU GLVVROYHG R[\JHQ LQ ELRGHJUDGDWLRQ WUHDWPHQWV $ ,% DQG & &RQFHQWUDWLRQ YV WLPH IRU GLVVROYHG R[\JHQ LQ ELRGHJUDGDWLRQ WUHDWPHQWV ,' ,( ,) DQG 5HODWLYH FRQFHQWUDWLRQV RI & &J DURPDWLF K\GURFDUERQV YV WLPH LQ ELRGHJUDGDWLRQ WUHDWPHQW % 5HODWLYH FRQFHQWUDWLRQV RI &A&J DURPDWLF K\GURFDUERQV YV WLPH LQ ELRGHJUDGDWLRQ WUHDWPHQW &RQFHQWUDWLRQ YV WLPH IRU GLVVROYHG R[\JHQ LQ ELRGHJUDGDWLRQ WUHDWPHQWV ( DQG ) (OHFWURQ WUDQVSRUW DFWLYLW\ LQ ELRGHJUDGDWLRQ WUHDWPHQWV ( DQG ) (OHFWURQ WUDQVSRUW DFWLYLW\ LQ ELRGHJUDGDWLRQ WUHDWPHQWV $ % DQG & %UHDNWKURXJK FXUYHV IRU DURPDWLF FRPSRXQGV LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQWV SHUIRUPHG DW D IORZ UDWH RI P/KU %UHDNWKURXJK FXUYH IRU EHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ %UHDNWKURXJK FXUYH IRU WROXHQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ %UHDNWKURXJK FXUYH IRU WULPHWK\OEHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ [[

PAGE 12

%UHDNWKURXJK FXUYH IRU ILHOG WUDFHU 1+ FOf H[SHULPHQW PHDVXUHG DW 5$3 'LVWULEXWLRQ RI EHQ]HQH XJ/f DW WKH /DNH $OIUHG ILHOG VLWH 'LVWULEXWLRQ RI R[\OHQH XJ/f DW WKH /DNH $OIUHG ILHOG VLWH [LL

PAGE 13

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a&J+"f ZHUH GHWHUPLQHG LQ PXOWLFRPSRQHQW H[SHULPHQWV ZLWK QDWXUDO DTXLIHU PDWHULDOV XQGHU VDWXUDWHG FRQGLWLRQV +\GURJHQ SHUR[LGH DLU R[\JHQ JDV DQG DPPRQLXP FKORULGH WUHDWPHQWV ZHUH HYDOXDWHG DV PHWKRGV WR HQKDQFH PLFURELDO GHJUDGDWLRQ RI DURPDWLF K\GURFDUERQV 7KH VROXWHV DQG VRUEHQWV ZHUH IURP D JDVROLQH FRQWDPLQDWHG DTXLIHU LQ FHQWUDO )ORULGD 7KLV VLWH ZDV W\SLFDO RI VDQG\ VXUILFLDO [LLL

PAGE 14

DTXLIHUV LQ )ORULGD ZLWK D ORZ RUJDQLF FDUERQ FRQWHQW bf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

PAGE 15

RU QLWURJHQ OLPLWHG +\GURJHQ SHUR[LGH LQFUHDVHG GLVVROYHG R[\JH ODE V FRQGL VKRZQ K\GUR Q EXW GLG QRW OHDG WR LQFUHDVHG K\GURFDUERQ UHPRYDO LQ WXGLHV $PPRQLXP FKORULGH SURGXFHG QLWULI\LQJ WLRQV 2[\JHQ DXJPHQWDWLRQ ZLWK DLU DQG R[\JHQ JDV ZDV WR HQKDQFH ELRORJLFDO UHPRYDO RI DURPDWLF FDUERQV [Y

PAGE 16

&+$37(5 ,1752'8&7,21 *URXQGZDWHU FRQWDPLQDWLRQ LV D WRSLF RI JUHDW VFLHQWLILF LQWHUHVW DQG SXEOLF FRQFHUQ *URXQGZDWHU SURYLGHV DSSUR[LPDWHO\ PLOOLRQ SHRSOH ZLWK SRWDEOH ZDWHU LQ WKH 8QLWHG 6WDWHV +RDJ DQG 0DUOH\ f DQG QHDUO\ HYHU\ VWDWH FRQWDLQV VRPH QXPEHU RI FRQWDPLQDWHG ZHOOV %DUEDVK DQG 5REHUWV f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b RI ZKLFK DUH XQSURWHFWHG VWHHO WDQNV ZLWK ILQLWH OLIHWLPHV +RDJ DQG 0DUOH\ f ,W LV H[SHFWHG WKDW WR b RI WKHVH WDQNV PD\ OHDN 'RZG f *DVROLQH FRQWDPLQDWLRQ RI JURXQGZDWHU LQ )ORULGD LV D SDUWLFXODUO\ VHULRXV SUREOHP 7KLV UHVXOWV IURP WKH FRQIOXHQFH RI WKUHH IDFWRUV WKH ODUJH QXPEHU RI SHWUROHXP VWRUDJH WDQNV LQ WKH VWDWH WKH UHOLDQFH RQ JURXQGZDWHU

PAGE 17

EDVHG SRWDEOH ZDWHU VXSSOLHV DQG WKH K\GURJHRORJ\ RI )ORULGD 7KH PDMRU VRXUFHV RI SHWUROHXP FRQWDPLQDWLRQ LQ )ORULGD DUH OHDNLQJ VWRUDJH WDQNV DQG SLSHV 7KH KLJK ZDWHU WDEOH LQ WKH VWDWH OHDGV WR FRQGLWLRQV IDYRUDEOH IRU FRUURVLRQ $V RI )HEUXDU\ WKHUH ZHUH NQRZQ VWRUDJH WDQN LQFLGHQWV UHVXOWLQJ LQ FDVHV RI JURXQGZDWHU FRQWDPLQDWLRQ 7KH WRWDO YROXPH RI VSLOOHG JDVROLQH H[FHHGV PLOOLRQ JDOORQV )/'(5 f 7KH UHPDLQLQJ SHWUROHXP VWRUDJH WDQNV LQ WKH VWDWH SURYLGH SRWHQWLDO VRXUFHV IRU IXWXUH JURXQGZDWHU SROOXWLRQ 7KHVH VRXUFHV RI FRQWDPLQDWLRQ DUH SDUWLFXODUO\ VLJQLILFDQW RZLQJ WR WKH LPSRUWDQFH RI JURXQGZDWHU LQ )ORULGD *URXQGZDWHU ZLWKGUDZDO IRU SRWDEOH ZDWHU XVH LV DSSUR[LPDWHO\ 0JDOG FRPSULVLQJ b RI SXEOLF ZDWHU DQG b RI UXUDO ZDWHU VXSSOLHV ,W LV QRWHZRUWK\ WKDW QHDUO\ PLOOLRQ UHVLGHQWV GULQN XQWUHDWHG ZDWHU IURP VKDOORZ SULYDWH ZHOOV ZKLFK DUH SDUWLFXODUO\ SURQH WR FRQWDPLQDWLRQ IURP XQGHUJURXQG VWRUDJH WDQNV )HUQDOG DQG 3DWWRQ f +\GURJHRORJ\ LV WKH WKLUG IDFWRU ZKLFK FRQWULEXWHV WR WKH VHQVLWLYLW\ RI )ORULGDnV ZDWHU VXSSOLHV WR JDVROLQH FRQWDPLQDWLRQ 0RVW RI WKH SRWDEOH ZDWHU DTXLIHUV DUH VXUILFLDO RU LQWHUPHGLDWH LQ GHSWK DQG DUH VXVFHSWLEOH WR FRQWDPLQDWLRQ ,Q DGGLWLRQ WKH JHQHUDOO\ SRURXV QDWXUH RI WRS VRLO LQ WKH VWDWH HQKDQFHV SROOXWDQW WUDQVSRUW WR WKH XQGHUO\LQJ DTXLIHUV 0RVW VRLOV LQ )ORULGD DUH VDQG\ ORDP

PAGE 18

VDQG\ FOD\ DQG VDQG\ FOD\ ORDPV DOO RI ZKLFK DUH QRWHG IRU WKHLU UHODWLYHO\ KLJK SHUPHDELOLWLHV )HUQDOG DQG 3DWWRQ f 7KH VDQG\ GHSRVLWV RI WKH 3OLRFHQH DQG 3OHLVWRFHQH DJHV FRPPRQ WR )ORULGD DUH DOVR PDUNHG E\ ORZ RUJDQLF FDUERQ DQG FOD\ FRQWHQW )HWWHU f UHVXOWLQJ LQ KLJK SHUPHDELOLW\ DQG ORZ VRUSWLYH FDSDFLW\ *LYHQ WKH PDJQLWXGH RI WKLV SUREOHP WKH WUDQVSRUW DQG HQYLURQPHQWDO UHDFWLRQV RI GLVVROYHG JDVROLQH FRPSRQHQWV LQ VKDOORZ VDQG\ DTXLIHUV LV DQ LPSRUWDQW DUHD RI VWXG\ 7KLV LV SDUWLFXODUO\ WUXH RI WKH DURPDWLF FRQVWLWXHQWV RI JDVROLQH RZLQJ WR WKHLU WR[LFLW\ FRQFHQWUDWLRQV LQ JDVROLQH DQG WKHLU KLJK DTXHRXV VROXELOLW\ *DVROLQH SURGXFWV ZKLFK DUH UHOHDVHG LQWR WKH YDGRVH ]RQH WUDYHO GRZQZDUG XQGHU WKH LQIOXHQFH RI FDSLOODU\ DQG JUDYLWDWLRQDO IRUFHV :KHQ WKH VRUSWLYH FDSDFLW\ RI WKH VRLO LV H[FHHGHG JDVROLQH PRYHV RQWR WKH JURXQGZDWHU WDEOH ZKHUH LW VSUHDGV ODWHUDOO\ DFURVV WKH WRS RI WKH VDWXUDWHG ]RQH 7KLV LV D UHVXOW RI WKH GHQVLW\ RI JDVROLQH JFP f *DVROLQH FRPSRQHQWV SDUWLWLRQ LQWR WKH ZDWHU WR WKH H[WHQW RI WKHLU ZDWHU VROXELOLW\ DQG PRYH LQ WKH GLUHFWLRQ RI WKH ZDWHU WDEOH JUDGLHQW 3K\VLFDO FKHPLFDO DQG ELRORJLFDO IDFWRUV PXVW DOO EH FRQVLGHUHG LQ WKH GHWHUPLQDWLRQ RI WKH IDWH DQG WUDQVSRUW RI GLVVROYHG JDVROLQH K\GURFDUERQV LQ JURXQGZDWHU 7KH LQWHUDFWLRQ RI WKHVH IDFWRUV PD\ EH FRQYHQLHQWO\ H[DPLQHG LQ WKH FRQWH[W RI D JHQHUDOL]HG PDVV WUDQVSRUW HTXDWLRQ $ RQHGLPHQVLRQDO IRUP RI WKLV HTXDWLRQ LV

PAGE 19

& DW & [ f Y & [ f S DV Wf 4 >@ ZKHUH & 6 W [ 3 'K 9 4L VROXWLRQ SKDVH FRQFHQWUDWLRQ RI VROXWH XJ/f DGVRUEHG SKDVH FRQFHQWUDWLRQ RIAVROXWH QJJf YROXPHWULF ZDWHU FRQWHQW P/FP WLPH PLQf KRUL]RQWDO GLVWDQFA FPf EXON GHQVLW\ JFUQ f K\GURG\QDPLF GLVSHUVLRQ FRHIILFLHQW FP PLQf DYHUDJH SRUH ZDWHU YHORFLW\ FPPLQf GHJUDGDWLRQ UDWH PLQ f 7KH FRPSRQHQWV RI WKLV HTXDWLRQ DUH FRQYHFWLRQ GLVSHUVLRQ VRUSWLRQ DQG GHJUDGDWLRQ WHUPV &RQYHFWLRQ GHVFULEHV WKH PRYHPHQW RI D GLVVROYHG FRQWDPLQDQW ZLWK WKH JURXQGZDWHU 'LVSHUVLRQ GHVFULEHV WKH VSUHDGLQJ RI WKH VROXWHV GXULQJ IORZ WKURXJK WKH DTXLIHU PDWHULDO 6RUSWLRQ WHUPV DFFRXQW IRU WKH UHWDUGDWLRQ RI WKH GLVVROYHG VROXWHV E\ LQWHUDFWLRQ ZLWK WKH DTXLIHU PDWUL[ DQG GHJUDGDWLRQ WHUPV HYDOXDWH WKH UHPRYDO RU WUDQVIRUPDWLRQ RI WKH FRQWDPLQDQWV 5HVHDUFK KDV VKRZQ WKDW VRUSWLRQ DQG ELRORJLFDO GHJUDGDWLRQ DUH WKH PDMRU DWWHQXDWLRQ PHFKDQLVPV IRU RUJDQLF VROXWHV LQ VRLOV DQG JURXQGZDWHU :RRGEXUQ f 0DWKHPDWLFDO PRGHOV EDVHG RQ VXFK HTXDWLRQV DUH LPSRUWDQW WRROV IRU WKH SUHGLFWLRQ RI FRQWDPLQDQW PRYHPHQW 3LQGHU f +RZHYHU WKH DGHTXDF\ RI WKHVH SUHGLFWLRQV LV GLUHFWO\ UHODWHG WR D NQRZOHGJHDEOH DQG DFFXUDWH TXDQWLILFDWLRQ RI WKH SURFHVVHV LQYROYHG 0DF.D\ HW DO f 7KH UHPHGLDWLRQ RI JURXQGZDWHU FRQWDPLQDWLRQ DOVR

PAGE 20

UHTXLUHV GHWDLOHG DQG XVXDOO\ VLWH VSHFLILF GDWD IRU WKHVH SURFHVVHV 7KLV GLVVHUWDWLRQ SUHVHQWV D GHWDLOHG LQYHVWLJDWLRQ RI WKH DWWHQXDWLRQ RI VHOHFWHG GLVVROYHG DURPDWLF JDVROLQH K\GURFDUERQV LQ D W\SLFDO VDQG\ VXUILFLDO DTXLIHU LQ )ORULGD XVLQJ D YDULHW\ RI EDWFK DQG FROXPQ WHFKQLTXHV 6RUSWLRQ FRHIILFLHQWV DQG ELRORJLFDO DQG DELRWLF GHJUDGDWLRQ UDWHV IURP ODERUDWRU\ VWXGLHV DUH SUHVHQWHG 7KHVH VWXGLHV VLPXODWHG FRQGLWLRQV DW D FRQWDPLQDWHG ILHOG VLWH DQG LQFOXGHG H[SHULPHQWV WR DVVHVV YDULRXV WUHDWPHQW DOWHUQDWLYHV $FWXDO ILHOG GDWD DUH VXPPDUL]HG DQG FRPSDUHG WR WKH ODERUDWRU\ GDWD 7KH LPSURYHG XQGHUVWDQGLQJ REWDLQHG IURP WKH FROOHFWLRQ DQG DQDO\VLV RI WKHVH GDWD VKRXOG DLG LQ WKH IRUPDWLRQ DQG LPSURYHG XVH RI SUHGLFWLYH PRGHOV GHVFULELQJ WKH PRYHPHQW DQG UHDFWLRQ UDWHV RI ZDWHU VROXEOH FRPSRQHQWV RI JDVROLQH LQ VKDOORZ JURXQGZDWHU V\VWHPV DQG DLG LQ WKH VHOHFWLRQ RI DSSURSULDWH JURXQGZDWHU UHFODPDWLRQ WHFKQRORJLHV

PAGE 21

&+$37(5 ,, 2%-(&7,9(6 7KH PDLQ REMHFWLYHV RI WKLV VWXG\ ZHUH f 7R HYDOXDWH WKH VRUSWLRQ FRHIILFLHQWV IRU VHOHFWHG DURPDWLF K\GURFDUERQV IRXQG LQ ZDWHU DW WKH /DNH $OIUHG UHVHDUFK VLWH HPSOR\LQJ EDWFK LVRWKHUPV DQG VRLO FROXPQV f 7R GHWHUPLQH WKH UDWHV RI K\GURO\VLV RI WKH VHOHFWHG DURPDWLF K\GURFDUERQV f 7R GHWHUPLQH WKH UDWHV RI ELRGHJUDGDWLRQ RI WKH VHOHFWHG DURPDWLF K\GURFDUERQV XQGHU VLPXODWHG ILHOG FRQGLWLRQV DQG DIWHU WUHDWPHQW ZLWK K\GURJHQ SHUR[LGH R[\JHQ JDV DQG DPPRQLXP FKORULGH f 7R GHWHUPLQH WKH PRVW DSSURSULDWH SUHGLFWLYH PRGHO IRU VRUSWLRQ RI WKH VHOHFWHG DURPDWLF K\GURFDUERQV LQ D VDQG\ VXUILFLDO DTXLIHU LQ )ORULGD f 7R FRUUHODWH PROHFXODU SURSHUWLHV RI WKH VHOHFWHG DURPDWLF K\GURFDUERQV ZLWK VRUSWLYH DQG ELRORJLFDO SDUDPHWHUV f 7R HYDOXDWH ILHOG GDWD EDVHG RQ WKH ODERUDWRU\ PHDVXUHPHQWV RI VRUSWLRQ DQG ELRGHJUDGDWLRQ DQG f 7R H[WUDSRODWH WKH ODERUDWRU\ GDWD IRU DSSOLFDWLRQ RI DTXLIHU UHPHGLDWLRQ SUDFWLFHV

PAGE 22

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f FRQVLVWLQJ RI DONDQH DONHQH DURPDWLF DQG QDSWKHQH K\GURFDUERQV $XWRPRELOH JDVROLQHV DUH FRPSULVHG RI &A&A K\GURFDUERQV ZLWK ERLOLQJ SRLQWV LQ WKH UDQJH & 8Qn OHDGHG JDVROLQHV FRQWDLQ JUHDWHUFRQFHQWUDWLRQV RI DURPDWLF K\GURFDUERQV WR SURYLGH IRU DQWLNQRFN SURWHFWLRQ DQG EUDQFKHG K\GURFDUERQV WR LQFUHDVH RFWDQH UDWLQJV 0RRUH DQG 0RRUH f

PAGE 23

'HVSLWH WKH ODUJH QXPEHU RI K\GURFDUERQV FRPSULVLQJ JDVROLQH PXFK RI WKH HQYLURQPHQWDO FRQFHUQ IRFXVHV RQ WKH ZDWHU VROXEOH FRPSRQHQWV RI JDVROLQH SDUWLFXODUO\ WKH VLQJOH ULQJ DURPDWLF FRPSRXQGV 7KHVH FRPSRXQGV DUH RI FRQFHUQ EDVHG RQ WKHLU WR[LFLW\ DTXHRXV VROXELOLW\ DQG FRQFHQWUDWLRQ LQ JDVROLQH %DUNHU DQG 3DWULFN f $FXWH WR[LFLW\ LV DVVRFLDWHG ZLWK WKH ZDWHU VROXEOH IUDFWLRQ RI RLOV %OXPHU HW DO f DQG WKH PDMRU FRPSRQHQWV RI WKH ZDWHU VROXEOH IUDFWLRQ DUH DURPDWLF &ROHPDQ HW DO f 'DWD IURP WKH ZRUN RI &ROHPDQ HW DO f VKRZHG WKDW DOWKRXJK DURPDWLF FRPSRQHQWV PDGH XS RQO\ b RI WKH XQOHDGHG JDVROLQH SURGXFW LQ WKHLU VWXG\ b RI WKH FRPSRQHQWV LQ WKH ZDWHU VROXEOH IUDFWLRQ ZHUH DURPDWLF 7KXV LQ D VSLOO VLWXDWLRQ D VLJQLILFDQW DPRXQW RI WKH FRQWDPLQDQWV LQ WKH ZDWHU SKDVH ZLOO EH DURPDWLF 6HOHFWHG SK\VLFDO SURSHUWLHV RI WKH FRPSRXQGV XVHG LQ WKLV VWXG\ DUH OLVWHG LQ 7DEOH 7KH KHDOWK HIIHFWV IURP WKH XVH RI JDVROLQH FRQWDPLQDWHG ZDWHU PD\ EH VLJQLILFDQW %HQ]HQH LV D FDUFLQRJHQ LQ UDWV DQG PLFH DQG H[SRVXUH LV OLQNHG ZLWK OHXNHPLD 863+6 f 7KH PD[LPXP FRQWDPLQDQW OHYHO IRU EHQ]HQH LQ FRPPXQLW\ GULQNLQJ ZDWHU VXSSOLHV LV SSE LQ )ORULGD 7ROXHQH HWK\OEHQ]HQH DQG P[\OHQH DIIHFW WKH FHQWUDO QHUYRXV V\VWHP :LQGKROW] f 8QOHDGHG JDVROLQH LQGXFHV UHQDO DQG KHSDWRFHOOXODU FDUFLQRPDV LQ UDWV DQG WKH XVH RI SHWUROHXP FRQWDPLQDWHG ZDWHU FDQ SURGXFH HOHYDWHG OHYHOV RI LQGRRU DLU SROOXWDQWV DOORZLQJ FKURQLF H[SRVXUH WR

PAGE 24

7DEOH 6HOHFWHG SK\VLFDO SURSHUWLHV RI VWXG\ FRPSRXQGV FL ,G FL 0ROHFXODU :DWHU %RLOLQJ rn 2 :HLJKW 6ROXELOLW\ 3RLQW 'HQVLW\ ORJ &RPSRXQG $08 PJ/ r& JPO .TZ ;D %HQ]HQH 7ROXHQH (WK\OEHQ]HQH PS;\OHQH R;\OHQH (WK\OWROXHQH 7ULPHWK\OEHQ]HQH (WK\OWROXHQH 7ULPHWK\OEHQ]HQH 7ULPHWK\OEHQ]HQH ,VRSURS\OEHQ]HQH Q3URS\OEHQ]HQH D&5& +DQGERRN RI &KHPLVWU\ DQG 3K\VLFV A%URRNPDQ HW DO &/HR HW DO G6DEOMLF N'

PAGE 25

K\GURFDUERQV 6KHKDWD f 'HUPDO DEVRUSWLRQ RI YRODWLOH RUJDQLF FRQWDPLQDQWV IURP JDVROLQH PD\ DOVR EH D VLJQLILFDQW H[SRVXUH %URZQ HW DO f )LUH DQG H[SORVLRQ KD]DUGV DUH DOVR D ULVN IDFWRU LQ WKH UHOHDVH RI JDVROLQH WR WKH HQYLURQPHQW 9RODWLOL]DWLRQ DQG VXEVHTXHQW JDV SKDVH WUDQVSRUW RI K\GURFDUERQV LQ WKH XQVDWXUDWHG ]RQH KDYH GHVWUR\HG EXLOGLQJV +RDJ DQG 0DUOH\ f &RQYHFWLYH'LVSHUVLYH 0RGHOV 7KH FRJHQW HYDOXDWLRQ RI FRQWDPLQDQW SOXPHV UHPHGLDO DFWLRQ DOWHUQDWLYHV DQG ULVN DVVHVVPHQW IRU RUJDQLF FRPSRXQGV LQ JURXQGZDWHU UHTXLUHV D WKRURXJK XQGHUVWDQGLQJ RI WKH EHKDYLRU RI WKHVH FRQWDPLQDQWV LQ JURXQGZDWHU V\VWHPV 7KLV LQFOXGHV DQ DVVHVVPHQW DQG TXDQWLILFDWLRQ RI WKH UHOHYDQW SURFHVVHV ZKLFK LQIOXHQFH WKHLU IDWH DQG WUDQVSRUW 0LOOHU DQG :HEHU f 7KH LQWHUDFWLRQ RI WKHVH SURFHVVHV PD\ EH H[DPLQHG LQ WKH FRQWH[W RI FRQYHFWLYHGLVSHUVLYH PRGHOV 7KHVH PRGHOV KDYH EHHQ UHYLHZHG $QGHUVRQ )UHH]H DQG &KHUU\ f DQG DUH PDUNHG E\ WKHLU FRPSXWDWLRQDO VLPSOLFLW\ UHDVRQDEOH GDWD UHTXLUHPHQWV DQG VXIILFLHQWO\ DFFXUDWH RXWSXW 5REHUWV HW DO f $OWKRXJK WKH DGHTXDF\ RI FRQYHFWLYHGLVSHUVLYH PRGHOV IRU GHVFULELQJ VROXWH WUDQVSRUW KDV EHHQ TXHVWLRQHG $QGHUVRQ 6PLWK DQG 6FKZDUW] f SDUWLFXODUO\ ZLWK UHJDUG WR GLVSHUVLYLW\

PAGE 26

DSSUR[LPDWLRQV WKHVH PRGHOV SURYLGH D FRQYHQLHQW IUDPHZRUN IRU XQGHUVWDQGLQJ WKH WUDQVSRUW RI GLVVROYHG VROXWHV LQ JURXQGZDWHU 7KH JHQHUDO IRUP RI WKH VROXWH WUDQVSRUW HTXDWLRQ XQGHU VDWXUDWHG IORZ FRQGLWLRQV LV JLYHQ E\ %HDU f $ RQH GLPHQVLRQDO IRUP RI WKLV HTXDWLRQ IRU FRQVHUYDWLYH FRQWDPLQDQWV XQGHU VWHDG\ IORZ FRQGLWLRQV LV &W &6[f Y G&G[f >@ ZKHUH & 6 [ 9 VROXWLRQ SKDVH FRQFHQWUDWLRQ RI VROXWH XJ/f VRUEHG SKDVH FRQFHQWUDWLRQ RI VROXWH QJJf K\GURG\PDQLF GLVSHUVLRQ FRHIILFLHQW FP PLQf WLPH PLQf KRUL]RQWDO GLVWDQFH FPf DYHUDJH SRUH ZDWHU YHORFLW\ FPPLQf 7KH PDMRU FRPSRQHQWV RI WKLV HTXDWLRQ DUH FRQYHFWLRQ EXON IORZf DQG GLVSHUVLRQ GHYLDWLRQ IURP EXON IORZf $ EULHI GLVFXVVLRQ RI GLVSHUVLRQ IROORZV ZLWK UHIHUHQFH WR H[WUDSRODWLRQ RI ODERUDWRU\ GDWD WR ILHOG VFDOH DSSOLFDWLRQV 7KH K\GURG\QDPLF GLVSHUVLRQ FRHIILFLHQW GHVFULEHV WKH VSUHDGLQJ RI D VROXWH DV LW PRYHV WKURXJK SRURXV PHGLD +\GURG\QDPLF GLVSHUVLRQ f LV WKH VXP RI PHFKDQLFDO GLVSHUVLRQ FDXVHG E\ GLIIHUHQFHV LQ ZDWHU YHORFLW\ WKURXJK VLQXRXV DQG WRUWXRXV SRUHV DQG PROHFXODU GLIIXVLRQ %LJJDU DQG 1LHOVHQ f 'LVSHUVLRQ YDOXHV UHIOHFW WKH KHWHURJHQHLW\ RI WKH DTXLIHU PDWHULDO 'LVSHUVLRQ LV XVXDOO\ GHWHUPLQHG E\ PHDVXULQJ WKH EUHDNWKURXJK RI D FRQVHUYDWLYH WUDFHU VXFK DV FKORULGH RU WULWLDWHG ZDWHU

PAGE 27

7KH SK\VLFDO DQG PDWKHPDWLFDO UHODWLRQVKLSV RI ZDWHU DQG VROXWH WUDQVSRUW ZHUH UHYLHZHG E\ 'DYLGVRQ HW DO f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f 7KLV LV D UHVXOW RI WKH JUHDWHU KHWHURJHQHLW\ RI D ILHOG VLWH YHUVXV D VPDOO KRPRJHQHRXV ODERUDWRU\ FROXPQ $ VROXWLRQ IRU HTXDWLRQ >@ IRU D ILQLWH FROXPQ XVLQJ GLPHQVLRQOHVV YDULDEOHV ZDV SUHVHQWHG E\ %UHQQHU f 7KH GLPHQVLRQOHVV 3HFOHW QXPEHU 3 f ZDV XVHG DV D PHDVXUH RI GLVSHUVLRQ 3H Y/'K >@ ZKHUH Y LV SRUH ZDWHU YHORFLW\ FPPLQf / LV WKH OHQJWK FPf RI WKH VRLO FROXPQ DQG LV WKH K\GURG\QDPLF GLVSHUVLRQ FRHIILFLHQW FP PLQf )RU YDOXHV RI 3J GLVSHUVLRQ LV DVVXPHG QHJOLJLEOH 9DOXHV RI 3A JHQHUDOO\ LQGLFDWH FRPSOHWH PL[LQJ %RXQGDU\ FRQGLWLRQV IRU GLVSODFHPHQW H[SHULPHQWV WKURXJK VKRUW ODERUDWRU\ FROXPQV ZHUH UHYLHZHG E\ YDQ *HQXFKWHQ DQG 3DUNHU f 7KH VROXWLRQ RI %UHQQHU f ZDV VKRZQ WR FRUUHFWO\ FRQVHUYH PDVV LQ ILQLWH ODERUDWRU\ VRLO FROXPQV EDVHG RQ PDVV

PAGE 28

EDODQFH FRQVLGHUDWLRQV )RU D IOX[ W\SH LQOHW ERXQGDU\ FRQGLWLRQ IORZLQJ FRQFHQWUDWLRQVf %UHQQHUnV VROXWLRQ ZDV DSSOLFDEOH SURYLGHG WKH FROXPQ 3HFOHW QXPEHU ZDV QRW PXFK OHVV WKDQ ILYH} 7KH VROXWLRQ RI /DSLGXV DQG $PXQGVRQ f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f ,Q WKLV OLWHUDWXUH UHYLHZ WKH OLTXLG SKDVH LV DVVXPHG WR EH ZDWHU FRQWDLQLQJ VROXELOL]HG RUJDQLF VROXWHV DQG WKH VROLG SKDVH LV WKH DTXLIHU PDWHULDO XQGHU VDWXUDWHG VWHDG\ IORZ FRQGLWLRQV 6RUSWLRQ LV LQIOXHQFHG E\ WKH SK\VLFDO DQG FKHPLFDO FKDUDFWHULVWLFV RI WKH DTXLIHU LH VRLO W\SH IUDFWLRQ RI RUJDQLF FDUERQf DQG WKH VROXWH LH VROXELOLW\ YRODWLOLW\ GHQVLW\f $OWKRXJK VRUSWLRQ LV D PDMRU FRPSRQHQW LQ WKH DWWHQXDWLRQ RI VROXWHV LQ WKH VXEVXUIDFH WKH IXQGDPHQWDO

PAGE 29

SURFHVVHV RI VROXWHVRLO LQWHUDFWLRQ DQG WKH WKHUPRG\QDPLFV RI WKLV SURFHVV DUH QRW FRPSOHWHO\ FKDUDFWHUL]HG 7KHUHIRUH VRUSWLRQ LV XVHG LQ WKLV VWXG\ DV D JHQHULF WHUP WR GHVFULEH VROXWH UHWHQWLRQ LH XSWDNH RI VROXWHf UHJDUGOHVV RI ZKHWKHU WKH SURFHVV LV RQH RI DGVRUSWLRQ DEVRUSWLRQ RU SDUWLWLRQLQJ :RRGEXUQ f 'HVRUSWLRQ LV XVHG KHUH WR GHVFULEH VROXWH UHPRYDO IURP WKH VROLG SKDVH 6RUSWLRQ 3URFHVVHV 7KH DWWUDFWLYH IRUFHV DFWLQJ WR HIIHFW VRUSWLRQ RI K\GURSKRELF FRPSRXQGV RQWR QDWXUDO VRUEHQWV ZHUH UHYLHZHG E\ 9RLFH DQG :HEHU f 7KH PDMRU WKHRU\ LV GLVFXVVHG EHORZ %RQGLQJ IRUFHV LQ VRUSWLRQ PD\ EH ERWK SK\VLFDO DQG FKHPLFDO WKRXJK ERWK DUH EDVLFDOO\ HOHFWURVWDWLF LQ QDWXUH 3K\VLFDO VRUSWLRQ UHVXOWV IURP 9DQ GHU :DDOV IRUFHV 7KH VWUHQJWK RI WKHVH LQWHUDFWLRQV LV JHQHUDOO\ RQ WKH RUGHU RI .FDOPROH 7KHVH HQHUJLHV PD\ EH DXJPHQWHG E\ D WKHUPRG\QDPLF JUDGLHQW GULYLQJ K\GURSKRELF PROHFXOHV RXW RI VROXWLRQ 7KLV LV EDVHG RQ HQWURSLF FRQVLGHUDWLRQV VROYRSKRELF WKHRU\f &KHPLFDO VRUSWLRQ LV WKH LQWHUDFWLRQ EHWZHHQ VSHFLILF VLWHV RI WKH VRUEHQW DQG LQGLYLGXDO VROXWH PROHFXOHV 7KLV DSSUR[LPDWHV D WUXH FKHPLFDO ERQG ZLWK KHDWV RI DGVRUSWLRQ EHWZHHQ .FDOPROH 9RLFH DQG :HEHU f SRLQW RXW WKDW LW LV GLIILFXOW WR DVVHVV WKH LPSRUWDQFH RI HDFK W\SH RI ERQGLQJ 7KH KHWHURJHQHRXV QDWXUH RI QDWXUDO VRUEHQW PDWHULDOV LV ODUJHO\ XQNQRZQ DQG VRUSWLRQ SURFHVVHV SUREDEO\ LQYROYH DOO W\SHV RI LQWHUDFWLRQV

PAGE 30

6RUSWLRQ (TXLOLEULD 7ZR H[SHULPHQWDO WHFKQLTXHV DUH ZLGHO\ XVHG WR HYDOXDWH WKH D6 W WHUP LQ HTXDWLRQ >@ 7KHVH DUH EDWFK HTXLOLEULXP DQG VRLO FROXPQ PHWKRGV %DWFK VWXGLHV DOORZ WKH HYDOXDWLRQ RI WKH OLQHDULW\ RI WKH VRUSWLRQ LVRWKHUP DQG WKHLU XVH LV ZHOO GRFXPHQWHG 6FKZDU]HQEDFK DQG :HVWDOO &KLRX HW DO f 7KH PRVW ZLGHO\ XVHG PRGHOV WR GHVFULEH VRUSWLRQ HTXLOLEULD LQ JURXQGZDWHU V\VWHPV DUH WKH OLQHDU >@ DQG )UHXQGOLFK PRGHOV >@ 0LOOHU DQG :HEHU f 6 .G r & >@ 6 .Ir&Q Q f >@ ZKHUH 6 XJJf DQG & XJ/f DUH WKH DGVRUEHG SKDVH DQG VROXWLRQ SKDVH FRQFHQWUDWLRQV UHVSHFWLYHO\ DW HTXLOLEULXP /Jf LV WKH OLQHDU VRUSWLRQ FRHIILFLHQW /Jf LV WKH )UHXQGOLFK VRUSWLRQ FRHIILFLHQW ERWK DQG LQGLFDWLQJ VRUSWLRQ FDSDFLW\f DQG Q LV DQ HPSLULFDO FRQVWDQW LQGLFDWLQJ VRUSWLRQ LQWHQVLW\f 7KH OLQHDU PRGHO LV LQ HIIHFW D VSHFLDO FDVH RI WKH )UHXQGOLFK PRGHO ZKHUH Q O 7KH )UHXQGOLFK HTXDWLRQ LV RIWHQ OLQHDUL]HG ORJ WUDQVIRUPHGf WR IDFLOLWDWH FDOFXODWLRQ RI YDULDEOHV DQG Q LQ EDWFK VWXGLHV ORJ 6 Q r ORJ & /RJ >@ ,Q FROXPQ VWXGLHV LV HYDOXDWHG WKURXJK WKH UHWDUGDWLRQ IDFWRU 5f 7KH PDVV WUDQVSRUW HTXDWLRQ IRU UHDFWLYH VROXWHV XQGHU VWHDG\ IORZ LV GHVFULEHG E\ HTXDWLRQ >@

PAGE 31

R DFDW S D VVW 'K VF D[ Y DFD[ >@ ZKHUH S LV WKH EXON GHQVLW\ LV WKH YROXPHWULF ZDWHU FRQWHQW DQG 6 LV WKH VRUEHG SKDVH FRQFHQWUDWLRQ 1RWH WKDW HTXDWLRQ >@ LV HTXLYDOHQW WR HTXDWLRQ >@ ZLWK WKH DGGLWLRQ RI WKH VRUSWLRQ WHUP D6 DW $VVXPLQJ OLQHDU UHYHUVLEOH VRUSWLRQ WKH VRUEHG FRQFHQWUDWLRQ RI D VROXWH LV UHODWHG WR WKH DTXHRXV FRQFHQWUDWLRQ RI WKH VROXWH E\ WKH UHODWLRQVKLS 6W .G &W >@ 6XEVWLWXWLRQ IRU 6 DW LQ HTXDWLRQ >@ ZLWK HTXDWLRQ >@ \LHOGV WKH UHODWLRQVKLS DFDW .G DFDW &SHf 'K DFD[ Y D FD[ >@ $IWHU VHSDUDWLRQ RI YDULDEOHV HTXDWLRQ >@ EHFRPHV DFDW > O S .GH@ 'K FD[ Y DF[ >@ DQG E\ GHILQLQJ WKH UHWDUGDWLRQ IDFWRU 5f DV 5 S .G >@ VXEVWLWXWLRQ RI HTXDWLRQ >@ LQWR >@ UHVXOWV LQ WKH LQFRUSRUDWLRQ RI WKH UHWDUGDWLRQ IDFWRU 5f LQWR WKH PDVV WUDQVSRUW HTXDWLRQ IRU VROXWH WUDQVSRUW XQGHU VDWXUDWHG VWHDG\ IORZ FRQGLWLRQV U DFDW 'K DF[ Y DFD[ >LL@ $QDO\VLV RI HTXDWLRQ >@ LQGLFDWHV WKDW WKH YDOXH RI 5 LV ODUJHO\ GHSHQGHQW RQ .G IRU D KRPRJHQHRXV DTXLIHU V\VWHP RU ODERUDWRU\ FROXPQ 'HWHUPLQDWLRQ RI 5 IURP VRLO

PAGE 32

FROXPQ VWXGLHV OHDGV WR WKH HYDOXDWLRQ RI IURP HTXDWLRQ >@ 1NHGL.L]]D HW DO f FRPSDUHG WHFKQLTXHV IRU WKH FDOFXODWLRQ RI 5 IURP VRLO FROXPQ OHDFKLQJ H[SHULPHQWV DQG IURP EDWFK LVRWKHUP H[SHULPHQWV 9DOXHV RI 5 FDOFXODWHG E\ GHWHUPLQLQJ WKH DUHD DERYH WKH EUHDNWKURXJK FXUYH ZHUH VKRZQ WR EH HTXLYDOHQW WR 5 YDOXHV FDOFXODWHG E\ XVLQJ HTXDWLRQ >@ 6RUSWLRQ (VWLPDWRUV 5HFHQWO\ DSSUR[LPDWLRQ PHWKRGV EDVHG RQ WKH DVVXPSWLRQ RI SDUWLWLRQLQJ DV WKH GRPLQDQW PHWKRG RI VROXWH LQWHUDFWLRQ KDYH EHFRPH FRPPRQ .DULFNKRII HW DO &KLRX HW DO .HQDJD DQG *RULQJ &KLRX HW DO f 7KHLU XVH LV ODUJHO\ D UHVXOW RI WKH WLPH DQG GLIILFXOW\ LQ WKH DFFXUDWH PHDVXUHPHQW RI VRUSWLRQ FRHIILFLHQWV .Af DQG WKH JHQHUDO ODFN RI GDWD RQ K\GURFDUERQ VRUSWLRQ WR HQYLURQPHQWDO VRUEHQWV 7KHVH DXWKRUV QRWH D FRUUHODWLRQ EHWZHHQ WKH IUDFWLRQDO RUJDQLF FDUERQ FRQWHQW RI WKH VRUEHQW PDWHULDO I f DQG 7KH QRUPDOL]HG WR I RI WKH RF G G RF VRUEHQW LV GHVFULEHG DV ZKHUH RF .I >@ RF Gn RF / 9DOXHV RI LV RF ZHOO FRUUHODWHG ZLWK DTXHRXV VROXELOLW\ ZVf & KLRX HW DO f DQG WKH RFWDQROZDWV VU SDUWLWLRQ FRHIILF LHQW f .DULFNKRII HW DO f 7KHVH DXWKRUV RZ VXJJHVW WKDW WKH VROXWHVRUEHQW LQWHUDFWLRQ LV D SDUWLWL RQLQJ SURF HVV UDWKHU WKDQ DQ LQWHUDFWLRQ EHWZHHQ VROXWH DQG WKH PL QHUDO VXUIDFH (YLGHQFH IRU SDUWLWLRQLQJ LV SDUWLDOO\ VXSSRUWHG E\ WKH K\GURSKRELF FKDUDFWHU RI VRLO

PAGE 33

RUJDQLF PDWWHU DQG E\ VROYRSKRELF WKHRU\ 5DR HW DO f 7KH JHQHUDO UHODWLRQVKLS EHWZHHQ DQG DQG :6 RF WDNHV WKH IRUP &XUWLV HW DO f /RJ D r /RJ /RJ I E >@ RF RZ A RF /RJ F r /RJ :6 /RJ I G >@ ZKHUH DEF DQG G UHVXOW IURP UHJUHVVLRQ DQDO\VLV RI ODERUDWRU\ LVRWKHUP GDWD DQG GHSHQG RQ WKH VROXWHVRUEHQW V\VWHP +RZHYHU WKHUH DUH VLJQLILFDQW OLPLWDWLRQV RQ WKH XVH RI WKHVH HVWLPDWRUV DQG WKH EDVLV RI SDUWLWLRQLQJ DV D VRUSWLRQ PHFKDQLVP LV TXHVWLRQDEOH 0LOJHOJULQ DQG *HUVWO f ,Q D VWULFW VHQVH WKHVH UHODWLRQVKLSV KROG RQO\ IRU WKRVH FRPSRXQGV DQG VRUEHQWV XVHG LQ WKH RULJLQDO VWXGLHV LH WKHVH DUH HPSLULFDO UHODWLRQVKLSVf 7KLV LV UHIOHFWHG LQ RUGHUV RI PDJQLWXGH YDULDWLRQ LQ HVWLPDWHV RI VRUSWLRQ XVLQJ WKHVH UHODWLRQVKLSV $SSOLFDWLRQ RI WKH SDUWLWLRQLQJ PRGHOV PD\ QRW EH DSSURSULDWH LQ H[SHULPHQWDO V\VWHPV ZLWK VROXWHV DQG VRUEHQWV ZKLFK DUH GLIIHUHQW IURP WKRVH XVHG WR GHYHORS WKHVH PRGHOV ,Q DGGLWLRQ WKHVH HTXDWLRQV PD\ QRW DSSO\ DW RUJDQLF FDUERQ IUDFWLRQV OHVV WKDQ b &XUWLV HW DO f 5DR DQG -HVVXS f QRWHG WKDW WKH XVH RI WR HVWLPDWH VRUSWLRQ FDQ OHDG WR VLJQLILFDQW HUURUV ZLWK VRLOV ZLWK YHU\ ORZ OHVV WKDQ bf RUJDQLF FDUERQ FRQWHQWV 0LOJHOJULQ DQG *HUVWO f UHYLHZHG WKH HYLGHQFH IRU SDUWLWLRQLQJ DQG QRWHG WKDW D FRUUHODWLRQ EHWZHHQ WKH RUJDQLF FDUERQ FRQWHQW RI WKH VRLO DQG VRUSWLRQ ZDV QRW

PAGE 34

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f EXW QRW LWV SDUWLWLRQLQJ EHWZHHQ DQ RUJDQLF SKDVH DQG ZDWHU 5HFHQWO\ ILUVW RUGHU PROHFXODU FRQQHFWLYLW\ LQGH[HV A;f ZHUH VKRZQ WR EH ZHOO FRUUHODWHG ZLWK YDOXHV RF 6DEOMLF 6DEOMLF f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r $Q DFF XUDWH PRGHO VRUSWLRQ PD\ LQFOXGH ERWK SDUW L WLRQLL QJ DQG VX U I DFH DUHD GHSHQGHQ W DIIHFWV 7KH UHODWLRQVKLS EH WZHHQ DQG RF LV 6DELM LF f

PAGE 35

/RJ r ; RF >@ 7KLV UHODWLRQVKLS LV EDVHG RQ OLWHUDWXUH YDOXHV RI IURP RF ODERUDWRU\ H[SHULPHQWV ZLWK FRPSRXQGV FRYHULQJ D EURDG UDQJH RI SRODULWLHV DQG FODVVHV DQG D YDULHW\ RI VRUEHQW V\VWHPV 7KH FRUUHODWLRQ FRHIILFLHQW LV ZKLFK H[SODLQV b RI WKH YDULDQFH 'HVRUSWLRQ ,Q PRVW FDVHV VRUSWLRQ LV FRQVLGHUHG WR EH FRPSOHWHO\ UHYHUVLEOH WKDW LV WKH DGVRUSWLRQGHVRUSWLRQ LVRWKHUPV DUH UHYHUVLEOH DQG VLQJOH YDOXHG +RZHYHU VHYHUDO LQYHVWLJDWRUV UHSRUW GHVRUSWLRQV ZKLFK GLVSOD\ K\VWHUHVLV LQ EDWFK VWXGLHV %DLOH\ DQG :KLWH %RXFKHU DQG /HH &DUULQJHU HW DO 'L7RUR DQG +RU]HPSD f 9DQ *HQXFKWHQ HW DO f IRXQG WKDW WKH H[SRQHQW IRU GHVRUSWLRQ LV FRQFHQWUDWLRQ GHSHQGHQW DQG GHVFULEHG WKH K\VWHUHWLF EHKDYLRU E\ XVLQJ VHSDUDWH LVRWK HUP HTXDWLRQV VRUSWLRQ DQG GHVRUSWLRQ 6 V ,8 & Q6 GV V > 6G N F QG GG G > ZKHUH VXEVFULSWV V DQG G LQGLFDWH VRUSWLRQ DQG GHVRUSWLRQ UHVSHFWLYHO\ +\VWHUHVLV LQ FROXPQ VWXGLHV ZDV QRWHG E\ 6FKZDU]HQEDFK DQG :HVWDOO f DOWKRXJK WKH UHDFWLRQ ZDV WHUPHG UHYHUVLEOH VLQFH DOO WKH VROXWH ZDV HYHQWXDOO\ HOXWHG IURP WKH FROXPQ

PAGE 36

6RUSWLRQ .LQHWLFV +\VWHUHWLFDO EHKDYLRU PD\ DFWXDOO\ EH D PDQLIHVWDWLRQ RI VRUSWLRQGHVRUSWLRQ NLQHWLFV 5DR DQG -HVVXS f QRWHG WKDW WKH LQIOXHQFH RI QRQVLQJXODU LVRWKHUPV LH LVRWKHUPV ZKLFK GLVSOD\ K\VWHUHVLVf RQ VROXWH PRYHPHQW PD\ EH OHVV VLJQLILFDQW WKDQ WKH HIIHFWV RI VRUSWLRQ QRQHTXLOLEULD ,Q D VWXG\ RI WKH WUDQVSRUW RI SHVWLFLGHV DW KLJK FRQFHQWUDWLRQV 5DR DQG 'DYLGVRQ f QRWHG WKDW WKH SRVLWLRQ RI DQ DGVRUEHG VROXWH LQ D EUHDNWKURXJK FXUYH ZDV JRYHUQHG E\ WKH QDWXUH RI WKH HTXLOLEULXP DGVRUSWLRQ LVRWKHUP HTXDWLRQ ZKHUHDV WKH VKDSH RI WKH FXUYH ZDV GHILQHG E\ WKH NLQHWLFV RI WKH VRUSWLRQGHVRUSWLRQ SURFHVV 6RUSWLRQ UHDFWLRQV EHWZHHQ K\GURSKRELF SROOXWDQWV DQG VHGLPHQWV DUH JHQHUDOO\ UDSLG DQG QRW UDWH OLPLWHG :HEHU HW DO f 5DR DQG 'DYLGVRQ f FRQFOXGHG WKDW PDQ\ VRUSWLRQ UHDFWLRQV DUH FRPSOHWH ZLWKLQ RQH PLQXWH LQ EDWFK VOXUU\ H[SHULPHQWV DOWKRXJK ORQJHU WLPHV WR HTXLOLEULXP ZHUH QRWHG LQ VHYHUDO VWXGLHV .DULFNKRII HW DO 0LOOHU DQG :HEHU f 6FKZDU]HQEDFK DQG :HVWDOO f LQ D FRPSDULVRQ RI VROXWH EUHDNWKURXJK DW YDULRXV IORZ YHORFLWLHV FRQFOXGHG WKDW YDOXHV IURP FROXPQ H[SHULPHQWV B ZKHUH YHORFLW\ ZDV OHVV WKDQ FPVHFRQG ZHUH VLPLODU WR YDOXHV IURP KRXU HTXLOLEULXP EDWFK VWXGLHV $URPDWLF 6RUSWLRQ 9DOXHV )URP 7KH /LWHUDWXUH 7KHUH DUH IHZ GDWD LQ WKH OLWHUDWXUH DGGUHVVLQJ VRUSWLRQ RI GLVVROYHG JDVROLQH FRPSRQHQWV LQ WKH VXEVXUIDFH 0XFK RI WKH UHVHDUFK LQYROYHG DURPDWLF FRPSRXQGV LQ VLQJOH

PAGE 37

VROXWH H[SHULPHQWV VLPSOH PL[WXUHV RU GDWD IURP FUXGH RLO VWXGLHV +RX]LP f REVHUYHG D GHFUHDVH LQ VRUSWLRQ LQ WKH RUGHU DONHQHV DURPDWLFV F\FORDONDQHV DONDQHV 1DWKDZDQL DQG 3KLOOLSV f LQ D VWXG\ RI KH[DGHFDQH R [\OHQH WROXHQH DQG EHQ]HQH LQ FUXGH RLO RQ VRLOV RI YDU\LQJ RUJDQLF PDWWHU SUHVHQWHG VRUSWLRQ FRHIILFLHQWV EDVHG RQ )UHXQGOLFK LVRWKHUPV 5RGJHUV HW DO f UHSRUWHG WKH DGVRUSWLRQ DQG GHVRUSWLRQ RI EHQ]HQH RQ VHYHUDO VRLOV DQG FOD\V DW & 7KH DTXHRXV SKDVH FRQFHQWUDWLRQ UDQJH ZDV WR XJ/ 6RUSWLRQ RI EHQ]HQH ZDV PLQLPDO H[FHSW RQ DOXPLQXP VDWXUDWHG FOD\ 7KHVH GDWD DUH VXPPDUL]HG LQ 7DEOH :LOVRQ HW DO f HYDOXDWHG WKH VRUSWLRQ RI WROXHQH RQ D ILQH VDQG LQ D FROXPQ VWXG\ $ UHWDUGDWLRQ IDFWRU OHVV WKDQ IRU WKH FRQFHQWUDWLRQ UDQJH RI XJ/ ZDV UHSRUWHG 7KLV LQGLFDWHV WKH UHODWLYHO\ ORZ UHWDUGDWLRQ SRWHQWLDO RI VDQG\ DTXLIHUV 7KH UHWDUGDWLRQ IDFWRU GHVFULEHV WKH H[WHQW RI VROXWH WUDQVSRUW UHODWLYH WR ZDWHU 7KH UHWDUGDWLRQ IDFWRU IRU ZDWHU LV GHILQHG DV XQLW\ 6ROXWHV ZLWK ODUJH UHWDUGDWLRQ IDFWRUV DUH OHVV PRELOH DQG DQG WKHLU PRYHPHQW LV UHWDUGHG UHODWLYH WR WKDW RI ZDWHU 6FKZDU]HQEDFK DQG :HVWDOO f SUHVHQWHG GDWD IRU WKH VRUSWLRQ RI VHYHUDO FKORULQDWHG DQG DON\O EHQ]HQHV RQ WZHOYH QDWXUDO DTXLIHU PDWHULDOV ZLWK YDU\LQJ DPRXQWV RI RUJDQLF FDUERQ 7KH LQLWLDO FRQFHQWUDWLRQV RI WKH DON\OEHQ]HQH FRPSRQHQWV ZHUH XJ/ 6RUSWLRQ FRHIILFLHQWV IURP EDWFK

PAGE 38

7DEOH 6XPPDU\ RI DGVRUSWLRQ GDWD IRU DURPDWLF K\GURFDUERQV 3HUFHQW %HQ]HQH 7ROXHQH R;\OHQH 2UJDQLF 6RLO &RQWHQW Q Q Q 6LOW\ &OD\ 6DQG\ /RDP 6LOW\ &OD\ 6LOW /RDP 6LOW\ &OD\ /RDP 6LOW\ &OD\ /RDP $O VDWXUDWHG 0RQWPRULO,RQLWH &X VDWXUDWHG 0RQWPRULOORQLWH $GDSWHG IURP %URRNPDQ HW DO

PAGE 39

VWXGLHV RI D VRLO ZLWK ORZ RUJDQLF FDUERQ J4&J VRLOf DUH VKRZQ LQ 7DEOH $V PD\ EH QRWHG IURP WKLV VKRUW UHYLHZ PRVW RI WKH DERYH VWXGLHV LQYROYH GDWD IURP LQGLYLGXDO FRPSRQHQWV RU IURP RLO EDVHG SURGXFWV *LYHQ WKH GLIIHUHQFHV LQ FRPSRVLWLRQ DPRQJ WKHVH SHWUROHXP SURGXFWV DQG JDVROLQH H[WUDSRODWLRQ PD\ EH LQVXIILFLHQW WR SURYLGH DFFXUDWH GDWD %URRNPDQ HW DO f %LRGHJUDGDWLRQ RI $URPDWLF +\GURFDUERQV LQ *URXQGZDWHU %LRORJLFDO DFWLYLW\ LV DQ LPSRUWDQW SURFHVV LQ WKH DWWHQXDWLRQ RI JDVROLQH K\GURFDUERQV LQ WKH VXEVXUIDFH HQYLURQPHQW 7KLV UHDOL]DWLRQ LV RQO\ UHFHQW (DUO\ WHFKQLTXHV IRU WKH HQXPHUDWLRQ RI PLFUREHV LQ WKH VXEVXUIDFH :DNVPDQ f XQGHUUHSUHVHQWHG WKH QXPEHUV RI PLFUREHV LQ WKH VXEVXUIDFH VKRZLQJ D GHFOLQH LQ SRSXODWLRQ ZLWK GHSWK 7KHVH GDWD UHVXOWHG IURP WKH XVH RI QXWULHQW ULFK JURZWK PHGLD LQDSSURSULDWH IRU WKH HQXPHUDWLRQ RI JURXQGZDWHU EDFWHULD :LOVRQ DQG 0F1DEE f 5HFHQW ZRUN VKRZV WKDW PRUH VXEVWDQWLDO SRSXODWLRQV RI KHWHURWURSKLF RUJDQLVPV H[LVW LQ VKDOORZ ZDWHU WDEOH DTXLIHUV WKDQ ZHUH SUHYLRXVO\ WKRXJKW :LOVRQ HW DO Df GHPRQVWUDWHG WKDW WKH QXPEHUV RI RUJDQLVPV ZHUH UHODWLYHO\ FRQVWDQW WR D GHSWK RI VL[ PHWHUV LQ D VKDOORZ ZDWHU WDEOH DTXLIHU 7KH SRSXODWLRQV RI KHWHURWURSKLF EDFWHULD ZHUH HVWLPDWHG WR EH DSSUR[LPDWHO\ A RUJDQLVPVJUDP GU\ ZHLJKW VRLO *KLRUVH DQG %DONZLOO f

PAGE 40

7DEOH 6RUSWLRQ FRHIILFLHQWV RI VHOHFWHG DURPDWLF K\GURFDUERQV RQ ORZ RUJDQLF FDUERQ VRLO &RPSRXQG .G DYHUDJH VWDQGDUG GHYLDWLRQ 7ROXHQH S;\OHQH 7ULPHWK\OEHQ]HQH 7ULPHWK\OEHQ]HQH 6RXUFH 6FKZDU]HQEDFK DQG :HVWDOO

PAGE 41

$ UHYLHZ RI WKH WHFKQLTXHV IRU WKH HQXPHUDWLRQ DQG HVWLPDWLRQ RI PLFURELDO ELRPDVV ZHUH SUHVHQWHG E\ $WODV f DQG :HEVWHU HW DO f %RXZHU DQG 0F&DUW\ f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f LV WKH YROXPHWULF ZDWHU FRQWHQW POFPAfDQG & LV WKH VROXWLRQ SKDVH FRQFHQWUDWLRQ RI D VROXWH XJ/f (QYLURQPHQWDO )DFWRUV $IIHFWLQJ %LRGHJUDGDWLRQ 0DQ\ IDFWRUV FDQ DIIHFW WKH WUDQVIRUPDWLRQ RI RUJDQLF FRQWDPLQDQWV LQ WKH VXEVXUIDFH 0F&DUW\ f LQFOXGHG ORZ VXEVWUDWH FRQFHQWUDWLRQV WR[LF FRQGLWLRQV PROHFXODU VWUXFWXUH RI WKH VXEVWUDWH LQDFFHVVLELOLW\ RI WKH VXEVWUDWH DQG DEVHQFH RI HVVHQWLDO DURZWK IDUFHUV %LRORJLFDO DFWLYLW\ LV RIWHQ OLPLWHG EY FHUWDLQ PAIVKRnLA UHTXLUHPHQWV RI WKH FHOO VXSSOLHG IURP WKH HQYLURQPHQW ,PSRUWDQW JHRFKHPLFDO SURSHUWLHV LQFOXGH G+ UHGR[ SRWHQWLDO QLWURJHQ DQG SKRVSKRUXV FRQFHQWUDWLRQV DQG WKH

PAGE 42

DYDLODELOLW\ RI DQ DSSURSULDWH HOHFWURQ DFFHSWRU 2[\JHQ LV XVHG DV WKH XOWLPDWH HOHFWURQ DFFHSWRU IRU DHURELF GHJUDGDWLRQ SURFHVVHV DQG LV RIWHQ D OLPLWLQJ IDFWRU LQ WKH GHJUDGDWLRQ RI K\GURFDUERQV 0ROHFXODU R[\JHQ LV DOVR HVVHQWLDO WR WKH DHURELF PHWDEROLVP RI DURPDWLF FRPSRXQGV EHFDXVH LW LV LQFRUSRUDWHG LQWR WKH VWUXFWXUH RI WKH PHWDEROLF SURGXFWV (YDQV f 7KH ELRFKHPLVWU\ RI WKH DHURELF PHWDEROLVP RI DURPDWLF FRPSRXQGV LV ZHOO HVWDEOLVKHG 'DJOH\ f 7KH ILUVW VWHS LQ WKLV PHWDEROLF SDWKZD\ LV WKH UHPRYDO RI VLGH FKDLQV IROORZHG E\ WKH HQ]\PH R[\JHQDVHVf PHGLDWHG K\GUR[\ODWLRQ RI WKH DURPDWLF ULQJ $VVXPLQJ b FRQYHUVLRQ RI FDUERQ WR ELRPDVV DQG LQFRPSOHWH R[LGDWLRQ RI WKH K\GURFDUERQ PROHFXOHV WZR SDUWV RI R[\JHQ DUH UHTXLUHG IRU WKH GHJUDGDWLRQ RI HDFK SDUW K\GURFDUERQ :LOVRQ HW DO f 7KH FRPSOHWH R[LGDWLRQ RI K\GURFDUERQ PROHFXOHV WR &2A DQG +' PD\ UHTXLUH WKUHH WR IRXU SDUWV RI R[\JHQ SHU SDUW K\GURFDUERQ 7KHUH LV VRPH HYLGHQFH IRU WKH DQDHURELF ELRGHJUDGDWLRQ RI DURPDWLF FRPSRXQGV LQ WKH HQYLURQPHQW ,Q WKH DEVHQFH RI R[\JHQ QLWUDWHV VXOIDWHV DQG &&! EHFRPH HOHFWURQ DFFHSWRUV %RXZHU DQG 0F&DUW\ f SUHVHQWHG D UHYLHZ RI WKHVH SURFHVVHV 1LWUDWH UHVSLUDWLRQ 3VXHGRPRQDV DQG 0RUD[HOOD VSf DQG PHWKDQRJHQLF IHUPHQWDWLRQ SURFHVVHV FDQ UHGXFH WKH EHQ]HQH QXFOHXV IROORZHG E\ K\GURO\VLV WR \LHOG DOLSKDWLF DFLGV (YDQV f :LOVRQ DQG 5HHV f VKRZHG WKH DQDHURELF GHJUDGDWLRQ RI EHQ]HQH WROXHQH [\OHQHV DQG DON\OEHQ]HQHV XQGHU PHWKDQRJHQLF FRQGLWLRQV

PAGE 43

2YHU D VL[ ZHHN SHULRG RQO\ WROXHQH VKRZHG VXEVWDQWLDO GHJUDGDWLRQ EXW DIWHU ZHHNV EHQ]HQH ZDV UHGXFHG E\ b WROXHQH E\ b HWK\OEHQ]HQH E\ b DQG R[\OHQH E\ b 1XWULHQW DGGLWLRQ GHFUHDVHG WKH UDWH RI K\GURFDUERQ UHPRYDO 7KH PHWDEROLF SURGXFWV IURP WKH DQDHURELF GHJUDGDWLRQ RI WKH DURPDWLF PROHFXOHV ZHUH QRW LQYHVWLJDWHG 1LWUDWH UHVSLUDWLRQ RI [\OHQH LQ D ULYHU DOOXYLXP ZDV GHPRQVWUDWHG E\ .XKQ HW DO f +RZHYHU DQDHURELF ELRWUDQVIRUPDWLRQV RFFXU H[WUHPHO\ VORZO\ PRQWKVf UHODWLYH WR DHURELF SURFHVVHV ZKLFK PD\ EH FRPSOHWHG LQ D PDWWHU RI KRXUV :LOVRQ f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f GHPRQVWUDWHG DQ LQFUHDVH LQ WKH WLPH UHTXLUHG IRU DFFOLPDWLRQ ODJ WLPHf RI EDFWHULDO FXOWXUHV ZLWK LQFUHDVLQJ FRQFHQWUDWLRQV RI QDSWKHOHQH /DJ WLPHV SULRU WR VXEVWDQWLDO PLFURELDO GHJUDGDWLRQ RI D VROXWH QXWULHQW UHIOHFWV WKH WLPH UHTXLUHG E\ WKH LQGLJHQRXV RU

PAGE 44

PLFURIORUD WR DGDSW WR WKH DGGHG VXEVWDQFH $GDSWLRQ LV D SKHQRPHQRQ UDWKHU WKDQ D PHFKDQLVP RU SURFHVV DQG WKH WHUP UHIHUV WR DQ LQFUHDVH LQ WKH UDWH RI ELRWUDQVIRUPDWLRQ RI D VXEVWDQFH UHVXOWLQJ IURP H[SRVXUH WR WKDW VXEVWDQFH :LOVRQ HW DO Ef /RZ VROXWH FRQFHQWUDWLRQV PD\ UHVXOW LQ WKH RFFXUUHQFH RI D WKUHVKROG OLPLW EHORZ ZKLFK WKH PLFURIORUD DUH XQDEOH WR XWLOL]H WKH VROXWH ZLWK RXW D FRVROXWH :LOVRQ DQG 0F1DEE f -HQVHQ HW DO f GHPRQVWUDWHG WKH GHJUDGDWLRQ RI DURPDWLF PROHFXOHV WR OHVV WKDQ XJ/ LPSO\LQJ WKDW WKHUH ZDV D YHU\ ORZ WKUHVKROG OLPLW IRU WKH DURPDWLF K\GURFDUERQV 7KH UHODWLRQVKLS EHWZHHQ FRQFHQWUDWLRQ DQG ELRGHJUDGDWLRQ ZDV UHYLHZHG E\ $OH[DQGHU f +H VWUHVVHG WKH LPSRUWDQFH RI VWXG\LQJ FRQWDPLQDQW OHYHOV WKDW H[LVW LQ WKH HQYLURQPHQW $URPDWLF %LRGHJUDGDWLRQ 9DOXHV )URP WKH /LWHUDWXUH 0F.HH HW DO f UHSRUWHG WKH R[LGDWLRQ RI JDVROLQH E\ 3VHXGRPRQDV DQG $UWKUREDFWHU XQGHU DHURELF EXW QRW DQDHURELF FRQGLWLRQV 'HJUDGDWLRQ RI JDVROLQH E\ 3VHXGRPRQDV ZDV UHSRUWHG E\ :LOOLDPV DQG :LOGHU f DQG /LWFKILHOG DQG &ODUN f VKRZHG VLJQLILFDQW QXPEHUV FHOOVP/f RI fK\GURFDUERQ GHJUDGLQJ EDFWHULD LQ JURXQGZDWHU FRQWDPLQDWHG ZLWK SHWUROHXP K\GURFDUERQV IURP WZHOYH VLWHV %DFWHULDO SRSXODWLRQV DSSHDUHG WR EH UHODWHG WR WKH FRQFHQWUDWLRQV RI K\GURFDUERQV 7KHVH GDWD LQGLFDWH WKH DGDSWDWLRQ RI PLFURELDO FRPPXQLWLHV WR WKH FKDQJLQJ QXWULHQW VRXUFH LH JDVROLQHf 7KH WZR PDMRU PHFKDQLVPV RI DGDSWDWLRQ DUH LQGXFWLRQ RI PHWDEROLF SDWKZD\V RU WKH

PAGE 45

DFWLYDWLRQ RU WUDQVIHU RI SODVPLGV /LWFKILHOG f 7KLV DELOLW\ RI PLFURRUJDQLVPV WR DGDSW WR WKH SUHVHQFH RI FRQWDPLQDQWV IRUPV WKH EDVLV RI LQVLWX ELRGHJUDGDWLRQ 6HYHUDO UHVHDUFKHUV KDYH UHSRUWHG WKH ELRGHJUDGDWLRQ RI DURPDWLF FRPSRXQGV LQ JURXQGZDWHU 2QH VKRUWFRPLQJ RI PRVW RI WKLV UHVHDUFK LV WKH ODFN RI GHJUDGDWLRQ UDWH FRHIILFLHQW GDWD UHTXLUHG IRU XVH LQ JURXQGZDWHU WUDQVSRUW PRGHOV DQG LQVXIILFLHQW GDWD RQ VROXWH FRQFHQWUDWLRQV -DPLVRQ HW DO f UHSRUWHG WKH XVH RI EHQ]HQH DV D VROH FDUERQ VRXUFH 1R UDWH FRHIILFLHQW GDWD ZHUH JLYHQ 0F.HQQD DQG +HDWK f QRWHG WKH VORZ R[LGDWLRQ RI EHQ]HQH E\ 3 SXWLGD 'HOILQR DQG 0LOHV f VKRZHG WKH GHJUDGDWLRQ RI EHQ]HQH LQ GD\V XQGHU DHURELF FRQGLWLRQV LQ )ORULGDQ JURXQGZDWHU ZLWK DQ HLJKW GD\ ODJ SKDVH (WK\OEHQ]HQH ZDV GHJUDGHG DV D VROH FDUERQ VRXUFH *LEVRQ DQG
PAGE 46

GD\ DW & DQG GD\V DW & ZHUH UHSRUWHG LQ FROXPQ VWXGLHV ZLWK PL[HG DXWRFKWKRQRXV IORUD IURP FOHDQ JURXQGZDWHU 7KH PHWD DQG SDUD LVRPHUV RI [\OHQH DQG WULPHWK\OEHQ]HQH ZHUH GHJUDGHG PRUH UDSLGO\ WKDQ R[\OHQH WMULPHWK\ ,EHQ] HQH RU WULPHWK\ OEHQ] HQH 7KHVH VWXGLHV E\ .DSSHOHU DQG :XKUPDQQ DEf PDNH XS WKH EXON RI WKH ZRUN RQ GHJUDGDWLRQ RI DON\O VXEVWLWXWHG EHQ]HQHV ,QVLWX %LRGHJUDGDWLRQ $SSOLFDWLRQ RI LQVLWX ELRUHPHGLDWLRQ WHFKQRORJ\ IRU WKH UHQRYDWLRQ RI K\GURFDUERQ FRQWDPLQDWHG DTXLIHUV LV EDVHG SULPDULO\ RQ WKH ZRUN RI 5D\PRQG HW DO DEf DQG 5D\PRQG HW DO f DW 6XQWHFK 1XWULHQWV DQG R[\JHQ ZHUH LQWURGXFHG ZLWK LQMHFWLRQ ZHOOV DQG FLUFXODWHG WKURXJK WKH DTXLIHU ZLWK SXPSLQJ ZHOOV 7KLV WHFKQLTXH DQG RWKHU ELRn UHPHGLDWLRQ PHWKRGV ZHUH UHYLHZHG E\ :LOVRQ HW DO f 7KHVH DXWKRUV QRWHG WKDW VWXGLHV DUH QHHGHG WR LQYHVWLJDWH WKH HIIHFWLYHQHVV RI QDWXUDO ELRUHVWRUDWLRQ DQG WR HYDOXDWH ZKHWKHU HQKDQFHPHQW RI QDWXUDO SURFHVVHV LV SRVVLEOH RU GHVLUDEOH 7UDQVSRUW RI VXIILFLHQW R[\JHQ WR VXEVXUIDFH PLFUREHV LV D PDMRU WHFKQLFDO SUREOHP 2[\JHQ LV RQO\ VOLJKWO\ VROXEOH LQ ZDWHU DQG LV TXLFNO\ GHSOHWHG GXULQJ DHURELF ELRGHJUDGDWLRQ 2[\JHQ DGGLWLRQ E\ DLU VSDUJLQJ R[\JHQ VSDUJLQJ DQG WKH XVH RI K\GURJHQ SHUR[LGH DUH GRFXPHQWHG LQ WKH OLWHUDWXUH /HH DQG :DUG f 7KH XVH RI K\GURJHQ SHUR[LGH DSSHDUV SDUWLFXODUO\ DGYDQWDJHRXV 75, f +\GURJHQ SHUR[LGH LV UHODWLYHO\ LQH[SHQVLYH QRQSHUVLVWHQW

PAGE 47

DQG LV PRUH VROXEOH LQ ZDWHU WKDQ DLU RU PROHFXODU R[\JHQ +RZHYHU LW LV DOVR F\WRWR[LF DQG PD\ EH FKHPLFDOO\ UHGXFHG HVSHFLDOO\ LQ WKH SUHVHQFH RI LURQ VDOWV 7KH ELRORJLFDO GHFRPSRVLWLRQ RI K\GURJHQ SHUR[LGH LV HQ]\PDWLF FDWDODVH +r +r r >@ SHUR[LGDVH + ;+ + ; >@ ZKHUH ; LV D ELRORJLFDO UHGXFLQJ DJHQW 1RQHQ]\PDWLF GHFRPSRVLWLRQ RFFXUV PRVW IUHTXHQWO\ LQ WKH SUHVHQFH RI LURQ VDOWV )H + )H 2+ 2+r >@ 2+r + + + rB >@ %ULWWRQ f UHSRUWHG WKDW K\GURJHQ SHUR[LGH ZDV UHODWLYHO\ VWDEOH LQ FRPELQDWLRQ ZLWK SKRVSKDWHV HYHQ LQ WKH SUHVHQFH RI PRGHUDWH LURQ FRQFHQWUDWLRQV DQG WKDW EDFWHULDO SRSXODWLRQV FDQ WROHUDWH +&! FRQFHQWUDWLRQV XS WR PJ/ +\GURJHQ SHUR[LGH ZDV VKRZQ %ULWWRQ f WR LQFUHDVH PLFURELDO FRXQWV E\ EXW WKHUH ZDV QR UHSRUWHG LQFUHDVH LQ K\GURFDUERQ UHPRYDO 0HDVXUHPHQW RI 0LFURELDO $FWLYLW\ 7KH UHGXFWLRQ RI ,17 SLRGRSKHQROSQLWURSKHQ\O SKHQ\O WHWUD]ROLXP FKORULGHf WR ,17IRUPD]DQ E\ WKH HOHFWURQ WUDQVSRUW V\VWHP LV D IXQFWLRQ RI FHOO UHVSLUDWLRQ DQG LV ZLGHO\ XVHG DV D JHQHUDO PHDVXUH RI PLFURELDO DFWLYLW\

PAGE 48

7KLV WHFKQLTXH LV UHFRPPHQGHG DV DQ LQGH[ RI J PLFURELDO DFWLYLW\ RI VRLO PLFURRUJDQLVPV .OH f 5HGXFWLRQ RI ,17 WR ,17IRUPD]DQ LV D VHQ IRU GHK\GURJHQDVH DFWLYLW\ 7KH ,17IRUPD]DQ H[WUDFWHG IURP VHGLPHQWV DQG VRLOV E\ PHWKDQRO IRUPD]DQ FRPSOH[ LV VWDEOH 7UHYRUV HW DO KLJK FRUUHODWLRQ EHWZHHQ HOHFWURQ WUDQVSRUW V\ DQG R[\JHQ FRQVXPSWLRQ .OHLQ HW DO f S UDSLG DQG VLPSOH SURFHGXUH IRU WKH GHWHUUQLQDW GHK\GURJHQDVH DFWLYLW\ XVLQJ ,17 LQ VRLOV ZLWK FDUERQ 6XPPDU\ 7KLV OLWHUDWXUH UHYLHZ KDV SUHVHQWHG VRPH SULQFLSOHV UHTXLUHG DV D EDVLV IRU WKH GLVFXVV H[SHULPHQWDO ZRUN UHSRUWHG LQ WKLV GLVVHUWDWLR KLJKOLJKWHG VRPH RI WKH LPSRUWDQW ILQGLQJV UHO GLVSHUVLRQ VRUSWLRQ DQG ELRGHJUDGDWLRQ RI DUR FRPSRXQGV LQ JURXQGZDWHU V\VWHPV HQHUDO LQ HW DO VLWLYH DVVD\ LV HDVLO\ DQG WKH ,17 f IRXQG D VWHP DFWLYLW\ UHVHQWHG D LRQ RI ORZ RUJDQLF RI WKH EDVLF LRQ RI WKH Q DQG KDV DWLYH WR WKH PDW LF

PAGE 49

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f DW /DNH $OIUHG ), 7KH VLWH ZDV ORFDWHG LQ WKH 7UDLO5LGJH /DNH :DOHV 5LGJH V\VWHP RI KLOOV FRQWDLQLQJ GHHS LQWHUQDOO\ GUDLQHG ODNH EDVLQV 8QFRQVROLGDWHG GHSRVLWV LQ WKH DUHD FRQVLVWHG RI VDQG DQG VDQG\ FOD\V XS WR IW WKLFN DERYH WKH OLPHVWRQH EHGURFN 7KH JHRORJ\ ZDV PDUNHG E\ PDQ\ VLQNKROHV IRUPHG WKURXJK VXEVLGHQFH RI WKH XQFRQVROLGDWHG GHSRVLWV LQWR VROXWLRQ FDYLWLHV LQ WKH OLPHVWRQH 6SDQJOHU f

PAGE 50

7KH UHVHDUFK VLWH ZDV ORFDWHG RQ WKH ULP RI DQ DQFLHQW VLQNKROH 7KH VXUILFLDO DTXLIHU ZDV FRPSRVHG RI VDQG DQG FOD\H\ VDQGV $Q FRQWLQXRXV FOD\H\ FRQILQLQJ OD\HU RI XQHYHQ GHSWK ZDV SUHVHQW EHWZHHQ WR IW EHORZ ODQG VXUIDFH 7KLV OD\HU VXSSRUWHG D VDWXUDWHG ]RQH EHWZHHQ WR IW LQ WKLFNQHVV /RFDO UHOLHI ZDV IURP IW DERYH PHDQ VHD OHYHOf DW WKH WRS RI WKH KLOO DW WKH HDVWHUQ ERXQGDU\ RI WKH VLWH WR IW LQ WKH ZHWODQG DUHD DW WKH ZHVW HGJH RI WKH VLWH $ VLWH PDS LV VKRZQ LQ )LJXUH 7KH VXUILFLDO DTXLIHU ZDV FRPSULVHG RI PHGLXP DQJXODU JUDLQHG VDQGV DQG ILOO PDWHULDO 7KH K\GURORJ\ RI WKH VLWH ZDV GLVFXVVHG E\ .LOODQ f 7KH VXUILFLDO DTXLIHU ZDV FRQWDPLQDWHG GXULQJ WKH VSULQJ RI E\ WKH ORVV RI JDOORQV RI OHDGHG JDVROLQH IURP D VWRUDJH WDQN )UHH IORDWLQJ JDVROLQH ZDV UHPRYHG E\ VXUIDFH VNLPPLQJ DV RI 0D\ 7KH RXWOLQH RI WKH FRQWDPLQDWHG DUHD DV RI 2FWREHU LV VKRZQ LQ )LJXUH 7KH SOXPH ZDV GHILQHG E\ GHWHUPLQDWLRQ RI H[SORVLYH JDV FRQFHQWUDWLRQV LQ ERUH KROHV WKURXJKRXW WKH VLWH 7KHVH GDWD ZHUH FRQILUPHG E\ *& DQDO\VLV RI VRLO FRUHV DQG WKH XVH RI JURXQG SHQHWUDWLQJ UDGDU 7KHVH WHFKQLTXHV ZHUH GHVFULEHG LQ GHWDLO E\ .LOODQ f $TXLIHU 0DWHULDO $TXLIHU PDWHULDOV XVHG LQ WKLV UHVHDUFK ZHUH REWDLQHG IURP WKH ILHOG UHVHDUFK VLWH DW WKH ,)$6&LWUXV 5HVHDUFK DQG (GXFDWLRQ &HQWHU DW /DNH $OIUHG )ORULGD $ VLWH PDS LV

PAGE 51

)LJXUH 6LWH SODQ RI WKH ILHOG UHVHDUFK VLWH DW WKH &LWUXV 5HVHDUFK DQG (GXFDWLRQ &HQWHU /DNH $OIUHG )/ Z FQ

PAGE 52

)LJXUH ([WHQW RI WKH K\GURFDUERQ SOXPH DW WKH ILHOG UHVHDUFK VLWH DV RI 2FWREHU

PAGE 53

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f XVLQJ VLV %ODFN f RI 6ROXWHV ZDWHU IURP WKH /DNH $OIUHG VRXUFH RI GLVVROYHG VROXWHV V LQ WKLV VWXG\ :LWK WKH ROXPQ VRUSWLRQ H[SHULPHQW ZLWK HU DOO H[SHULPHQWV ZHUH VROYHG K\GURFDUERQV DW

PAGE 54

FRQFHQWUDWLRQV RFFXUULQJ LQ WKH ILHOG 7KHVH FRQFHQWUDWLRQV DUH WKH UHVXOW RI WKH VROXELOL]DWLRQ DQG VXEVHTXHQW ZHDWKHULQJ RI JDVROLQH K\GURFDUERQV LQWR JURXQGZDWHU :HOO 2+0 ZDV XVHG DV WKH VRXUFH RI ZDWHU IRU WKHVH H[SHULPHQWV 7KLV ZHOO ZDV FKRVHQ EDVHG RQ FRQVLVWHQWO\ KLJK OHYHOV RI GLVVROYHG DURPDWLF K\GURFDUERQV +\GURFDUERQ IUHH JURXQGZDWHU ZDV REWDLQHG IURP D QRQFRQWDPLQDWHG SRUWLRQ RI WKH DTXLIHU :HOO 5$3f +\GURFDUERQ FRQFHQWUDWLRQV LQ WKHVH ZDWHUV ZHUH PRQLWRUHG PRQWKO\ :HOO 5$3 UHPDLQHG IUHH RI DURPDWLF K\GURFDUERQV WKURXJKRXW WKH FRXUVH RI WKHVH H[SHULPHQWV &RQFHQWUDWLRQV RI DURPDWLF K\GURFDUERQV YDULHG LQ :HOO 2+0 EXW UHPDLQHG KLJK HQRXJK WR SURYLGH VDPSOHV IRU ODERUDWRU\ H[SHULPHQWV :DWHU VDPSOHV ZHUH FROOHFWHG ZLWK D FP f LG SRO\ YLQ\O FKORULGH 39&f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

PAGE 55

7KH VLQJOH VROXWH FROXPQ H[SHULPHQW ZLWK EHQ]HQH XVHG 5$3 ZDWHU VSLNHG ZLWK EHQ]HQH $OGULFK JROG ODEHO bf WR \LHOG D VROXWLRQ RI XJ/ EHQ]HQH +\GURFDUERQ $QDO\VHV *DV FKURPDWRJUDSKLF DQDO\VHV RI K\GURFDUERQV IRU WKLV VWXG\ ZHUH SHUIRUPHG RQ WZR V\VWHPV 7KHVH DUH GHVFULEHG EHORZ *&06 $QDO\VHV )LHOG VDPSOHV FROOHFWHG EHIRUH 6HSWHPEHU DQG WKH LQLWLDO K\GURO\VLV YLDOV ZHUH DQDO\]HG IRU YRODWLOH DURPDWLF FRQVWLWXHQWV XVLQJ D +HZOHWW 3DFNDUG PRGHO % *&06&203 V\VWHP HTXLSSHG ZLWK D SRUW 7HNPDU $XWRPDWLF /LTXLG 6DPSOHU $/6f DQG /LTXLG 6DPSOH &RQFHQWUDWRU /6&f SXUJH DQG WUDS V\VWHP (3$ PHWKRG ZDV XVHG 6HSDUDWLRQ RI DQDO\WHV ZDV DFKLHYHG ZLWK D PP LG PHWHU ORQJ '% XUQ ILOP WKLFNQHVVf IXVHG VLOLFD FDSLOODU\ FROXPQ t : 6FLHQWLILFf ZLWK PDQXDO OLTXLG QLWURJHQ FU\RIRFXVLQJ 7KH LVRPHU RI GLFKORUREHQ]HQH ZDV XVHG DV DQ LQWHUQDO VWDQGDUG 5HVSRQVH IDFWRUV IRU EHQ]HQH WROXHQH HWK\OEHQ]HQH DQG R[\OHQH ZHUH GHWHUPLQHG UHODWLYH WR WKH LQWHUQDO VWDQGDUG DQG XVHG IRU TXDQWLWDWLRQ 5HVSRQVH IDFWRUV IRU PHWD DQG SDUD [\OHQH ZHUH DVVXPHG WR EH WKH VDPH DV WKH RUWKR LVRPHU $ UHVSRQVH IDFWRU RI ZDV DVVXPHG IRU WKH &A+A K\GURFDUERQV &KURPDWRJUDSKLF FRQGLWLRQV ZHUH DV IROORZV

PAGE 56

PDVV UDQJH 7HPS 7HPS 5DWH +ROG WLPH &U\RIRFXV WLPH 3UHFRRO DPX & & &PLQ PLQXWHV PLQXWHV PLQXWHV *& $QDO\VHV +\GURFDUERQ DQDO\VHV ZHUH SHUIRUPHG RQ D 3HUNLQ (OPHU PRGHO JDV FKURPDWRJUDSK ZLWK D IODPH LRQL]DWLRQ GHWHFWRU DQG PLFURSURFHVVRU GDWD V\VWHP 6DPSOHV ZHUH FRQFHQWUDWHG E\ SXUJH DQG WUDS ZLWK D 7HNPDU /6&$/6 V\VWHP HPSOR\LQJ D PRGLILHG YHUVLRQ RI (3$ PHWKRG $QDO\WLFDO VHSDUDWLRQ ZDV DFKLHYHG ZLWK D PP LG PHWHU ORQJ IXVHG VLOLFD 0HJDERUH '% b PHWK\OSRO\VLOR[DQHf FROXPQ t : 6FLHQWLILFf ZLWK D XUQ ILOP WKLFNQHVV %HQ]HQH WROXHQH HWK\OEHQ]HQH R[\OHQH DQG PS[\OHQH ZHUH TXDQWLILHG XVLQJ WKH LQWHUQDO VWDQGDUG PHWKRG GLFKORUREHQ]HQHf GXULQJ $XJXVW DQG 6HSWHPEHU IRU PRQWKO\ DQDO\VLV RI ILHOG VDPSOHV DQG IRU GD\ K\GURO\VLV DPSXOHV $IWHU WKLV GDWH HLJKW LVRPHUV RI &A+A ZHUH LGHQWLILHG DQG FRQILUPHG E\ DQDO\VLV RI LQGLYLGXDO VWDQGDUGV DQG ZHUH TXDQWLILHG LQ DOO FKURPDWRJUDPV DORQJ ZLWK %7(; EHQ]HQH WROXHQH HWK\OEHQ]HQH PSR[\OHQHf FRPSRXQGV 7KH LQWHUQDO VWDQGDUG ZDV FKDQJHG IURP GLFKORUREHQ]HQH WR FKORUREHQ]HQH WR DYRLG FRHOXWLRQ SUREOHPV $ FRPSOHWH GHVFULSWLRQ RI WKLV DQDO\WLFDO PHWKRG DQG D VXPPDU\ RI WKH TXDOLW\ FRQWURO SDUDPHWHUV IRU WKLV PHWKRG DUH LQ $SSHQGL[ $

PAGE 57

7KH PHWD DQG SDUD LVRPHUV RI [\OHQH ZHUH QRW UHVROYHG RQ HLWKHU FKURPDWRJUDSKLF V\VWHP HPSOR\HG LQ WKLV UHVHDUFK 7KH FRPELQDWLRQ RI WKHVH DQDO\WHV ZDV UHSRUWHG DV PS [\OHQH /LNHZLVH HWK\OWROXHQH DQG HWK\OWROXHQH ZHUH QRW UHVROYHG ZLWK WKH DQDO\WLFDO V\VWHP HPSOR\HG LQ WKLV VWXG\ DQG WKH FRPELQHG FRQFHQWUDWLRQV RI WKHVH DQDO\WHV ZHUH UHSRUWHG LQ WKLV VWXG\ ZLWK WKH DEEUHYLDWLRQ HWK\OWROXHQH +\GURO\VLV 6WXGLHV +\GURO\VLV VWXGLHV ZHUH SHUIRUPHG LQ P/ JODVV DPSXOHV )LVKHU 6FLHQWLILFf $PSXOHV ZHUH ULQVHG ZLWK PHWKDQRO DQG RYHQ GULHG DW & 7HQ PLFUROLWHUV RI K\GURFDUERQ FRQWDPLQDWHG JURXQGZDWHU ZHUH VSLNHG LQWR DPSXOHV FRQWDLQLQJ P/ RI EXIIHU VROXWLRQ %XIIHU VROXWLRQV ZHUH SUHSDUHG ZL WK QRQ FRQWD PLQDWHG Z HOO ZDWHU DQG WKH S+ ZDV DGMXVWHG WR S+ DQG ZLWK 0 SKRVSKDW H EXIIHUV 7K H DPSXO HV ZH UH VHDOHG ZLWK DQ DPSXOH V HDOHU 2F HDQRJUDSKLF ,Q WHUQDWL RQDO &ROOHJH 6WDWLRQ 7;f DQG DXWRFODYHG KRXU DW &f 2Q H VHW RI DPSXOHV ZDV DQDO\]HG DW WL PH ] HUR $QRWKHU V HW RI DPSXOHV ZDV VWRUHG LQ WKH GDUN DW DQG & DQG DQDO \ ]HG E\ JD V FKURPDWRJUDSK\ *&f DIWHU GD\V

PAGE 58

%DWFK 6RUSWLRQ 6WXGLHV 6RUSWLRQ EDWFK VWXGLHV ZHUH SHUIRUPHG LQ P/ 92$ YLDOV ZLWK 7HIORQ FRDWHG VHSWD )LVKHU 6FLHQWLILF f 9LDOV ZHUH ILUVW ILOOHG ZLWK J RI DTXLIHU PDWHULDO DQG WKHQ DXWRFODYHG DW & IRU KRXU RQ HDFK RI WKUHH FRQVHFXWLYH GD\V :DWHU IURP Z HOO 2+0 FRQ WDLQLQJ D PL[WXUH RI GLVVROYHG DURPDWLF K\GURFDUERQV ZDV XVHG LQ WKH EDWFK VRUSWLRQ H[SHULPHQWV $V D UHVXOW DOO WKHVH H[SHULPHQWV DUH PXOWLVROXWH DW FRQFHQWUDWLRQV UHSUHVHQWDWLYH RI WKRVH IRXQG DFURVV WKH DTXLIHU DW /DNH $OIUHG 6RUSWLRQ ([SHULPHQWV :DWHU XVHG LQ WKH VRUSWLRQ H[SHULPHQWV ZDV ILOWHU VWHULOL]HG WKURXJK XUQ PHPEUDQH ILOWHUV *HOPDQ 0HWULFHOf DQG WKHQ DGGHG WR HDFK YLDO 7KH UDQJH RI VROXWH FRQFHQWUDWLRQV ZDV DFKLHYHG E\ GLOXWLRQ RI :HOO 2+0 ZDWHU ZLWK :HOO 5$3 ZDWHU DW UDWLRV EHWZHHQ WR (DFK GLOXWLRQ ZDV SHUIRUPHG LQ WULSOLFDWH 1RQVRLO FRQWUROV VROXWH ZDWHU ZLWK QR VRLOf ZHUH DOVR VHW XS LQ WULSOLFDWH 7R PLQLPL]H KHDGVSDFH WKH YLDOV ZHUH SUHPL[HG RQ D URWDU\ WXPEOHU IRU DSSUR[LPDWHO\ KRXU WR UHPRYH LQWHUVWLWLDO DLU DQG WR GLVSHUVH WKH IRDP WKDW IRUPHG GXULQJ PL[LQJ 7KH YLDOV ZHUH WKHQ RSHQHG FRPSOHWHO\ ILOOHG ZLWK VDPSOH DQG UHFDSSHG $ KLJK VROLGV WR VROXWLRQ UDWLR J J f ZDV XVHG WR PD[LPL]H WKH IUDFWLRQDO GHFUHDVH LQ VROXWLRQ

PAGE 59

FRQFHQWUDWLRQ RZLQJ WR VRUSWLRQ DQG WR PRUH FORVHO\ VLPXODWH QDWXUDO DTXLIHU FRQGLWLRQV 9LDOV XVHG LQ VRUSWLRQ H[SHULPHQWV ZHUH HTXLOLEUDWHG DW URRP WHPSHUDWXUH &f RQ D URWDU\ WXPEOHU DW DSSUR[LPDWHO\ USP IRU KRXUV DQG WKHQ FHQWULIXJHG DW IRU PLQXWHV 6DPSOHV ZHUH DQDO\]HG E\ SXUJH DQG WUDSJDV FKURPDWRJUDSK\ 9LDOV XVHG LQ WKH EDWFK VRUSWLRQ NLQHWLF UDWH VWXG\ ZHUH VDPSOHG DW DQG KRXUV 'HVRUSWLRQ H[SHULPHQWV 'HVRUSWLRQ H[SHULPHQWV ZHUH FRQGXFWHG VXEVHTXHQW WR D VRUSWLRQ H[SHULPHQW )ROORZLQJ FHQWULIXJDWLRQ DQG VDPSOLQJ IRU VRUSWLRQ ORVVHV DSSUR[LPDWHO\ P/ RI VXSHUQDWDQW ZHUH UHPRYHG DQG UHSODFHG ZLWK K\GURFDUERQ IUHH ZDWHU :HOO 5$3 f 7KH YLDOV ZHUH UHHTXLOLEUDWHG IRU KRXUV RQ WKH URWDU\ WXPEOHU FHQWULIXJHG DQG VDPSOHG (DFK YLDO ZDV RQO\ GHVRUEHG RQH WLPH 7KHVH H[SHULPHQWV ZHUH QRW GHVLJQHG WR FDOFXODWH GHVRUSWLRQ LVRWKHUPV RU WHVW LVRWKHUP QRQVLQJXODULW\ &DOFXODWLRQ RI 6RUSWLRQ &RHIILFLHQWV 7KH DPRXQW RI VROXWH VRUEHG WR WKH DTXLIHU PDWHULDO QJ VROXWHJUDP VRLOf ZDV FDOFXODWHG E\ GHWHUPLQLQJ WKH GLIIHUHQFH EHWZHHQ WKH VROXWLRQ FRQFHQWUDWLRQ RI WKH QRQn VRLO EODQNV DQG WKH VRLO FRQWDLQLQJ YLDOV 7KH DPRXQW RI VROXWH ORVW ZDV GLYLGHG E\ WKH VROXWLRQ WR VRLO UDWLR WR QRUPDOL]H WKH GDWD WR D QJJUDP EDVLV 6RUSWLRQ FRHIILFLHQWV ZHUH FDOFXODWHG E\ ILWWLQJ LVRWKHUP GDWD WR WKUHH PRGHOV OLQHDU OLQHDU ZLWK LQWHUFHSW IRUFHG WKURXJK

PAGE 60

]HUR DQG WKH ORJ QRUPDOL]HG )UHXQGOLFKf PRGHOV 0LOOHU DQG :HEHU f &ROXPQ 6RUSWLRQ 6WXGLHV ([SHULPHQWDO 3URFHGXUHV /HDFKLQJ FROXPQ H[SHULPHQWV ZHUH SHUIRUPHG ZLWK D [ PP JODVV SUHSDUDWLYH FKURPDWRJUDSK\ FROXPQ $OWH[ FDW QR f ZLWK D 7HIORQ FRDWHG DGMXVWDEOH SOXQJHU 1NHGL .L]]D HW DO f $TXLIHU PDWHULDO ZDV GU\ SDFNHG LQWR WKH FROXPQ ZKLFK ZDV WKHQ DXWRFODYHG DW & IRU KRXU 7KH VROXWHV ZHUH SXPSHG IURP / 7HIORQ JDV VDPSOLQJ EDJV $OOWHFK $VVRFLDWHV 'HHUILHOG ,/f ZLWK D *LOVRQ PRGHO +3/& SXPS ILWWHG ZLWK D PRGHO V SXPS KHDG *LOVRQ 0HGLFDO (OHFWURQLFV 0LGGOHWRQ :,f 7KH IORZ UDQJH RI WKLV V\VWHP ZDV P/ SHU PLQXWH $OO WUDQVIHU OLQHV DQG FRQQHFWLRQV ZHUH 7HIORQ RU VWDLQOHVV VWHHO WR PLQLPL]H LQWHUDFWLRQ RI VROXWHV ZLWK UHDFWLYH VXUIDFHV &ROXPQ OHQJWK ZDV DGMXVWHG WR FP )ORZ UDWHV WKURXJK WKH FROXPQ ZHUH VHW DW POPLQ FPPLQf IRU VRUSWLRQ VWXGLHV &ROXPQ HIIOXHQW EUHDNWKURXJK FXUYHV %7&Vf ZHUH PHDVXUHG XQGHU VWHDG\ VDWXUDWHG ZDWHU IORZ FRQGLWLRQV ZLWK FRQWLQXRXV DSSOLFDWLRQ RI VROXWH FRQWDLQLQJ ZDWHU (IIOXHQWV IURP WKH VRUSWLRQ FROXPQV ZHUH FROOHFWHG PDQXDOO\ LQ PO FULPS VHDO YLDOV 7KHVH FROXPQ HIIOXHQWV ZHUH HLWKHU DQDO\]HG LPPHGLDWHO\ RU VWRUHG DW & LQ P/

PAGE 61

FULPS VHDO YLDOV ZLWK 7HIORQ FRDWHG VHSWD IRU ODWHU DQDO\VLV $OO VDPSOHV ZHUH DQDO\]HG ZLWKLQ KRXUV 7KH EUHDNWKURXJK RI DQ XQUHWDLQHG VROXWH ZDV GHWHUPLQHG IRU HDFK FROXPQ XVLQJ FDOFLXP FKORULGH POPLQ FROXPQVf %UHDNWKURXJK FXUYHV ZHUH GHWHUPLQHG E\ VSLNLQJ K\GURFDUERQ IUHH JURXQGZDWHU IURP /DNH $OIUHG 5$3f ZLWK FKORULGH PJ/ &D&/Af &KORULGH DQDO\VHV ZHUH SHUIRUPHG ZLWK D FKORULGRPHWHU DXWRPDWLF WLWUDWRU %XFKOHU&RWORYHf &KORULGH LRQ ZDV QRW H[SHFWHG WR EH DGVRUEHG RZLQJ WR WKH ORZ FDWLRQ H[FKDQJH FDSDFLW\ RI WKH /DNH $OIUHG VRLO :HOO ZDWHU XVHG LQ WKH VRUSWLRQ H[SHULPHQWV ZDV ILOWHUHG WKURXJK XP PHPEUDQH ILOWHUV *HOPDQ 0HWULFHOf GLUHFWO\ LQWR WKH 7HIORQ EDJV 7KH EDJV ZHUH DXWRFODYHG SULRU WR HDFK XVH &ROXPQV ZHUH VDWXUDWHG ZLWK ILOWHU VWHULOL]HG ZDWHU IURP ZHOO 5$3 SULRU WR WKH LQSXW RI VROXWH FRQWDLQLQJ ZDWHU (VWLPDWLRQ RI 5HWDUGDWLRQ )DFWRU 5f LQ &ROXPQV 7KUHH PHWKRGV ZHUH XVHG WR HVWLPDWH WKH YDOXH RI 5 IURP WKH FROXPQ GDWD ,Q PHWKRG UHWDUGDWLRQ IDFWRUV 5 f ZHUH FDOFXODWHG E\ ILWWLQJ WKH VROXWLRQ RI %UHQQHU f WR WKH FROXPQ HIIOXHQW FXUYHV 3HFOHW QXPEHUV XVHG IRU WKHVH FDOFXODWLRQV ZHUH GHWHUPLQHG IURP WKH EUHDNWKURXJK RI WKH QRQUHWDLQHG VROXWHV KDYLQJ UHWDUGDWLRQ IDFWRUV HTXDO WR XQLW\ 0HWKRG ZDV EDVHG RQ WKH FRQVHUYDWLRQ RI PDVV SULQFLSOH 7KLV PHWKRG FDOFXODWHG UHWDUGDWLRQ IDFWRUV 5 f FO E\ HYDOXDWLQJ WKH DUHD DERYH WKH EUHDNWKURXJK FXUYH XVLQJ 6LPSVRQnV 5XOH 6ZRNRZVNL f 7KH 5 YDOXH ZDV DVVXPHG FO

PAGE 62

HTXDO WR WKH DUHD DERYH WKH %7& ZKHQ WKH HIIOXHQW FRQFHQWUDWLRQ &f GLYLGHG E\ WKH LQIOXHQW FRQFHQWUDWLRQ & f ZDV SORWWHG YV SRUH YROXPH DV GHVFULEHG E\ HTXDWLRQ >@ 5 >&&T@ GSY >@ ZKHUH SY LV WKH WRWDO QXPEHU RI SRUH YROXPHV GLVSODFHG WKURXJK WKH FROXPQ DQG SY LV SRUH YROXPHV 1NHGL.L]]D HW DO f 7KLV PHWKRG DVVXPHG D PDVV EDODQFH H[LVWHG LQ WKH VRLO FROXPQV 7KH WKLUG PHWKRG VHW WKH UHWDUGDWLRQ IDFWRU 5 f WR HTXDO WKH QXPEHU RI SRUH YROXPHV UHTXLUHG IRU WKH HIIOXHQW FRQFHQWUDWLRQ RI HDFK DQDO\WH WR UHDFK RI WKH LQIOXHQW FRQFHQWUDWLRQ 7KH XVH RI WKLV PHWKRG DVVXPHV WKDW WKH EUHDNWKURXJK FXUYH LV V\PPHWULFDO DQG VLJPRLGDO DQG WKDW HTXLOLEULXP FRQGLWLRQV H[LVW EHWZHHQ WKH VROXWLRQ DQG VRUEHG FRQFHQWUDWLRQV GXULQJ OHDFKLQJ WKURXJK WKH FROXPQ 1NHGL.L]]D HW DO f 7KH YDOXH RI ZDV FDOFXODWHG IURP WKH YDULRXV 5 YDOXHV ZLWK HTXDWLRQ >@ +\GURJHQ 3HUR[LGH (YDOXDWLRQ 7KH UHDFWLRQ UDWH RI K\GURJHQ SHUR[LGH LQ WKH DTXLIHU HQYLURQPHQW ZDV VLPXODWHG E\ PRQLWRULQJ WKH GLVVROYHG R[\JHQ '2f <6, PRGHO SUREH DQG <6, PRGHO $ '2 PHWHUf UHGR[ SRWHQWLDO SODWLQXP UHGR[ HOHFWURGH )LVKHU 6FLHQWLILFf DQG S+ JHO PHPEUDQH HOHFWURGH )LVKHU 6FLHQWLILFf RI ZHOO ZDWHU DQG DTXLIHU PDWHULDO LQ D DUP P/ UHDFWLRQ IODVN &RQWDPLQDWHG ZHOO ZDWHU ZDV

PAGE 63

HTXLOLEUDWHG DW URRP WHPSHUDWXUH &f LQ WKH VHDOHG IODVN +\GURJHQ SHUR[LGH bf ZDV DGGHG XQGLOXWHG LQ PLFUROLWHU TXDQWLWLHV DQG DW YDULRXV GLOXWLRQV $TXLIHU PDWHULDO ZDV WKHQ DGGHG WR DVVHVV WKH DELOLW\ RI WKH PDWHULDO WR FDWDO\]H WKH UHDFWLRQ 7KH b K\GURJHQ SHUR[LGH VWRFN ZDV WLWUDWHG ZLWK 1 SRWDVVLXP SHUPDQJDQDWH 'XSRQW f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f WR D P/ HUOHQPH\HU IODVN DQG WKHQ DPHQGHG ZLWK K\GURJHQ SHUR[LGH bf DPPRQLXP FKORULGH

PAGE 64

7DEOH ([SHULPHQWDO H[SHULPHQW GHVLJQ IRU EDWFK ELRGHJUDGDWLRQ +\GURJHQ 6RGLXP 3HUR[LGH 1+ &O $]LGH 7UHDWPHQW PJ/f PJ/f PJ/f $ QRQH QRQH QRQH ,% QRQH QRQH & QRQH QRQH ,' QRQH QRQH ,( QRQH ,) QRQH QRQH QRQH

PAGE 65

5HDJHQW JUDGH )LVKHU 6FLHQWLILFf DQG b ZYf DTXHRXV VROXWLRQ RI VRGLXP D]LGH )LVKHU 6FLHQWLILFf DV RXWOLQHG LQ 7DEOH 7ULSOLFDWH VDPSOHV ZHUH DQDO\]HG IRU HDFK WUHDWPHQW DW DQG GD\V 7UHDWPHQW QXPEHU ZDV D VWHULOH FRQWURO +\GURJHQ SHUR[LGH ZDV DGGHG EDVHG RQ GDWD IURP WKH K\GURJHQ SHUR[LGH HYDOXDWLRQ H[SHULPHQW DQG RQ GDWD IURP %ULWWRQ f ZKR GHPRQVWUDWHG WKDW F\WRWR[LFLW\ ZDV PLQLPDO DW K\GURJHQ SHUR[LGH FRQFHQWUDWLRQV OHVV WKDQ PJ/ $PPRQLXP FKORULGH ZDV DGGHG EDVHG RQ GDWD IURP 0LWFKHOO f ZKR IRXQG WKDW DPPRQLD QLWURJHQ LV DVVLPLODWHG TXLFNO\ GXULQJ PLFURELDO JURZWK $PPRQLD DV 1+A&/f ZDV DGGHG WR DFKLHYH TXDQWLWLHV FDOFXODWHG WR PHHW QLWURJHQ UHTXLUHPHQWV RI WKH EDFWHULD %LRGHJUDGDWLRQ H[SHULPHQW QXPEHU ZDV GHVLJQHG WR HYDOXDWH WKH HIILFDF\ RI R[\JHQ JDV LQ DGGLWLRQ WR K\GURJHQ SHUR[LGH 7DEOH f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s &f DQG LQYHUWHG RQFH HYHU\ WZR GD\V WR SURYLGH PL[LQJ 6DPSOHV ZHUH WDNHQ DW DQG GD\V

PAGE 66

7DEOH ([SHULPHQWDO GHVLJQ IRU EDWFK ELRGHJUDGDWLRQ H[SHULPHQW 7UHDWPHQW 2[\JHQ DGGLWLRQ 1+& PJ/f 6RGLXP $]LGH PJ/f $ DLU QRQH QRQH % DLU QRQH & DLU QRQH PJ/ Ar QRQH QRQH ( PJ/ +r QRQH ) PJ/ + QRQH A VDWXUDWLRQ QRQH QRQH + A VDWXUDWLRQ QRQH 2 VDWXUDWLRQ QRQH

PAGE 67

)ROORZLQJ VDPSOH UHPRYDO IRU *& DQDO\VLV GLVVROYHG R[\JHQ ZDV PHDVXUHG LQ HDFK EDWFK ELRGHJUDGDWLRQ YLDO EDWFK H[SHULPHQWV DQG f ZLWK D <6, PRGHO '2 SUREH DQG <6, PRGHO $ '2 PHWHU
PAGE 68

FDOFXODWH WKH DPRXQW RI VROXWH ORVW WR VRUSWLRQ LQ HDFK EDWFK YLDO 7KH H[WHQW RI WKH VRUSWLRQ ORVV FRUUHFWLRQ YDULHG ZLWK WKH FRQFHQWUDWLRQ RI WKH DQDO\WH DQG WKH VRUSWLRQ SDUDPHWHUV DQG Q 7KLV FRUUHFWLRQ IDFWRU DGGHG DV PXFK DV b WR WKH PHDVXUHG FRQFHQWUDWLRQ YDOXHV 7KHVH SUHGLFWHG ORVVHV UHVXOWLQJ IURP VRUSWLRQ ZHUH DGGHG WR WKH DTXHRXV FRQFHQWUDWLRQ IRU HDFK DQDO\WH LQ HDFK YLDO WR FDOFXODWH WKH WRWDO FRQFHQWUDWLRQ RI HDFK VROXWH LQ WKH YLDO & f 7KHVH & YDOXHV ZHUH HPSOR\HG WR REYLDWH WKH QHHG IRU VLPXOWDQHRXV FDOFXODWLRQ RI ELRGHJUDGDWLRQ RQ ERWK VRUEHG DQG DTXHRXV FRQFHQWUDWLRQV DQG DQ\ FDOFXODWLRQ RI UDWHV RI VRUSWLRQGHVRUSWLRQ GXULQJ ELRGHJUDGDWLRQ 7KH & YDOXHV ZHUH XVHG WR PRGHO WKH ELRORJLFDO UDWH FRHIILFLHQWV 7KH UDWH GDWD ZHUH ILWWHG WR ]HUR RUGHU ILUVW RUGHU VHFRQG RUGHU DQG PL[HG RUGHU UDWH HTXDWLRQV /HYHQVSLHO f DQG WR WKH 7KRPDV VORSH PHWKRG 7KRPDV f &ROXPQ %LRGHJUDGDWLRQ 6WXGLHV ([SHULPHQWDO 3URFHGXUH &ROXPQ ELRORJLFDO GHJUDGDWLRQ H[SHULPHQWV ZHUH SHUIRUPHG ZLWK WKH VDPH FROXPQ V\VWHP GHVFULEHG LQ VHFWLRQ 7ZR IORZ UDWHV ZHUH XVHG LQ WKHVH H[SHULPHQWV 7KHVH ZHUH POPLQ FPPLQf DQG POKU FUDPLQf &ROXPQV RSHUDWHG DW POKU ZHUH ILWWHG ZLWK D ORZ GHDG YROXPH LQOLQH VHSWD (IIOXHQW ZDV ZLWKGUDZQ ZLWK D XO V\ULQJH +DPLOWRQ &Rf DQG DQDO\]HG LPPHGLDWHO\ (IIOXHQWV

PAGE 69

IURP WKH P/PLQ FROXPQV ZHUH FROOHFWHG DQG DQDO\]HG DV GHVFULEHG LQ VHFWLRQ %UHDNWKURXJK FXUYHV IRU D QRQ UHWDLQHG VROXWH ZHUH REWDLQHG ZLWK WULWLDWHG ZDWHU XFL + IRU POKU FROXPQVf RU &D&O POPLQ FROXPQVf $QDO\VHV RI +A2 HIIOXHQWV ZHUH SHUIRUPHG RQ D 'HOWD PRGHO /LTXLG 6FLQWLOODWLRQ &RXQWHU &HDUOH $QDO\WLFDOf XVLQJ 6FLQWLYHUVH ,, VFLQWLOODWLRQ FRFNWDLO )LVKHU 6FLHQWLILFf &ROXPQV RSHUDWHG IRU ELRGHJUDGDWLRQ H[SHULPHQWV ZHUH VHW XS LQ WKH VDPH PDQQHU DV WKH VRUSWLRQ FROXPQV 6ROXWH FRQWDLQLQJ ZDWHU ZDV ILOWHUHG WKURXJK XP PHPEUDQH ILOWHUV *HOPDQ 0HWULFHOf WR UHPRYH SDUWLFXODWHV $ VWDQGLQJ PLFURELDO SRSXODWLRQ ZDV GHYHORSHG LQ WKH FROXPQV RSHUDWHG DW POPLQ E\ LQRFXODWLRQ ZLWK ZDWHU IURP ZHOO 2+0 &DOFXODWLRQ RI 5DWH &RQVWDQWV 5DWH FRQVWDQWV IRU WKH ELRORJLFDO GHJUDGDWLRQ RI DURPDWLF VROXWHV IURP FROXPQ EUHDNWKURXJK FXUYHV ZHUH GHWHUPLQHG E\ DSSOLFDWLRQ RI WKH ILUVW RUGHU UDWH HTXDWLRQ WR WKH EUHDNWKURXJK FXUYH GDWD DW VWHDG\ VWDWH 0LFURELDO GHJUDGDWLRQ SURFHVVHV DUH RIWHQ DVVXPHG WR EH ILUVW RUGHU %RVVHUW DQG %DUWKD f 6XEVWLWXWLRQ RI HTXDWLRQ >@ LQWR HTXDWLRQ >@ LQFRUSRUDWHV WKH GHJUDGDWLRQ WHUP LQWR WKH RQH GLPHQVLRQDO PDVV WUDQVSRUW HTXDWLRQ & [ Y & [ N & K 5 & W >@

PAGE 70

'LYLGLQJ DOO WHUPV RI HTXDWLRQ >@ WKURXJK E\ 5 DQG GHILQLQJ 'r '5 Yr Y5 DQG Nr N5 HTXDWLRQ >@ EHFRPHV &W 'Kr & J[ Yr J & J[ Nr & >@ DW VWHDG\ VWDWH FRQGLWLRQV ZKHUH 6&W HTXDWLRQ UHGXFHV WR & [ Y & [ N & >@ K )RU VWHDG\ VWDWH FRQGLWLRQV WKHUH LV QR VRUSWLRQ HIIHFW VLQFH WKH 5 WHUP FDQFHOV RXW DQG WKH UDWH RI ELRGHJUDGDWLRQ Nf PD\ WKHQ EH FDOFXODWHG E\ DSSOLFDWLRQ RI WKH ILUVW RUGHU UDWH HTXDWLRQ WR WKH SRUWLRQ RI WKH %7& ZKLFK LV DW VWHDG\ VWDWH 7KH ILUVW RUGHU UDWH HTXDWLRQ IRU WKLV V\VWHP LV && H aNW >@ R )RU D FROXPQ RI OHQJWK [ DQG ZLWK D SRUH ZDWHU YHORFLW\ RI Y WLPH PD\ EH H[SUHVVHG DV W [Y >@ DQG VXEVWLWXWLRQ RI >@ LQWR >@ DQG UHDUUDQJHPHQW DOORZV FDOFXODWLRQ RI WKH UDWH FRQVWDQW IRU ELRGHJUDGDWLRQ N ,Q &&T f Y[ >@

PAGE 71

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f RI WHFKQLFDO JUDGH DPPRQLXP FKORULGH LQ JDO /f RI WDS ZDWHU 7KH UHVXOWLQJ FRQFHQWUDWLRQ ZDV PJ/ DPPRQLXP FKORULGH 7KH DPPRQLXP FKORULGH VROXWLRQ ZDV LQMHFWHG LQWR WKH GRVLQJ ZHOO DQG VLPXOWDQHRXVO\ GLOXWHG ZLWK WDS ZDWHU DW D PHWHUHG UDWH RI JDOORQ SHU PLQXWH JSPf 'RVLQJ FRQWLQXHG IRU KRXUV UHVXOWLQJ LQ D WRWDO GRVH YROXPH RI JDOORQV RI WUDFHU VROXWLRQ 'HWHFWLRQ RI WKH WUDFHU ZDV PRQLWRUHG LQ ZHOOV 5$3 DQG 5$3 XVLQJ D FRQGXFWLYLW\ PHWHU ZLWK D ILHOG SUREH 0HDVXUHPHQWV ZHUH REWDLQHG DW RQH KDOI WR RQHKRXU LQWHUYDOV IRU WKH ILUVW KRXU SHULRG :HOOV 3

PAGE 72

3 8)( 5$3 2+0 8)0 DQG 8): ZHUH DOVR PRQLWRUHG SHULRGLFDOO\ IRU WKH IROORZLQJ WZR ZHHNV 7KH EUHDNWKURXJK RI WKH WUDFHU ZDV FDOFXODWHG LQ SRUH YROXPHV XVLQJ WKH HTXDWLRQ SY YW/ >@ ZKHUH SY LV SRUH YROXPHV W LV WLPH KRXUVf / LV WKH GLVWDQFH EHWZHHQ 5$3 DQG 5$3 IWf DQG Y LV WKH VHHSDJH YHORFLW\ IWKRXUfIURP ZRUN E\ .LOODQ f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f $OO SKRVSKRUXV IRUPV ZHUH FRQYHUWHG WR RUWKRSKRVSKDWH E\ DXWRFODYLQJ ZLWK SRWDVVLXP SHUPDQJDQDWH LQ DQ DFLGLF PHGLXP 2UWKRSKRVSKDWH ZDV GHWHUPLQHG VSHFWURSKRWRPHWULFDOO\ DW QP ZLWK D 3HUNLQ (OPHU PRGHO VSHFWURSKRWRPHWHU &KORULGH ZDV GHWHUPLQHG FRORURPHWULFDOO\ LQ HDFK PRQLWRULQJ ZHOO RYHU VHYHUDO PRQWKV WR GHWHUPLQH EDFNJURXQG OHYHOV RI FKORULGH YLD (3$ PHWKRG $YHUDJH EDFNJURXQG FRQFHQWUDWLRQV ZHUH PJ/ 1LWUDWH ZDV PHDVXUHG ZLWK

PAGE 73

DQ 2ULRQ QLWUDWH HOHFWURGH YLD VWDQGDUG PHWKRG E $3+$ f 0LFURELDO DQDO\VHV 9LDEOH PLFURELDO FHOOV ZHUH HQXPHUDWHG E\ SODWH FRXQW WHFKQLTXH XVLQJ GLOXWH VRLO H[WUDFW DJDU '6($f PHGLD 7KLV WHFKQLTXH ZDV GHYHORSHG EDVHG RQ ZRUN E\ *KLRUVH DQG %DONZLOO f DQG :LOVRQ HW DO f ? '6($ ZDV SUHSDUHG E\ DXWRFODYLQJ J RI VXUIDFH VRLO LQ P/ RI GLVWLOOHG ZDWHU IRU RQH KRXU DW & 7KH VXSHUQDWDQW ZDV ILOWHUHG :KDWPDQ JODVV ILEHU ILOWHUVf WR UHPRYH SDUWLFXODWHV DQG GLOXWHG WHQ IROG ZLWK GLVWLOOHG ZDWHU DQG DPHQGHG b ZYf ZLWK DJDU )LVKHU 6FLHQWLILFf 7HQ JUDPV RI VXEVXUIDFH PDWHULDO ZHUH VXVSHQGHG DVHSWLFDOO\ LQ P/ b VRGLXP S\URSKRVSKDWH )LVKHU 6FLHQWLILFf WKHQ DSSURSULDWH GLOXWLRQV ZHUH SODWHG LQ WULSOLFDWH RQ '6($ PHGLD $OO SODWHV ZHUH LQFXEDWHG DHURELFDOO\ DW & IRU WHQ GD\V

PAGE 74

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n IROORZHG E\ WKH SUHVHQWDWLRQ RI ILHOG GDWD DQG WKH FRUUHODWLRQ RI ILHOG GDWD ZLWK ODERUDWRU\ H[SHULPHQWV +\GURO\VLV RI $URPDWLF +\GURFDUERQV 7KH UHVXOWV RI LQLWLDO PHDVXUHPHQWV WLPH f RI WKH K\GURO\VLV DPSXOHV ZHUH LQFRQFOXVLYH UHVXOWLQJ IURP RYHUn GLOXWLRQ RI WKH VDPSOHV 6HYHUDO DQDO\WHV ZHUH EHORZ WKH OLPLW RI GHWHFWLRQ RI WKH *&06 DQDO\WLFDO V\VWHP WKHUHIRUH QR FRQFOXVLYH VWDWHPHQWV PD\ EH PDGH UHODWLYH WR WKH UDWHV RI DURPDWLF K\GURO\VLV 6WDWLVWLFDO DQDO\VLV RI GDWD IURP DPSXOHV DIWHU GD\V RI WHPSHUDWXUH FRQWUROOHG VWRUDJH LQGLFDWHG WKDW IRU D JLYHQ WHPSHUDWXUH WKHUH ZDV QR VLJQLILFDQW VWXGHQWnV WWHVW

PAGE 75

OHYHOf FKDQJH LQ FRQFHQWUDWLRQ RI DQDO\WHV RYHU WKH S+ UDQJH WHVWHG S+ f 2QO\ RQH FRPSRXQG WULPHWK\OEHQ]HQH GHPRQVWUDWHG D VLJQLILFDQW VWXGHQWnV WWHVW OHYHOf WHPSHUDWXUH HIIHFW DW S+ YDOXHV RI DQG 7KLV FKDQJH LQ FRQFHQWUDWLRQ RFFXUV RQO\ DW & DQG WKH FRQFHQWUDWLRQ YDOXHV DW DQG & DUH HTXLYDOHQW IRU DOO S+ YDOXHV 7KHVH GDWD DUH QRW FRQVLVWHQW ZLWK GDWD IURP RWKHU DURPDWLF FRPSRXQGV LQ WKLV VWXG\ ZKLFK VKRZHG QR FKDQJH LQ FRQFHQWUDWLRQ ZLWK YDU\LQJ WHPSHUDWXUHV 7KH DSSDUHQW ORVV RI VROXWH VHHQ IRU WULPHWK\OEHQ]HQH ZDV OLNHO\ WKH UHVXOW RI ZRUNLQJ QHDU WKH GHWHFWLRQ OLPLW RI WKH DQDO\WLFDO V\VWHP RU WKH UHVXOW RI H[SHULPHQWDO HUURU 7KH DEVHQFH RI FRQFHQWUDWLRQ GLIIHUHQFHV DFURVV D ZLGH UDQJH RI S+ DQG WHPSHUDWXUH IRU WKH GD\ DPSXOHV LPSOLHV WKDW K\GURO\VLV ZDV QRW D VLJQLILFDQW PHFKDQLVP IRU UHPRYDO RI DURPDWLF K\GURFDUERQV 7KLV ZDV H[SHFWHG RZLQJ WR WKH UHVLVWDQFH RI DURPDWLF VWUXFWXUHV WR QXFOHRSKLOLF DWWDFN E\ ZDWHU 7KLV UHVXOWV IURP WKH HOHFWURQHJDWLYLW\ DVVRFLDWHG ZLWK WKH GHORFDOL]DWLRQ RI HOHFWURQV LQ WKH SL ERQGV RI WKH DURPDWLF QXFOHRXV 0F&DUW\ f KDV QRWHG WKDW FKHPLFDO K\GURO\VLV PD\ RFFXU EXW WKDW IRU PRVW FRPSRXQGV WKLV SURFHVV ZDV VORZ UHODWLYH WR ELRORJLFDO UHPRYDO UDWHV ,Q DGGLWLRQ K\GURO\VLV UHVXOWV LQ VLPSOH FKDQJHV LQ WKH PROHFXODU VWUXFWXUH ZKHUHDV ELRORJLFDO WUDQVIRUPDWLRQV RIWHQ UHVXOW LQ WKH PLQHUDOL]DWLRQ RI RUJDQLF FRPSRXQGV WR FDUERQ GLR[LGH DQG ZDWHU

PAGE 76

&KDUDFWHUL]DWLRQ RI $TXLIHU 0DWHULDOV $Q DQDO\VLV RI D VXEVDPSOH RI WKH DTXLIHU PDWHULDOV XVHG LQ WKH ODERUDWRU\ H[SHULPHQWV LV SUHVHQWHG LQ 7DEOH $OO H[SHULPHQWV ZLWK DTXLIHU PDWHULDO ZHUH SHUIRUPHG ZLWK VXEVDPSOHV RI ZHOOPL[HG DTXLIHU PDWHULDO 6LQJOH VL]H IUDFWLRQV RI DTXLIHU PDWHULDO ZHUH QRW XVHG VLQFH H[WUDSRODWLRQ IURP RQH VL]H IUDFWLRQ WR DQRWKHU KDV EHHQ VKRZQ WR OHDG WR HUURUV LQ WKH HVWLPDWLRQ RI VRUSWLRQ YDOXHV $EGXO HW DO f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

PAGE 77

7DEOH 6HOHFWHG SK\VLFDO DQG FKHPLFDO 3URSHUWLHV RI WKH /DNH $OIUHG DTXLIHU PDWHULDO 3DUDPHWHU 9DOXH 3+ 0 &D&Of 3DUWLFOH 'HQVLW\ JP/ :DWHU &RQWHQW E\ ZHLJKWf b 2UJDQLF &DUERQ b %XON 'HQVLW\ JP/ 3DUWLFOH 6L]H $QDO\VLV FOD\ b VLOW b YHU\ ILQH VDQG b ILQH VDQG b PHGLXP VDQG b FRDUVH VDQG b YHU\ FRDUVH VDQG b

PAGE 78

D D 9 ; [ rf§r r‘ [! L U L L L L L L L L f§L 72/ R 7,0( (%= +2856f $ PS;
PAGE 79

PDUNHG E\ DQ LQLWLDO UDSLG VRUSWLRQ DQG HTXLOLEULXP FRQGLWLRQV DUH HVWDEOLVKHG ZLWKLQ VHYHUDO WR f KRXUV 7KHVH GDWD DUH LQ DJUHHPHQW ZLWK :HEHU HW DO f ZKR VWDWHG WKDW VRUSWLRQ UHDFWLRQV ZLWK QDWXUDO VRUEHQWV ZHUH JHQHUDOO\ UDSLG DQG QRW UDWH OLPLWHG %DVHG RQ WKHVH GDWD DQ HTXLOLEUDWLRQ WLPH RI KRXUV ZDV FKRVHQ (LJKWHHQ KRXUV ZDV FKRVHQ WR PD[LPL]H WKH WLPH IRU VRUSWLRQ \HW PLQLPL]H WKH WLPH IRU ORVVHV IURP WKH V\VWHP LH YLD GLIIXVLRQ RI VROXWHV WKURXJK WKH 7HIORQ VHSWXPf 7KLV ZDV HTXLYDOHQW WR WLPH VFDOHV XVHG LQ SUHYLRXV VWXGLHV &KLRX HW DO 6FKZDU]HQEDFK DQG :HVWDOO f /RQJHU HTXLOLEUDWLRQ WLPHV ZHUH QRW SRVVLEOH XVLQJ WKLV H[SHULPHQWDO WHFKQLTXH VLQFH ORVVHV LQ QRQVRLO EODQNV DIWHU GD\V PDGH LW GLIILFXOW WR GLIIHUHQWLDWH EHWZHHQ VRUSWLRQ DQG ORVV IURP WKH V\VWHP 7KH HTXLOLEUDWLRQ WLPH XVHG LQ WKLV VWXG\ GLG QRW JXDUDQWHH WKDW WKH VRUSWLRQ SURFHVV ZDV FRPSOHWH EXW WKDW LW ZDV FRPSOHWH WR WKH H[WHQW WKDW LW FRXOG EH DFFXUDWHO\ PHDVXUHG %DWFK 6RUSWLRQ ,VRWKHUP 'DWD 'DWD IRU WKH HTXLOLEULXP EDWFK VRUSWLRQ LVRWKHUPV DUH SUHVHQWHG LQ $SSHQGL[ & 6ROXWLRQ FRQFHQWUDWLRQV DUH LQ XJ/ DQG VRUEHG FRQFHQWUDWLRQV DUH LQ QJJ 7KUHH PRGHOV ZHUH ILWWHG WR WKHVH GDWD XVLQJ WKH PHWKRG RI OHDVW VTXDUHV UHJUHVVLRQ DQDO\VLV 7KHVH PRGHOV ZHUH WKH OLQHDU OLQHDU ZLWK VXSSUHVVHG ILW IRUFHG WKURXJK WKH RULJLQf DQG WKH )UHXQGOLFK ORJORJ WUDQVIRUPHGf 7KH UHVXOWV RI WKHVH DQDO\VHV IRU WKH OLQHDU PRGHOV DUH SUHVHQWHG LQ 7DEOH

PAGE 80

7DEOH 5HJUHVVLRQ SDUDPHWHUV IRU WKH DQDO\VLV RI DYHUDJH YDOXHV VRUSWLRQ GDWD RI HTXLOLEULXP ZLWK WKH OLQHDU EDWFK PRGHO LVRWKHUP &RPSRXQG LL LL LL LL LL ,, ,, ,, & E X6"f Y VWG& \ fPW VWG U %HQ]HQH 7ROXHQH PS;\OHQH R;\OHQH RU (7H f§70%I (7 70% f§70% QXPEHU RI GDWD SRLQWV APD[LPXP FRQFHQWUDWLRQ F VWDQGDUG GHYLDWLRQ G\LQWHUFHSW H RU (WK\OWROXHQH A7ULPHWK\OEHQ]HQH (WK\OWROXHQH EO7ULPHWK\OEHQ]HQH O7ULPHWK\OEHQ]HQH

PAGE 81

DQG 7DEOH 7KH )UHXQGOLFK UHJUHVVLRQ SDUDPHWHUV DUH SUHVHQWHG LQ 7DEOH 7KHUH LV QR VLJQLILFDQW GLIIHUHQFH VWXGHQWnV WWHVW OHYHOf EHWZHHQ VRUSWLRQ FRHIILFLHQWV SUHGLFWHG ZLWK WKH OLQHDU PRGHO DQG WKRVH SUHGLFWHG ZLWK WKH OLQHDU PRGHO ZLWK VXSSUHVVHG LQWHUFHSW 7KH VRUSWLRQ FRHIILFLHQWV DUH GHWHUPLQHG IRUP WKH VORSH RI WKH OLQHDU LVRWKHUPV ,Q DGGLWLRQ VWDWLVWLFDO GHWHUPLQDWLRQ RI WKH FRQILGHQFH LQWHUYDOV RI WKH \LQWHUFHSWV LQGLFDWH WKDW WKHUH LV QR VLJQLILFDQW GLIIHUHQFH EHWZHHQ WKH SUHGLFWHG YDOXH RI WKH \ LQWHUFHSW LQ WKH OLQHDU PRGHO DQG ]HUR DW WKH VLJQLILFDQFH OHYHO FRQILUPLQJ WKDW WKHVH WZR PRGHOV DUH DQDORJRXV (TXLYDOHQFH EHWZHHQ WKHVH WZR PRGHOV LV H[SHFWHG VLQFH WKH VRUEHG FRQFHQWUDWLRQ VKRXOG HTXDO ]HUR ZKHQ QR VROXWH LV DGGHG WR WKH V\VWHP $ QRQ ]HUR LQWHUFHSW LV DQ LQGLFDWLRQ RI QRQOLQHDULW\ LQ WKH LVRWKHUP ,Q PRVW FDVHV ERWK OLQHDU PRGHOV ILW WKH GDWD ZHOO DV HYLGHQFHG E\ WKH UHODWLYHO\ KLJK FRHIILFLHQWV RI GHWHUPLQDWLRQ U f %DVHG RQ WKHVH DQDO\VHV WKH LVRWKHUPV IRU WKH VRUSWLRQ RI DURPDWLF VROXWHV IURP /DNH $OIUHG ZDWHU RQWR /DNH $OIUHG DTXLIHU PDWHULDO ZHUH FRQFOXGHG WR EH OLQHDU 7KH FRHIILFLHQWV RI GHWHUPLQDWLRQ IRU WROXHQH LQ ERWK OLQHDU PRGHOV ZHUH VXEVWDQWLDOO\ ORZHU WKDQ IRU RWKHU FRPSRXQGV LQ WKLV VWXG\ 7KH OLQHDU PRGHO ZLWK VXSSUHVVHG LQWHUFHSW DFFRXQWHG IRU RQO\ b RI WKH WRWDO VXP RI VTXDUHV GHYLDWLRQV DERXW WKH PHDQV IRU WKH YDOXHV LQ WKH WROXHQH LVRWKHUP 7KLV VXJJHVWHG WKDW WKLV PRGHO ZDV QRW

PAGE 82

7DEOH 5HJUHVVLRQ SDUDPHWHUV IRU WKH DQDO\VLV RI DYHUDJH YDOXHV RI HTXLOLEULXP EDWFK LVRWKHUP VRUSWLRQ GDWD ZLWK WKH OLQHDU PRGHO VXSSUHVVHG LQWHUFHSWf &RPSRXQG 1D F E 6W"/f 9 VWG& ‘ \LQW U %HQ]HQH 7ROXHQH PS;\OHQH R;\OHQH RU (7H f§70%I (7 f§70%K f§70% DQXPEHU RI GDWD SRLQWV E PD[LPXP FRQFHQWUDWLRQ F VWDQGDUG GHYLDWLRQ G \LQWHUFHSW H RU (WK\OWROXHQH A7ULPHWK\OEHQ]HQH J(WK\OWROXHQH EO7ULPHWK\OEHQ]HQH O7ULPHWK\OEHQ]HQH

PAGE 83

7DEOH 5HJUHVVLRQ SDUDPHWHUV IRU WKH DQDO\VLV RI DYHUDJH YDOXHV RI HTXLOLEULXP EDWFK LVRWKHUP GDWD ZLWK WKH )UHXQGOLFK PRGHO &RPSRXQG 1 F E XJ"/f ORJ .I ORU VWG G Q VWGH U %HQ]HQH 7ROXHQH PS;\OHQH R;\OHQH RU (7I 4 70% (7K 70% f§70% DQXPEHU RI GDWD SRLQWV E PD[LPXP FRQFHQWUDWLRQ 4 ORJ VWDQGDUG GHYLDWLRQ RI YDOXHV A)UHXQGOLFK H[SRQHQW VWDQGDUG GHYLDWLRQ RI )UHXQGOLFK H[SRQHQW A RU (WK\OWROXHQH A7ULPHWK\OEHQ]HQH 9B Q(WK\OWROXHQH O7ULPHWK\OEHQ]HQH A7ULPHWK\OEHQ]HQH

PAGE 84

DSSURSULDWH IRU HVWLPDWLRQ RI VRUSWLRQ +RZHYHU DQDO\VLV RI YDULDQFH ZLWK D JOREDO )WHVW LQGLFDWHG WKDW WKH PRGHO ZDV XVHIXO IRU SUHGLFWLQJ VRUSWLRQ DW WKH VLJQLILFDQFH OHYHO 7KHUHIRUH WKH OLQHDULW\ RI DOO LVRWKHUPV ZDV FRQILUPHG /LQHDU LVRWKHUPV KDYH EHHQ QRWHG E\ VHYHUDO DXWKRUV 6FKZDU]HQEDFK DQG :HVWDOO &KLRX HW DO .DULFNKRII HW DO f DQG WKH GDWD SUHVHQWHG LQ WKLV VWXG\ DUH LQ DJUHHPHQW ZLWK WKHVH VWXGLHV &XUWLV HW DO f QRWHG WKDW WKH XVH RI WKH OLQHDU UHJUHVVLRQ WHFKQLTXH ZDV QRW VWDWLVWLFDOO\ ULJRURXV VLQFH YDULDQFH LQ WKH GHSHQGHQW YDULDEOH ZDV QRW GLVWULEXWHG XQLIRUPO\ DFURVV WKH REVHUYHG FRQFHQWUDWLRQ UDQJH 7KHVH DXWKRUV VXJJHVWHG WKDW D OHDVW VTXDUHV ILW RQ WKH ORJ WUDQVIRUPHG GDWD )UHXQGOLFK PRGHOf JLYHV D EHWWHU DSSUR[LPDWLRQ E\ SURYLGLQJ D PRUH XQLIRUP GLVWULEXWLRQ RI YDULDQFH 7KH )UHXQGOLFK PRGHO SURYLGHG D JRRG ILW WR WKH GDWD LQ WKLV VWXG\ 7DEOH f DV HYLGHQFHG E\ WKH KLJK FRHIILFLHQWV RI GHWHUPLQDWLRQ IRU WKH )UHXQGOLFK PRGHO 7KH )UHXQGOLFK LVRWKHUP H[SODLQHG EHWZHHQ WR b RI WKH YDULDQFH LQ WKH GDWD DQG SURYLGHG D VOLJKWO\ LPSURYHG ILW WR WKH LVRWKHUP GDWD UHODWLYH WR WKH OLQHDU PRGHOV 7KH U YDOXH IRU WROXHQH ZDV ZKLFK ZDV PXFK LPSURYHG RYHU WKH FRHIILFLHQW RI GHWHUPLQDWLRQ IRU WROXHQH LQ WKH OLQHDU PRGHO 7KH ORJ YDOXHV IRU WKH VWXG\ FRPSRXQGV DUH DOVR SUHVHQWHG LQ 7DEOH 9DOXHV IRU VHYHUDO FRPSRQHQWV HWK\OEHQ]HQH DQG WKH SURS\OEHQ]HQHVf ZHUH QRW LQFOXGHG LQ WKH WDEOH RZLQJ WR WKHLU ORZ FRQFHQWUDWLRQV LQ :HOO 2+0

PAGE 85

ZDWHU RQ WKH GD\ VDPSOHV ZHUH FROOHFWHG IRU WKLV VWXG\ 7KH OLQHDULW\ RI WKHVH LVRWKHUPV ZDV FRQILUPHG E\ WKH YDOXHV RI WKH UHJUHVVLRQ FRHIILFLHQWV DQG WKH )UHXQGOLFK H[SRQHQWV Qf ERWK RI ZKLFK ZHUH FORVH WR XQLW\ $V Q DSSURDFKHV XQLW\ WKH PRGHOV VKRXOG FRQYHUJH VLQFH WKH OLQHDU PRGHO LV LQ HIIHFW D VSHFLDO FDVH RI WKH )UHXQGOLFK PRGHO $ FRPSDULVRQ RI WKH )UHXQGOLFK DQG OLQHDU PRGHOV LV SUHVHQWHG LQ 7DEOH 7KH GHYLDWLRQ EHWZHHQ SUHGLFWHG DPRXQWV RI VRUSWLRQ IRU WKH OLQHDU PRGHO ZLWK VXSSUHVVHG LQWHUFHSW DQG )UHXQGOLFK PRGHOV DUH H[SUHVVHG DV UDWLRV EHWZHHQ WKH FDOFXODWHG VRUEHG FRQFHQWUDWLRQV 7KLV PHWKRG ZDV XVHG WR HYDOXDWH WKH SUHGLFWLYH HTXLYDOHQFH RI ERWK PRGHOV RYHU WKH FRQFHQWUDWLRQ UDQJHV HQFRXQWHUHG LQ WKLV VWXG\ 7KLV PHWKRG ZDV FKRVHQ VLQFH GLUHFW FRPSDULVRQ RI DQG YDOXHV PD\ EH PLVOHDGLQJ RZLQJ WR WKH ORJ WUDQVIRUPDWLRQ RI WKH GDWD LQ WKH )UHXQGOLFK LVRWKHUP PRGHO 7KH ODUJHVW GHYLDWLRQV RFFXUUHG IRU WROXHQH DW XJ/ ,Q JHQHUDO WKH UDWLRV DSSURDFKHG XQLW\ DV WKH FRQFHQWUDWLRQV LQFUHDVHG EXW GLYHUJHG LQ WKH UDQJH EHWZHHQ WR XJ/ 7KLV FRPSDULVRQ LQGLFDWHV WKDW WKH PRGHOV ZHUH HVVHQWLDOO\ VLPLODU DV LV SUHGLFWHG IURP WKH YDOXHV RI WKH )UHXQGOLFK H[SRQHQW Qf $V Q DSSURDFKHV XQLW\ WKH )UHXQGOLFK LVRWKHUP DSSURDFKHV WKH OLQHDU LVRWKHUP 7KH FRQYHUJHQFH RI WKHVH PRGHOV LV FRQILUPHG E\ DQ H[DPLQDWLRQ RI HWK\OWROXHQH LQ 7DEOH 7KLV FRPSRXQG KDV WKH KLJKHVW )UHXQGOLFK FRQVWDQW Q f DQG WKH UDWLRV RI SUHGLFWHG

PAGE 86

7DEOH 5DWLR RI VRUEHG FRQFHQWUDWLRQV FDOFXODWHG IURP )UHXQGOLFK DQG OLQHDU HTXLOLEULXP PRGHOV 6ROXWH FRQFHQWUDWLRQV XJ/f %HQ]HQH D 7ROXHQH PS;\OHQH R;\OHQH RU (7E 70%& (7G f§70%6 f§70%I DWKH UDWLR RI WKH DPRXQW VRUEHG DV FDOFXODWHG IURP WKH )UHXQGOLFK PRGHO WR WKH DPRXQW VRUEHG SUHGLFWHG IURP WKH OLQHDU PRGHO ZLWK VXSSUHVVHG LQWHUFHSW DW WKH VDPH VROXWLRQ FRQFHQWUDWLRQ X RU (WK\OWROXHQH F 7ULPHWK\OEHQ]HQH (WK\OWROXHQH HO7ULPHWK\OEHQ]HQH A7ULPHWK\OEHQ]HQH

PAGE 87

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f ZLWK D VDQG\ DTXLIHU PDWHULDO b RUJDQLF FDUERQf RUJDQLF FDUERQ LQ WKLV VWXG\ ZDV QRW H[SHFWHG WR GHFUHDVH WKH YDOXHV RI E\ PRUH WKDQ b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

PAGE 88

24 $02817 625%(6 )LJXUH )UHXQGOLFK VRUSWLRQ LVRWKHUP IRU EHQ]HQH DW HTXLOLEULXP 8f

PAGE 89

/22 c02817 625%(' /22 62/87,21 &21&(175$7,21 ’ 62537,21 R '(62537,21 )LJXUH )UHXQGOLFK VRUSWLRQ LVRWKHUP IRU WROXHQH DW HTXLOLEULXP

PAGE 90

%DWFK 'HVRUSWLRQ ([SHULPHQWV 'HVRUSWLRQ GDWD DUH DOVR SUHVHQWHG LQ )LJXUHV DQG ILW ZLWK WKH )UHXQGOLFK W\SH PRGHO 9LVXDO LQVSHFWLRQ RI WKH GHVRUSWLRQ GDWD VXJJHVWV VRPH GHJUHH RI LUUHYHUVLELOLW\ RU VRPH GLIIHUHQFH LQ GHVRUSWLRQ NLQHWLFV EDVHG RQ WKH XSZDUG GLVSODFHPHQW RI WKH GHVRUSWLRQ UHJUHVVLRQ OLQHV +RZHYHU WKH FDOFXODWHG YDOXHV RI WKH SDUWLWLRQ FRHIILFLHQW IRU GHVRUSWLRQ ZLWK WKH OLQHDU W\SH PRGHO 7DEOH f DQG IRU WKH OLQHDU W\SH PRGHO ZLWK VXSSUHVVHG LQWHUFHSW 7DEOH f ZHUH QRW VLJQLILFDQWO\ GLIIHUHQW IURP VRUSWLRQ YDOXHV .Gf DW WKH SUREDELOLW\ OHYHO 'HVRUSWLRQ FRHIILFLHQWV IURP WKH )UHXQGOLFK W\SH PRGHO .eAf ZHUH DOVR QRW VLJQLILFDQWO\ GLIIHUHQW IURP YDOXHV DW WKH OHYHO 7DEOH f 6WDWLVWLFDO DQDO\VHV RI WKH PRGHOV XVHG WR HYDOXDWH WKH GHVRUSWLRQ FRHIILFLHQWV LQGLFDWHG WKDW DOO WKUHH PRGHOV JDYH H[FHOOHQW ILW WR WKH GDWD DV HYLGHQFHG E\ WKH KLJK FRHIILFLHQWV RI GHWHUPLQDWLRQ 7KHVH GDWD VXJJHVWHG WKH UHYHUVLELOLW\ RI WKH VRUSWLRQ SURFHVV DQG GHPRQVWUDWHG WKDW WKH K\VWHUHWLFDO EHKDYLRU RI WKH GHVRUSWLRQ GDWD ZHUH QRW VLJQLILFDQW 7KLV ZDV FRQVLVWHQW ZLWK D PDMRULW\ RI WKH SXEOLVKHG OLWHUDWXUH RQ VRUSWLRQ RI RUJDQLF FRPSRXQGV WR QDWXUDO VRUEHQWV 0LOOHU DQG :HEHU f )RU SXUSRVHV RI GLVFXVVLRQ WKH .G YDOXHV IURP WKH OLQHDU PRGHO ZLWK VXSSUHVVHG LQWHUFHSW DUH XVHG LQ WKH IROORZLQJ VHFWLRQV $V GLVFXVVHG HDUOLHU WKHVH GDWD ZHUH

PAGE 91

7DEOH 5HJUHVVLRQ SDUDPHWHUV IRU WKH DQDO\VLV RI DYHUDJH YDOXHV RI HTXLOLEULXP EDWFK GHVRUSWLRQ GDWD ZLWK WKH OLQHDU PRGHO &RPSRXQG 1 F E X"ef .GGn VWG& \PW VWG U %HQ]HQH 7ROXHQH PS;\OHQH R;\OHQH RU (7H f§70% I (7 f§70%K f§70% DQXPEHU RI GDWD SRLQWV APD[LPXP FRQFHQWUDWLRQ FVWDQGDUG GHYLDWLRQ A\LQWHUFHSW H RU (WK\OWROXHQH A7ULPHWK\OEHQ]HQH (WK\OWROXHQH EO7ULPHWK\OEHQ]HQH O7ULPHWK\OEHQ]HQH

PAGE 92

7DEOH 5HJUHVVLRQ SDUDPHWHUV IRU WKH DQDO\VLV RI DYHUDJH YDOXHV RI HTXLOLEULXP EDWFK GHVRUSWLRQ GDWD ZLWK WKH OLQHDU PRGHO VXSSUHVVHG LQWHUFHSWf &RPSRXQG 1D F E .GGn VWG& \LQW U %HQ]HQH 7ROXHQH P S;\OHQH R;\OHQH RU (7 f§70% I (7 70%K f§70% QXPEHU RI GDWD SRLQWV E PD[LPXP FRQFHQWUDWLRQ 4 VWDQGDUG GHYLDWLRQ G \LQWHUFHSW H RU (WK\OWROXHQH A7ULPHWK\OEHQ]HQH J(WK\OWROXHQH QO7ULPHWK\OEHQ]HQH O7ULPHWK\OEHQ]HQH

PAGE 93

7DEOH 5HJUHVVLRQ SDUDPHWHUV IRU WKH DQDO\VLV RI DYHUDJH YDOXHV RI HTXLOLEULXP EDWFK GHVRUSWLRQ GDWD ZLWK WKH )UHXQGOLFK PRGHO &RPSRXQG 1D F E XJA/f ORJ .I ORJ VWGF G Q W W H VWG U %HQ]HQH 7ROXHQH PS;\OHQH R;\OHQH RU (7I 70% (7K 70% f§70% DQXPEHU RI GDWD SRLQWV E PD[LPXP FRQFHQWUDWLRQ FORJ VWDQGDUG GHYLDWLRQ RI YDOXHV X)UHXQGOLFK H[SRQHQW W VWDQGDUG GHYLDWLRQ RI )UHXQGOLFK H[SRQHQW A RU (WK\OWROXHQH JO7ULPHWK\OEHQ]HQH (WK\OWROXHQH O7ULPHWK\OEHQ]HQH r7ULPHWK\OEHQ]HQH

PAGE 94

RU OLQHDU PRGHOV DQG WKLV PRGHO LV PRUH FRQYHQLHQW IRU WKH DSSOLFDWLRQ RI HTXDWLRQ >@ %UHDNWKURXJK &XUYHV IRU $URPDWLF 6ROXWHV 0HDVXUHPHQW RI &ROXPQ 'LVSHUVLRQ %UHDNWKURXJK FXUYHV %7&Vf IRU D QRQUHWDLQHG VROXWH ZHUH GHWHUPLQHG IRU HDFK FROXPQ XVHG LQ WKHVH H[SHULPHQWV $QDO\VLV RI WKHVH GDWD DOORZHG WKH GHWHUPLQDWLRQ RI WKH 3HFOHW QXPEHU XVHG WR PRGHO WKH EUHDNWKURXJK RI WKH DURPDWLF VROXWHV (YDOXDWLRQ RI WKHVH GDWD DOVR DOORZHG WKH FDOFXODWLRQ RI GLVSHUVLRQ LQ WKH FROXPQ &KORULGH DQG WULWLDWHG ZDWHU ZHUH XVHG LQ WKHVH H[SHULPHQWV 'LVSHUVLRQ 'Af ZDV FDOFXODWHG IURP WKH VORSH RI D SORW RI &&R YV SRUH YROXPHV SYf DW SY DFFRUGLQJ WR WKH HTXDWLRQ 5DR f 'K & Y / SL %@ >@ ZKHUH K LV WKH K\GURG\QDPLF GLVSHUVLRQ FRHIILFLHQW Y LV WKH IORZ YHORFLW\ FPPLQf / LV WKH OHQJWK RI WKH FROXPQ FPf DQG % LV WKH VORSH RI WKH %7& DW &&R 7KLV DVVXPHV D VLJPRLGDO VKDSHG FXUYH DQG WKLV DVVXPSWLRQ ZDV YDOLG IRU WKHVH EUHDNWKURXJK FXUYHV $ W\SLFDO EUHDNWKURXJK FXUYH LV VKRZQ LQ )LJXUH 6RPH YDOXHV RI 'A DUH SUHVHQWHG LQ 7DEOH &ROXPQV ZLWK IORZ UDWHV RI POPLQ H[KLELWHG KLJKHU YDOXHV RI VLQFH GLVSHUVLRQ

PAGE 95

& & R )LJXUH 325( 92/80(6 Â’ &+/25,'( %UHDNWKURXJK FXUYH IRU FKORULGH IRU D FP VRUSWLRQ FROXPQ FR R

PAGE 96

7DEOH 9DOXHV RI GLVSHUVLRQ FRHIILFLHQWV FDOFXODWHG IURP WKH EUHDNWKURXJK FXUYHV RI XQUHWDLQHG VROXWHV LQ ODERUDWRU\ FROXPQV 7UDFHU )ORZ P/PLQf 9HORFLW\ FPPLQf 'LVSHUVLRQ FPPLQf 9 D DYJ E VWG 9 + mQ KR &D& R f Uf§^ &D&O &D&O R f Lf§ DDYHUDJH YDOXHV RI GLVSHUVLRQ PHDVXUHPHQWV VWDQGDUG GHYLDWLRQ RI GLVSHUVLRQ PHDVXUHPHQWV

PAGE 97

POPLQ H[KLELWHG KLJKHU YDOXHV RI VLQFH GLVSHUVLRQ LQFUHDVHV ZLWK LQFUHDVLQJ SRUH ZDWHU YHORFLW\ 5REHUWV HW DO f ,W PD\ EH QRWHG WKDW WKH SRUH ZDWHU YHORFLW\ RI FPPLQ ZDV HTXLYDOHQW WR WKH VHHSDJH YHORFLW\ LQ VRPH SRUWLRQV RI WKH DTXLIHU DW WKH /DNH $OIUHG ILHOG VLWH 7KHVH GDWD DUH FRPSDUHG WR ILHOG GLVSHUVLRQ GDWD LQ VHFWLRQ $URPDWLF 6ROXWH %UHDNWKURXJK &XUYHV %UHDNWKURXJK FXUYHV IRU VHOHFWHG GLVVROYHG DURPDWLF VROXWHV LQ WKH FROXPQ HIIOXHQW :HOO 2+0 ZDWHUf DUH VKRZQ LQ )LJXUH EHQ]HQHf )LJXUH WROXHQHf DQG )LJXUH QSURS\,EHQ]HQHf %UHDNWKURXJK FXUYHV IRU WKHVH VROXWHV DUH SUHVHQWHG EHFDXVH WKH\ VKRZ WKH WKH EUHDNWKURXJK RI WKH OHDVW UHWDLQHG FRPSRXQGV EHQ]HQH DQG WROXHQHf DQG WKH PRVW UHWDLQHG QSURS\OEHQ]HQHf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

PAGE 98

& & R 26 )LJXUH %UHDNWKURXJK FXUYH IRU EHQ]HQH IURP /DNH $OIUHG ZDWHU & XJ/f RR /2 $ M%f§Tf§%f§ $ X$ $ $ 9n I L U U a7f 7f 325( 92/80(6 Q &+/25,'( %(1=(1(

PAGE 99

& & R )LJXUH %UHDNWKURXJK FXUYH IRU WROXHQH IURP /DNH $OIUHG ZDWHU & XJ/f R A g %f§t 6Tf§4 I I L LW 7a 325( 92/80(6 ’ &+/25,'( 72/8(1( RR

PAGE 100

R 2 ? 2 ? 22 % I -Ua}Tf§f§t4 $ }N f§. ? g g g A \ f 7 f7 ’ FKORULGH 325( 92/80(6 135239/%(1=(1( )LJXUH %UHDNWKURXJK FXUYH IRU QSURS\OEHQ]HQH IURP /DNH $OIUHG ZDWHU & XJ/f 8Q

PAGE 101

f DUH VKRZQ LQ 7DEOH %UHDNWKURXJK FXUYH GDWD DUH FRPSLOHG LQ $SSHQGL[ 5HWDUGDWLRQ IDFWRUV IRU WKHVH VROXWH EUHDNWKURXJK FXUYHV ZHUH DOVR HYDOXDWHG E\ HVWLPDWLQJ WKH DUHD DERYH WKH FXUYH XVLQJ 6LPSVRQnV PHWKRG 7KLV PHWKRG RI FDOFXODWLRQ \LHOGHG 5 YDOXHV ZKLFK ZHUH VOLJKWO\ JUHDWHU WKDQ WKH ILWWHG YDOXHV 7DEOH f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f 7KLV W\SH RI UHVSRQVH KDV EHHQ UHSRUWHG E\ VHYHUDO LQYHVWLJDWRUV IRU SHVWLFLGH EUHDNWKURXJK 1NHGL.L]]D HW DO f

PAGE 102

7DEOH &DOFXODWHG YDOXHV RI 5 DQG IURP DQDO\VLV RI VROXWH EUHDNWKURXJK FXUYHV &RPSRXQG F D LQI 5E .G& G RF ORJ RF %HQ]HQH 7ROXHQH (WK\OEHQ]HQH PS;\OHQH R;\OHQH ,VRSURS\OEHQ]HQH Q3URS\OEHQ]HQH RU (WK\OWROXHQH O70%H (WK\OWROXHQH 70% I 70% DLQIOXHQW FRQFHQWUDWLRQ FDOFXODWHG E\ FXUYH ILWWLQJ ZLWK %UHQQHU f ZLWK 3 H 4 FDOFXODWHG IURP WKH UHODWLRQVKLS 5Of TS ZKHUH DQG S G G. I ZKHUH I RF G RF RF 7ULPHWK\OEHQ]HQH A7ULPHWK\OEHQ]HQH JO7ULPHWK\OEHQ]HQH

PAGE 103

7DEOH 5HWDUGDWLRQ IDFWRUV FDOFXODWHG IURP OHDFKLQJ FROXPQ DQG HTXLOLEULXP EDWFK LVRWKHUP GDWD &RPSRXQG LL LL ,,4,, 8 ,, ,, ,, ,, ,, ,, 5 E eg LL 2 f+OO && ,, LL LL LL 5 G %HQ ]HQH 7ROXHQH (WK\OEHQ]HQH H QG PS;\OHQH R;\OHQH ,VRSURS\OEHQ]HQH QG Q3URS\OEHQ]HQH QG RU (WK\OWROXHQH 7ULPHWK\OEHQ]HQH (WK\OWROXHQH 7ULPHWK\OEHQ]HQH 7ULPHWK\OEHQ]HQH D5 UHWDUGDWLRQ IDFWRU EUHDNWKURXJK FXUYH FDOFXODWHG IURP WKH DUHD RI WKH 5 UHWDUGDWLRQ IDFWRU YROXPHV DW && R FDOFXODWHG IURP WKH QXPEHU RI SRUH F 5 UHWDUGDWLRQ IDFWRU FDOFXODWHG IURP HTXLOLEULXP EDWFK LVRWKHUP GDWD -D UHWDUGDWLRQ IDFWRU FDOFXODWHG IURP ILWWLQJ FROXPQ GDWD WR WKH VROXWLRQ RI %UHQQHU f QRW GHWHUPLQHG

PAGE 104

1NHGL.L]]D HW DO f SUHVHQWHG D PHWKRG WR DVVHVV WKH DV\PPHWU\ LQ D %7& E\ PHDVXULQJ WKH GLIIHUHQFH LQ WKH 5 YDOXHV FDOFXODWHG E\ WKH SRUH YROXPH PHWKRG 5 ` IURP SY WKRVH FDOFXODWHG IURP WKH DUHD DERYH WKH %7& 5 f $Q FO HPSLULFDO LQGH[ IRU VRUSWLRQ QRQHTXLOLEULXP ,61(f ZDV GHILQHG DV ,61( >5 5 f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n HTXLOLEULXP 5HJUHVVLRQ RI 5A YDOXHV ZLWK ,61( YDOXHV \LHOGHG D PRGHO ZLWK D U YDOXH RI 6WDWLVWLFDO DQDO\VLV RI WKLV UHJUHVVLRQ PRGHO LQGLFDWHG WKDW WKH PRGHO ZDV XVHIXO IRU SUHGLFWLQJ ,61( IURP 5 YDOXHV DW WKH FO VLJQLILFDQFH OHYHO 7KH FDXVH RI QRQHTXLOLEULXP PD\ EH WKH UHVXOW RI VHYHUDO SK\VLFDO RU FKHPLFDO SKHQRPHQD ZKLFK OLPLW WKH UDWH

PAGE 105

7DEOH $Q HPSLULFDO LQGH[ RI VRUSWLRQ QRQHTXLOLEULXP ,61(f IRU VHOHFWHG DURPDWLF VROXWHV OHDFKLQJ WKURXJK /DNH $OIUHG DTXLIHU PDWHULDO &RPSRXQG ,61( %HQ]HQH 7ROXHQH (WK\OEHQ]HQH PS;\OHQH R;\OHQH ,VRSURS\OEHQ]HQH Q3URS\OEHQ]HQH RU (WK\OWROXHQH 7ULPHWK\OEHQ]HQH (WK\OWROXHQH 7ULPHWK\OEHQ]HQH 7ULPHWK\OEHQ]HQH

PAGE 106

RI VRUSWLRQ 3K\VLFDO OLPLWDWLRQV WR HTXLOLEULXP LQFOXGH GLIIXVLRQ FRQWUROOHG DGVRUSWLRQGHVRUSWLRQ SURFHVVHV 5DR DQG 'DYLGVRQ f RU WKH SUHVHQFH RI SK\VLFDO EDUULHUV OLPLWLQJ WKH LQWHUDFWLRQ RI WKH VRUEHQW DQG VROXWH HJ VRLO DJJUHJDWHV VXUIDFH ILOPVf 7KH NLQHWLFV RI FKHPLFDO UHDFWLRQV EHWZHHQ WKH VRUEHQW DQG VROXWH PD\ EH OLPLWLQJ WKHUHE\ H[SODLQLQJ WKH QRQHTXLOLEULXP LQ WKH FROXPQ EUHDNWKURXJK FXUYHV 0XOWLVLWH PRGHOV KDYH EHHQ SURSRVHG WR DFFRXQW IRU VRUSWLRQ QRQHTXLOLEULXP 5DR HW DO f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f ZKHUH UHWDUGDWLRQ IDFWRUV GHFUHDVHG ZLWK LQFUHDVHG IORZ UDWHV LQGLFDWLQJ VORZ VRUSWLRQ NLQHWLFV 5DR DQG 'DYLGVRQ f LOOXVWUDWHG WKDW WKH UHWDUGDWLRQ IDFWRU PD\ DOVR EH D IXQFWLRQ RI FRQFHQWUDWLRQ ZLWK LQFUHDVHG FRQFHQWUDWLRQ RI VROXWHV OHDGLQJ WR GHFUHDVHG

PAGE 107

VRUSWLRQ 7KLV UHVXOWV IURP QRQOLQHDULW\ RI WKH VRUSWLRQ LVRWKHUP ZKLFK JRYHUQV WKH SRVLWLRQ RI WKH EUHDNWKURXJK FXUYH 7KH %7& GDWD LQ WKLV VWXG\ ZHUH REWDLQHG IRU D VLQJOH IORZ YHORFLW\ DQG DW RQO\ RQH UDQJH RI FRQFHQWUDWLRQV +RZHYHU WKH LPSRUWDQFH RI LQFUHDVHG IORZ YHORFLW\ DQG KLJK FRQFHQWUDWLRQ RQ WKH WUDQVSRUW RI FRQWDPLQDQWV PD\ EH VLJQLILFDQW DW WKH /DNH $OIUHG ILHOG VLWH .LOODQ f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f

PAGE 108

&RPSDULVRQ RI &ROXPQ DQG (TXLOLEULXP ,VRWKHUP 'DWD 5HWDUGDWLRQ IDFWRUV 7DEOH f DQG VRUSWLRQ FRHIILFLHQWV 7DEOHV DQG f IURP WKH FROXPQ GDWD DQG WKH HTXLOLEULXP GDWD LVRWKHUP FRPSDUH IDYRUDEO\ 2Q DYHUDJH YDOXHV IURP UHJUHVVLRQ DQDO\VLV RI LVRWKHUP GDWD XVLQJ WKH OLQHDU PRGHO RYHUHVWLPDWH WKH YDOXH RI WKH VRUSWLRQ FRHIILFLHQWV E\ b DQG WKH )UHXQGOLFK PRGHO XQGHUHVWLPDWHV WKH YDOXH RI WKH VRUSWLRQ FRHIILFLHQWV E\ b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b WKH UDWH RI ZDWHU PRYHPHQW 7KXV VROXWHV PD\ EH H[SHFWHG WR PRYH UHODWLYHO\ UDSLGO\ WKURXJK WKH VLWH

PAGE 109

(YDOXDWLRQ RI 6RUSWLRQ 0RGHOV 7KH DFWXDO PHFKDQLVPV WKURXJK ZKLFK VRUSWLRQ UHWDUGV WKH PRYHPHQW RI VROXWHV DUH QRW ZHOO NQRZQ 9DULRXV FRQFHSWXDO PRGHOV DUH DYDLODEOH WR KHOS GHVFULEH WKHVH VRUSWLRQ SURFHVV 7KHVH LQFOXGH WKH SDUWLWLRQLQJ EHWZHHQ RUJDQLF PDWWHU RQ WKH DTXLIHU PDWUL[ &KLRX HW DO .DULFNKRII HW DO f LQWHUDFWLRQV ZLWK WKH PLQHUDO VXUIDFHV 6DEOMLF f DQG VROYRSKRELF WKHRU\ 5DR HW DO f 7R DVVHVV WKH VLJQLILFDQFH RI WKHVH PRGHOV VRUSWLRQ GDWD IURP WKH FROXPQ H[SHULPHQWV ZHUH FRPSDUHG WR VHYHUDO WKHRUHWLFDO PRGHOV 7KH FROXPQ GDWD ZHUH QRUPDOL]HG WR WKH RUJDQLF FDUERQ FRQWHQW RI WKH /DNH $OIUHG DTXLIHU 7KHVH YDOXHV RI DUH VKRZQ LQ 7DEOH RF 5HODWLRQVKLS EHWZHHQ DQG L HUH 6HYHUDO DXWKRUV FLWH WKH OLQHDULW\ RI WKH VRUSWLRQ LVRWKHUPV DV HYLGHQFH RI WKH GRPLQDQFH RI WKH SDUWLWLRQLQJ PHFKDQLVP &KLRX HW DO &KLRX HW DO f +RZHYHU WKLV HYLGHQFH PD\ EH VXVSHFW LI WKH UDQJH RI FRQFHQWUDWLRQV LV IDU UHPRYHG IURP WKH PD[LPXP VROXELOLW\ RI WKH FRPSRXQGV ,Q DGGLWLRQ PDQ\ VRUSWLRQ PRGHOV DUH LQGLVWLQJXLVKDEOH RYHU VXIILFLHQWO\ VPDOO FRQFHQWUDWLRQ UDQJHV &XUWLV HW DO f ,Q WKLV VWXG\ VROXWH FRQFHQWUDWLRQV DUH IDU EHORZ WKH VROXELOLW\ OLPLWV 7KH OHDVW VROXEOH FRPSRXQGV LQ WKLV ZRUN DUH HWK\OWROXHQH DQG HWK\OWROXHQH ZLWK DTXHRXV VROXELOLWLHV RI PJ/ +RZHYHU WKH PD[LPXP FRQFHQWUDWLRQ HPSOR\HG LQ WKLV VWXG\ LV XJ/ ZKLFK LV RQO\ b RI WKH

PAGE 110

PD[LPXP VROXELOLW\ OHYHO 7KHUHIRUH WKH IDFW WKDW WKH LVRWKHUPV DUH OLQHDU LQ WKLV VWXG\ GRHV QRW FRQILUP WKH GRPLQDQFH RI WKH SDUWLWLRQLQJ WKHRU\ $Q LPSURYHG PHWKRG WR DVVHVV WKH LPSRUWDQFH RI SDUWLWLRQLQJ LQ WKH VRUSWLRQ SURFHVV DW WKH /DNH $OIUHG VLWH LV WR FRPSDUH YDOXHV IURP WKLV ZRUN ZLWK RFWDQROZDWHU RF SDUWLWLRQ FRHIILFLHQWV )LJXUH f DQG ZDWHU VROXELOLW\ )LJXUH f IURP WKH OLWHUDWXUH 7KH UHJUHVVLRQ FRHIILFLHQWV IRU WKHVH FRUUHODWLRQV DUH VKRZQ LQ 7DEOH 7KHVH H[SHULPHQWDOO\ GHULYHG UHODWLRQVKLSV FDQ QRZ EH FRPSDUHG ZLWK WKRVH IURP SUHYLRXV VWXGLHV 7KH H[SHULPHQWDOO\ GHULYHG UHODWLRQVKLSV EHWZHHQ A RF DQG DQG DQG :6 ZHUH GHWHUPLQHG E\ UHJUHVVLRQ RI RZ RF OLWHUDWXUH YDOXHV RI DQG ZDWHU VROXELOLW\ ZLWK GDWD RZ RF IURP WKH VRUSWLRQ %7& GDWD 7KHVH UHODWLRQVKLSV DUH ORJ ORJ RF RF r ORJ .RZ r ORJ :6 XPROHV/f >@ >@ 7DEOH FRPSDUHV WKH SUHGLFWHG YDOXHV RI IURP RF WKH ZRUN RI VHYHUDO DXWKRUV .DULFNKRII HW DO 0HDQV HW DO &KLRX HW DO .HQDJD DQG *RULQJ %ULJJV f 7KH .TF GDWD IURP WKLV VWXG\ 7DEOH f FRQVLVWHQWO\ IDOO ZLWKLQ WKH XSSHU UDQJH RI WKH SUHGLFWHG YDOXHV VKRZQ LQ 7DEOH 7KH UHODWLRQVKLSV XVHG WR FDOFXODWH WKH YDOXHV LQ 7DEOH ZHUH EDVHG RQ D ZLGH UDQJH RI RUJDQLF VROXWHV DQG QDWXUDO VRUEHQW PDWHULDOV ,W

PAGE 111

D U L > L L  $ L ? U f§U aa L U L U /22 &RZ L f§ $ )LJXUH /RJ .TF YV ORJ .TZ IRU VWXG\ FRPSRXQGV &K

PAGE 112

R R 9 2 2 /22 :$7(5 62/8%,/,7< 2& )LJXUH /RJ IURP FROXPQ GDWDf YV ORJ :6 IRU VWXG\ FRPSRXQGV U A

PAGE 113

7DEOH 5HJUHVVLRQ FRHIILFLHQWV IRU SORWV RI ORJ YV ORJ DQG ORJ YV ORJ :6 RF A RZ A RF A /RJ YV /RJ RF A RZ /RJ .TF YV /RJ :6D 6ORSH 6WG HUURU RI VORSH
PAGE 114

7DEOH &RPSDULVRQ RI UHODWLRQVKLSV WR SUHGLFW IURP YDOXHV RZ RF ORJ RZ ORJ YDOXHV IURP RF 5DQJH &RPSRXQG .DULFNRII D E 0HDQV &KLRX& L] G .HQDJD %ULJJV S LrJ RF %HQ]HQH PLQf PD[f 7ROXHQH PLQf PD[f (WK\OEHQ]HQH PS;\OHQH R;\OHQH PLQf PD[f ,VRSURS\OEHQ]HQH Q3URS\OEHQ]HQH PLQf PD[f 7ULPHWK\OEHQ]HQH PLQf PD[f 7ULPHWK\OEHQ]HQH D.DULFNRII HW DO ORJ r A RF ORJ A RZ 0HDQV HW DO ORJ N RF r ORJ RZ &&KLRX HW DO ORJ r ORJ RF A RZ G.HQDJD DQG *RULQJ ORJ r A RF ORJ RZ H%ULJJV /RJ .TF r ORJ A RZ

PAGE 115

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f HUURU LQ WKH PHDVXUHPHQW RI RUJDQLF FDUERQ f LQFUHDVHG K\GURSKRELFLW\ RI WKH RUJDQLF PDWWHU DW /DNH $OIUHG FRPSDUHG WR WKH UHIHUHQFHG VWXGLHV f VRUSWLRQ WR WKH PLQHUDO VXUIDFH RU f DQ\ FRPELQDWLRQ RI WKH DERYH &XUWLV HW DO f ,W LV XQOLNHO\ WKDW WKH RUJDQLF PDWWHU LQ WKLV VWXG\ LV PRUH K\GURSKRELF WKDQ WKDW XVHG E\ RWKHU UHVHDUFKHUV 7KLV LV FRQILUPHG E\ DQDO\VLV RI WKH VORSHV RI WKH UHJUHVVLRQ OLQHV LQ WKH UHODWLRQVKLSV EHWZHHQ RF DQG RZ 7KH VORSH RI D SORW RI YV PD\ EH UV Y RF RZ YLHZHG DV D PHDVXUH RI WKH K\GURSKRELFLW\ RI WKH RUJDQLF SKDVH LQ WKH SDUWLWLRQLQJ PRGHO /HR HW DO f ,Q WKH H[SHULPHQWDO GDWD SUHVHQWHG KHUH WKH VORSH RI HTXDWLRQ >@ ZDV OHVV WKDQ WKDW REVHUYHG LQ SUHYLRXV VWXGLHV ZKHUH SDUWLWLRQLQJ LV WKRXJKW WR SUHGRPLQDWH 7KLV LV SUHVHQWHG JUDSKLFDOO\ LQ )LJXUH 7KHUHIRUH LQFUHDVHG K\GURSKRELFLW\ RI WKH RUJDQLF PDWWHU DW /DNH $OIUHG ZDV UXOHG RXW

PAGE 116

a? U U L L L L L L /22 .RZ )LJXUH 5HJUHVVLRQ HTXDWLRQV IRU VHYHUDO PRGHOV GHVFULELQJ WKH UHODWLRQVKLS EHWZHHQ .F DQG .RZ Df &XUWLV HW DO Ef 6FKZDU]HQEDFK DQG :HVWDOO Ff WKLV VWXG\ Gf %ULJJV DQG Hf &KLRX HW DO R

PAGE 117

,W LV PRUH OLNHO\ WKDW WKH LQFUHDVHG VRUSWLRQ UHVXOWV IURP VRPH DIILQLW\ RI WKH DURPDWLF VROXWHV LQ WKLV VWXG\ IRU WKH PLQHUDO VXUIDFH RI WKH DTXLIHU PDWHULDO 7KLV LV FRQVLVWHQW ZLWK WKH ILQGLQJV RI 6FKZDU]HQEDFK DQG :HVWDOO f DQG &XUWLV HW DO f 7KHVH DXWKRUV GHPRQVWUDWH WKDW WKH PLQHUDO VXUIDFH DUHD DQG WKH QDWXUH RI WKH PLQHUDO VXUIDFH H[HUW D JUHDWHU LQIOXHQFH RQ VRUSWLRQ WKDQ RUJDQLF FDUERQ IRU VRUEHQWV ZLWK ORZ DPRXQWV RI QDWXUDOO\ RFFXUULQJ RUJDQLF PDWHULDO 5HODWLRQVKLS %HWZHHQ DQG 7R DVVHVV WKH FRQWULEXWLRQ RI WKH PLQHUDO VXUIDFH LQ WKH VRUSWLRQ RI DURPDWLF VROXWHV IURP WKH /DNH $OIUHG DTXLIHU .TF YDOXHV IURP WKLV VWXG\ ZHUH FRUUHODWHG ZLWK ILUVW RUGHU PROHFXODU FRQQHFWLYLW\ LQGLFHV A;f 7KLV UHODWLRQVKLS LV VKRZQ LQ )LJXUH DQG WKH UHJUHVVLRQ SDUDPHWHUV DUH VKRZQ LQ 7DEOH 7KH XVH RI WKLV FRUUHODWLRQ ZDV EDVHG RQ WKH VXJJHVWLRQ RI 0LOJHOJULQ DQG *HUVWO f WKDW PROHFXODU VWUXFWXUH RU WRSRORJ\ PD\ EH PRUH HIIHFWLYHO\ FRUUHODWHG ZLWK VRUSWLRQ WKDQ .TZ RU :6 6DEOMLF f VXJJHVWHG WKH XVH RI ILUVW RUGHU PROHFXODU FRQQHFWLYLW\ LQGLFHV A;f DV DQ HVWLPDWRU RI PROHFXODU WRSRORJ\ 7KH UHJUHVVLRQ HTXDWLRQ GHYHORSHG E\ 6DEOMLF f LV DOVR VKRZQ LQ )LJXUH 7KLV UHODWLRQVKLS ZDV EDVHG RQ WKH UHJUHVVLRQ RI FDOFXODWHG A; YHUVXV OLWHUDWXUH YDOXHV RI GDWD RF 7KH VORSHV RI WKHVH OLQHV DUH QRW VLJQLILFDQWO\ GLIIHUHQW DW WKH VLJQLILFDQFH OHYHO 7KH FRUUHODWLRQ

PAGE 118

4 r 2 R m)LJXUH /RJ .TF YV L; IRU DURPDWLF VROXWHV LQ Df WKLV VWXG\ DQG IURP Ef 6DELMLF f

PAGE 119

7DEOH 5HJUHVVLRQ FRHIILFLHQWV IRU WKH UHODWLRQVKLS EHWZHHQ ORJ DQG r; U RF 6ORSH 6WG HUURU RI VORSH
PAGE 120

FRHIILFLHQWV DUH DOVR FRPSDUDEOH IRU WKLV VWXG\ YV IRU 6DEOMLF f 6DEOMLF f GHPRQVWUDWHG WKDW ILUVW RUGHU PROHFXODU FRQQHFWLYLW\ ZDV D TXDQWLWDWLYH PHDVXUH RI WKH DUHD RFFXSLHG E\ WKH SURMHFWLRQ RI WKH QRQn K\GURJHQ VNHOHWRQ RI D PROHFXOH 7KH JRRGQHVV RI ILW EHWZHHQ r; DQG .TF GDWD LQ WKLV VWXG\ VXSSRUWV WKH K\SRWKHVLV WKDW VRUSWLRQ GHSHQGV DW OHDVW LQ SDUW RQ VRPH W\SH RI VXUIDFH LQWHUDFWLRQ +RZHYHU FRPSDULVRQ RI FRUUHODWLRQ FRHIILFLHQWV EHWZHHQ WKH WKUHH PRGHOV :6 DQG A;f LQGLFDWHV WKDW QHLWKHU RI R Z WKHVH PRGHOV FRPSOHWHO\ GHVFULEH WKH VRUSWLRQ SURFHVV VHH 7DEOHV DQG f 7KLV VXJJHVWV WKDW WKH VRUSWLRQ PHFKDQLVP LV LQ UHDOLW\ D FRPELQDWLRQ RI SURFHVVHV LQWHUDFWLQJ WR \LHOG DQ RYHUDOO VRUSWLRQ HIIHFW 7KH ODFN RI DQ\ GRPLQDQW PHFKDQLVP PD\ EH PRUH SURQRXQFHG LQ WKLV VWXG\ UHVXOWLQJ IURP WKH ORZ RUJDQLF FDUERQ FRQWHQW RI WKH /DNH $OIUHG DTXLIHU PDWHULDO 7KLV VHUYHV WR UHGXFH WKH SDUWLWLRQLQJ HIIHFW E\ HOLPLQDWLQJ WKH VRUSWLRQ VXEVWUDWH RUJDQLF FDUERQf ,Q DGGLWLRQ 6FKZDU]HQEDFK DQG :HVWDOO f GHPRQVWUDWHG WKDW RUJDQLF SRRU VRUEHQWV ZLWK KLJK VSHFLILF VXUIDFH DUHDV PD\ VWLOO H[KLELW VPDOO YDOXHV LQGLFDWLQJ WKDW VXUIDFH LQWHUDFWLRQV DORQH GLG QRW FRPSOHWHO\ DFFRXQW IRU VRUSWLRQ 7KHVH GDWD VXSSRUW WKH REVHUYDWLRQ RI 9RLFH DQG :HEHU f WKDW JLYHQ WKH KHWHURJHQHRXV QDWXUH RI QDWXUDO VRUEHQW PDWHULDOV VRUSWLRQ PHFKDQLVPV RI RUJDQLF VROXWHV LQ WKH HQYLURQPHQW SUREDEO\ LQYROYH PDQ\ W\SHV RI LQWHUDFWLRQV 7KH LPSRUWDQFH RI D

PAGE 121

JLYHQ UHDFWLRQ PHFKDQLVP GHSHQGV RQ WKH QDWXUH RI WKH VRUEHQW VXUIDFH 3DUWLWLRQLQJ LV SUREDEO\ PRUH LPSRUWDQW LQ VRLOV ZLWK KLJK RUJDQLF FDUERQ FRQWHQWV 7KH YDU\LQJ GHJUHHV RI VRUSWLRQ LQ VRLOV ZLWK ORZ RUJDQLF FDUERQ FRQWHQWV UHSRUWHG E\ 0LOJHOJULQ DQG *HUVWO f UHIOHFW WKH YDULDWLRQ LQ WKH DELOLW\ RI PLQHUDO VXUIDFHV WR VRUE RUJDQLF FRPSRXQGV &RPSDULVRQ RI 0L[HG 6ROXWH DQG 6LQJOH 6ROXWH 5HWDUGDWLRQ 1NHGL.L]]D HW DO f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f 7R HYDOXDWH WKLV SRVVLELOLW\ D VLQJOH VROXWH EHQ]HQH PJ/ GLVVROYHG LQ 5$3 ZHOO ZDWHUf ZDV SDVVHG WKURXJK D VRLO FROXPQ 7KH EUHDNWKURXJK RI WKLV VROXWH LV VKRZQ LQ )LJXUH (YDOXDWLRQ RI WKH UHWDUGDWLRQ IDFWRU IRU WKLV FROXPQ \LHOGHG DQ 5 YDOXH RI ZKLFK LV HTXLYDOHQW WR WKH 5 YDOXH IRU EHQ]HQH IURP WKH PL[HG VROXWH VDPSOH %DVHG RQ WKHVH GDWD QR FRVROXWH HIIHFW RQ EHQ]HQH ZDV REVHUYHG ,I D

PAGE 122

& & R 325( 92/80(6 D %(1=(1( )LJXUH %UHDNWKURXJK FXUYH IRU EHQ]HQH VLQJOH VROXWHf VSLNHG LQWR 5$3 ZHOO ZDWHU & XJ/f

PAGE 123

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f 7KH SXUSRVH RI WKLV H[SHULPHQW ZDV WR HYDOXDWH WKH UHDFWLRQ NLQHWLFV DQG WKH H[WHQW RI FRQYHUVLRQ RI K\GURJHQ SHUR[LGH WR A LQ WKH /DNH $OIUHG DTXLIHU V\VWHP ,QLWLDO H[SHULPHQWV ZLWK GLVWLOOHG GHLRQL]HG ZDWHU DQG NQRZQ DGGLWLRQV RI GLOXWH K\GURJHQ SHUR[LGH VKRZHG QR LQFUHDVHV LQ GLVVROYHG R[\JHQ (YHQ DIWHU DGGLWLRQ RI P/ RI b K\GURJHQ SHUR[LGH WR WKH UHDFWLRQ IODVN QR LQFUHDVH LQ GLVVROYHG R[\JHQ ZDV QRWHG RYHU D PLQXWH LQWHUYDO 7KH WLWHU RI WKH b VWRFN VROXWLRQ bf ZDV FRQILUPHG E\ WLWUDWLRQ ZLWK SRWDVVLXP SHUPDQJDQDWH 7KHVH GDWD LQGLFDWHG WKH VWDELOLW\ RI K\GURJHQ SHUR[LGH LQ WKH DEVHQFH RI D FDWDO\VW 7KH UHDFWLRQ RI K\GURJHQ SHUR[LGH LQ ILOWHU VWHULOL]HG /DNH $OIUHG ZDWHU ZDV LQYHVWLJDWHG WR DVVHVV WKH

PAGE 124

DYDLODELOLW\ RI QRQELRORJLFDO FDWDO\VWV LQ WKH DTXHRXV SKDVH :DWHU IURP ZHOOV 2+0 ZLWK DURPDWLF VROXWHVf DQG 5$3 QR DURPDWLF VROXWHVf ZHUH WLWUDWHG ZLWK K\GURJHQ SHUR[LGH VROXWLRQV RI DQG PJ/ ZLWK QR DSSDUHQW LQFUHDVH LQ GLVVROYHG R[\JHQ LQGLFDWLQJ DQ WKH DEVHQFH RI D DFWLYH FDWDO\VW LQ ERWK WKHVH ZDWHU VDPSOHV 7KH UHVSRQVH RI QRQILOWHUHG ZDWHU IURP ZHOO 2+0 WR WKH DGGLWLRQ RI b K\GURJHQ SHUR[LGH LV VKRZQ LQ )LJXUH 7KH S+ RI WKH ZDWHU LQ WKH UHDFWLRQ IODVN ZDV DQG WKLV YDOXH UHPDLQHG FRQVWDQW WKURXJKRXW WKH FRXUVH RI WKH H[SHULPHQW 7KH UHGR[ SRWHQWLDO LQFUHDVHG IURP PLOOLn YROWV PYf WR PY LPPHGLDWHO\ IROORZLQJ WKH DGGLWLRQ RI XO RI b +HXLYDOHQW WR PJ/ +2f 7KLV DGGLWLRQ RI ZDV VXIILFLHQW WR PDLQWDLQ DQ LQFUHDVH RI PJ/ RYHU WKH DPELHQW '2 LQ WKH UHDFWLRQ IODVN 7KH DGGLWLRQ RI VWHULOH DTXLIHU PDWHULDO IURP WKH /DNH $OIUHG VLWH LQFUHDVHG WKH '2 RI WKH UHDFWLRQ IODVN LPPHGLDWHO\ DIWHU LQWURGXFWLRQ 7KLV LQGLFDWHG WKH FDWDO\WLF DELOLW\ RI WKH /DNH $OIUHG DTXLIHU DQG ZDV PRVW OLNHO\ DVVRFLDWHG ZLWK WKH SUHVHQFH RI LURQ VDOWV %ULWWRQ f DOWKRXJK LURQ FRQFHQWUDWLRQV ZHUH QRW GHWHUPLQHG IRU WKH /DNH $OIUHG DTXLIHU PDWHULDO 7KLV VPDOO VFDOH VWXG\ KHOSHG WR GHWHUPLQH WKH UHDFWLYLW\ RI WKH K\GURJHQ SHUR[LGH LQ WKH /DNH $OIUHG DTXLIHU V\VWHP DQG SURYLGHG UDQJHV IRU XVH RI K\GURJHQ SHUR[LGH LQ WKH ELRORJLFDO H[SHULPHQWV *DV FKURPDWRJUDSKLF DQDO\VHV RI DURPDWLF FRPSRXQGV GXULQJ WKH FRXUVH RI WKLV H[SHULPHQW VKRZHG WKDW WKHUH ZHUH QR

PAGE 125

X/ +3 DGGHG D 7LPH KRXUV 5HDFWLRQ RI 2+0 ZHOO ZDWHU WR WKH DGGLWLRQ RI b K\GURJHQ SHUR[LGH DQG DTXLIHU PDWHULDO

PAGE 126

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f GHPRQVWUDWHG WKDW VHYHUDO GD\V ZHUH UHTXLUHG IRU PLFURELDO DGDSWDWLRQ WR K\GURJHQ SHUR[LGH 7KH GDWD IURP WKLV H[SHULPHQW VLPSO\ FRQILUP WKDW WKHUH DUH VXIILFLHQW FDWDO\VWV DYDLODEOH WR PHGLDWH WKH FRQYHUVLRQ RI WR &!f $SSOLFDWLRQ RI + p W WrLH /DAH $OIUHFA DTXLIHU LV XQGHUZD\ 3UHOLPLQDU\ GDWD LQGLFDWH WKDW GLVVROYHG R[\JHQ OHYHOV ZHUH LQFUHDVHG DQG WKDW K\GURFDUERQV FRQFHQWUDWLRQV ZHUH UHGXFHG IROORZLQJ DQ DGDSWDWLRQ SHULRG %DWFK %LRGHJUDGDWLRQ ([SHULPHQW 7ZR VHSDUDWH EDWFK ELRGHJUDGDWLRQ H[SHULPHQWV ZHUH SHUWRUPHG 7KH ILUVW H[SHULPHQW ZDV GHVLJQHG WR LQYHVWLJDWH WKH HIIHFW RI YDULRXV FRPELQDWLRQV RI K\GURJHQ SHUR[LGH DQG

PAGE 127

DPPRQLXP FKORULGH RQ WKH ELRGHJUDGDWLRQ RI WKH DURPDWLF FRPSRXQGV LQ WKH /DNH $OIUHG DTXLIHU DQG WR DVVHVV WKH GHJUDGDWLRQ RI WKHVH FRPSRXQGV LQ WKH SUHVHQFH RI GLVVROYHG R[\JHQ 7KH DYHUDJH FRQFHQWUDWLRQV RI DURPDWLF K\GURFDUERQV LQ WKH PLFURFRVPV RI H[SHULPHQW RYHU WKH WLPH FRXUVH RI WKH H[SHULPHQW GD\Vf DUH VKRZQ LQ 7DEOH $ GHWDLOHG SUHVHQWDWLRQ DQG VWDWLVWLFDO DQDO\VLV RI WKHVH GDWD DUH SUHVHQWHG LQ $SSHQGL[ ( 7KHVH GDWD ZHUH ILW WR VHYHUDO UDWH HTXDWLRQV =HUR RUGHU ILUVW RUGHU DQ HPSLULFDOO\ EDVHG ILUVW RUGHU UDWH HTXDWLRQ 7KRPDVVORSH PHWKRGf VHFRQG RUGHU DQG D PL[HG RUGHU ]HUR WR ILUVW RUGHUf UDWH HTXDWLRQV ZHUH ILW WR WKH ELRGHJUDGDWLRQ GDWD 2QO\ WKH ILUVW RUGHU UDWH HTXDWLRQV JDYH DGHTXDWH ILW WR WKH GDWD EDVHG RQ DQ DQDO\VLV RI WKH FRHIILFLHQWV RI GHWHUPLQDWLRQ IRU WKH YDULRXV PRGHOV *OREDO )WHVW VLJQLILFDQFH OHYHOf 7KH UHVXOWV RI OLQHDU UHJUHVVLRQ DQDO\VLV RI WKH GDWD WR WKH ILUVW RUGHU PRGHOV DUH VKRZQ LQ 7DEOH ILUVW RUGHUf DQG 7DEOH 7KRPDVVORSHf ,Q ERWK WDEOHV WKH UDWH FRQVWDQWV FDOFXODWHG KDOI OLYHV DQG WKH FRHIILFLHQWV RI GHWHUPLQDWLRQ IRU HDFK VROXWH XQGHU HDFK WUHDWPHQW FRQGLWLRQ DUH SUHVHQWHG 5HJUHVVLRQ DQDO\VHV DQG UDWH GDWD IRU ERWK W\SHV RI ILUVW RUGHU UDWH HTXDWLRQV DUH SUHVHQWHG VLQFH QHLWKHU PHWKRG \LHOGV FRHIILFLHQWV RI GHWHUPLQDWLRQ ZKLFK FRQVLVWHQWO\ SURYLGH VXSHULRU ILW WR WKH GDWD )LUVW RUGHU DQG 7KRPDV VORSH UDWH HTXDWLRQV HDFK SURYLGH DGHTXDWH ILW WR WKH GDWD DV HYLGHQFHG E\ WKH U YDOXHV ,Q WKH VHFWLRQV

PAGE 128

7DEOH 7RWDO DYHUDJH K\GURFDUERQ YDOXHV XJ/f LQ WKH PLFURFRVPV RI EDWFK ELRGHJUDGDWLRQ H[SHULPHQW 7UHDWPHQW &RPSRXQG 'D\ $ ,% & ,' ,( ,) %HQ]HQH 7ROXHQH PS;\OHQH R;\OHQH

PAGE 129

7DEOH &RQWLQXHG 7UHDWPHQW &RPSRXQG 'D\ $ ,% & ,' ,( ,) (7D 70%E (7& O70%G

PAGE 130

7DEOH &RQWLQXHG 7UHDWPHQW &RPSRXQG 'D\ $ ,% & ,' ,( ,) n D(WK\OWROXHQH A7ULPHWK\OEHQ]HQH &(WK\OWROXHQH A7ULPHWK\OEHQ]HQH 7ULPHWK\OEHQ]HQH A'LVVROYHG R[\JHQ LQ PJ/

PAGE 131

7DEOH %LRGHJUDGDWLRQ UDWH FRQVWDQWV KDOIOLYHV DQG FRUUHODWLRQ FRHIILFLHQWV IRU WKH ILW RI ELRGHJUDGDWLRQ H[SHULPHQW GDWD WR D ILUVW RUGHU UDWH HTXDWLRQ 7UHDWPHQW %HQ]HQH 7ROXHQH PS;\OHQH R;\OHQH (7 $ N U ,% N WK U & N WK U ,' N WK U • ,( N WK U ,) N WK U N WK U

PAGE 132

7DEOH &RQWLQXHG 7UHDWPHQW O70%E (7r 70%& O70%H 'I $ N WK U ,% N WK U & N WK U ,' N WK U ,( N WK U ,) N WK U N WK U D(WK\OWROXHQH 7ULPHWK\OEHQ]HQH &(WK\OWROXHQH GO7ULPHWK\OEHQ]HQH 7QPHWK\OEHQ]HQH A'LVVROYHG R[\JHQ

PAGE 133

7DEOH %LRGHJUDGDWLRQ UDWH FRQVWDQWV KDOIOLYHV DQG FRUUHODWLRQ FRHIILFLHQWV IRU WKH ILW RI ELRGHJUDGDWLRQ H[SHULPHQW GDWD WR WKH 7KRPDV VORSH UDWH HTXDWLRQ 7UHDWPHQW %HQ]HQH 7ROXHQH PS;\OHQH R;\OHQH (7 $ ND WAE U ,% N WK U & N WK U ,' N WK U ,( N WrV f U ,) N WK U N WK U

PAGE 134

7DEOH &RQWLQXHG 7UHDWPHQW 70% (7 70% 70% '2 $ N W-r U ,% N WK U & N WK U ,' N WK U ,( N WK U ,) N WK U N WK U D GD\ E GD\V

PAGE 135

EHORZ HDFK WUHDWPHQW LV GLVFXVVHG LQGLYLGXDOO\ SULRU WR DQ RYHUDOO DQDO\VLV RI WKHVH H[SHULPHQWV 7UHDWPHQW $ 'DWD DUH SORWWHG LQ )LJXUHV DQG 7KH GLVVROYHG R[\JHQ LQ WKHVH PLFURFRVPV ZDV QRW DUWLILFLDOO\ LQFUHDVHG RWKHU WKDQ E\ DHUDWLRQ GXULQJ WKH WUDQVIHU DQG ILOOLQJ RI WKH VROXWH FRQWDLQLQJ ZDWHU LQWR WKH ELRGHJUDGDWLRQ YLDOV 7KH '2 RI WKHVH YLDOV DW WLPH ZDV PJ/ $Q H[DPLQDWLRQ RI WKH KDOI OLYHV RI WKHVH VROXWHV VKRZHG WKDW EHQ]HQH GD\Vf DQG WROXHQH GD\Vf ZHUH UHDGLO\ UHPRYHG IURP WKH PLFURFRVP FRPSDUHG WR D KDOI OLIH RI IRU WULPHWK\OEHQ]HQH 7KLV LV LQ FRQWUDGLFWLRQ WR VWXGLHV ZKLFK QRWH WKH UHFDOFLWUDQFH RI WKHVH FRPSRXQGV WR ELRGHJUDGDWLRQ %RVVHUW DQG %DUWKD f 7KH RUWKR LVRPHU RI [\OHQH ZDV PRUH UHVLVWDQW WR PLFURELDO DWWDFN WKDQ ZHUH WKH PHWD DQG SDUD LVRPHUV 7KLV FRQILUPHG WKH GDWD RI .DSSHOHU DQG :XKUPDQQ D Ef &RPSOHWH GHJUDGDWLRQ RI DOO VROXWHV ZDV DFKLHYHG E\ GD\V GHWHFWLRQ OLPLW XJ/f DQG LQ PDQ\ FDVHV GHJUDGDWLRQ ZDV FRPSOHWH LQ GD\V 7ROXHQH ZDV GHJUDGHG SDUWLFXODUO\ UDSLGO\ 7KH GHSOHWLRQ RI R[\JHQ LQ WKHVH PLFURFRVPV VXJJHVWHG WKDW WKLV ORVV ZDV PLFURELDOO\ PHGLDWHG )LJXUH f 7UHDWPHQW ,% 'DWD IRU WKLV WUHDWPHQW DUH VKRZQ LQ $SSHQGL[ ( 7KHVH GDWD GHPRQVWUDWH WKH HIIHFW RI PJ/ K\GURJHQ SHUR[LGH WUHDWPHQW RQ WKH GHJUDGDWLRQ RI WKH DURPDWLF

PAGE 136

& & R )LJXUH 5HODWLYH FRQFHQWUDWLRQ YV WLPH IRU ILYH DURPDWLF FRPSRXQGV LQ ELRGHJUDGDWLRQ WUHDWPHQW $

PAGE 137

R 2 2 2-2 2M% 26 2-2 2$ 2-2 2 2 D '$<6 Â’ 70% (7 R 70% $ 70% )LJXUH 5HODWLYH FRQFHQWUDWLRQ YV WLPH IRU IRXU &J+MA FRPSRXQGV LQ ELRGHJUDGDWLRQ WUHDWPHQW $

PAGE 138

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f ZDV DGGHG WR WKHVH YLDOV 7KLV FRQFHQWUDWLRQ ZDV FKRVHQ EDVHG RQ WKH FDOFXODWHG DPRXQW RI QLWURJHQ UHTXLUHG WR FRPSOHWHO\ GHJUDGH WKH DURPDWLF VROXWHV DVVXPLQJ D &1 UDWLR RI 7KH LQLWLDO '2 FRQFHQWUDWLRQ ZDV PJ/ 2[\JHQ FRQVXPSWLRQ DSSHDUHG UDSLG EXW IHOO DIWHU VHYHQ GD\V $GGLWLRQ RI DPPRQLXP FKORULGH VLJQLILFDQWO\ UHGXFHG WKH UDWH RI PLFURELDO GHJUDGDWLRQ RI

PAGE 139

Â’ 0 % R & )LJXUH &RQFHQWUDWLRQ YV WLPH IRU GLVVROYHG R[\JHQ LQ ELRGHJUDGDWLRQ WUHDWPHQWV $ ,% DQG &

PAGE 140

EHQ]HQH WROXHQH WULPHWK\OEHQ]HQH HWK\OWROXHQH DQG WULPHWK\OEHQ]HQH %RWK PS[\OHQH KDOI OLIH GD\Vf DQG WULPHWK\OEHQ]HQH KDOI OLIH GD\Vf ZHUH OHVV DIIHFWHG DQG ZHUH HDFK GHJUDGHG WR XJ/ $W WKH HQG RI GD\V b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f 7UHDWPHQW ,) 7UHDWPHQW ZLWK PJ/ AA DQG PJ/ 1+A&O LV VKRZQ LQ $SSHQGL[ ( DQG DYHUDJH GDWD DUH VKRZQ LQ 7DEOH 7KHUH ZDV DQ REYLRXV ODJ LQ WKH '2 SURILOH )LJXUH f DQG WKH KDOI OLIH IRU GLVVROYHG R[\JHQ ZDV LQFUHDVHG IURP GD\V LQ WUHDWPHQW $ WR GD\V LQ WKLV WUHDWPHQW 7KLV ZDV DOVR UHIOHFWHG LQ WKH FRQFHQWUDWLRQV RI EHQ]HQH R

PAGE 141

7, )LJXUH &RQFHQWUDWLRQ YV WLPH IRU GLVVROYHG R[\JHQ LQ ELRGHJUDGDWLRQ WUHDWPHQWV ,' ,( ,) DQG

PAGE 142

[\OHQH HWK\OWROXHQH WULPHWK\OEHQ]HQH DQG WULPHWK\OEHQ]HQH $OO FRPSRXQGV VKRZHG D VXEVWDQWLDO LQFUHDVH LQ KDOI OLYHV H[FHSW IRU PS[\OHQH DQG WULPHWK\OEHQ]HQH 7KURXJKRXW WKLV VWXG\ WKHVH FRPSRXQGV ZHUH ZHOO GHJUDGHG 7KHVH FRPSRXQGV ZHUH WKH PRVW UDSLGO\ UHPRYHG FRPSRXQGV LQ WKH ZRUN RI .DSSHOHU DQG :XKUPDQQ D Ef 7KH FKDQJHV LQ WKH GHJUDGDWLRQ UDWHV IRU WKH RWKHU DURPDWLF FRPSRXQGV PD\ UHIOHFW D FKDQJH LQ WKH FRPPXQLW\ VWUXFWXUH RI WKH ZHOO ZDWHU EDFWHULD 7KH EDFWHULD IURP WKH ILHOG VLWH PD\ EH DGDSWHG WR GHJUDGH DURPDWLF FRPSRXQGV WKDW DUH XVXDOO\ WKRXJKW WR EH UHFDOFLWUDQW RU GHJUDGHG VORZO\ LH EHQ]HQHf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f LQGLFDWLQJ WKH VWHULOLW\ RI WKH V\VWHP /RVVHV IURP WKH V\VWHP DUH LQ WKH UDQJH RI b IRU &A&J VROXWHV DQG b IRU &J+A VROXWHV 7KHVH ORVVHV ZHUH PRVW OLNHO\ WKH UHVXOW RI GLIIXVLRQ RI WKH YRODWLOH FRPSRQHQWV WKURXJK WKH

PAGE 143

WHIORQ VHSWD 7KH ORVV RI YRODWLOH FRPSRXQGV ZDV H[DFHUEDWHG E\ VWRUDJH DW & +RZHYHU WKLV GRHV QRW DFFRXQW IRU WKH LQFUHDVHG UHGXFWLRQ RI & +f FRQFHQWUDWLRQV \ s ] UHODWLYH WR WKH PRUH YRODWLOH &&Q &A&f YDOXHV ZRXOG ER '2 QRUPDOO\ H[KLELW JUHDWHU YRODWLOH ORVVHV 7KH ELRGHJUDGDWLRQ GDWD ZHUH QRW FRUUHFWHG IRU WKHVH ORVVHV %DWFK %LRGHJUDGDWLRQ ([SHULPHQW ZHUH R[\J VRPH H[SH EHWW H[SH DFWL RI ,17 WR ,17IRUPD 7KH GDWD IURP PRGHOV DV GHVFULEHG FRQVLVWHQWO\ JRRG I WR ILUVW RUGHUf DQG WKH GDWD ZHOO DV HY GHWHUPLQDWLRQ $YHUDJH YDOXHV VKRZQ LQ 7DEOH FRHIILFLHQWV IRU WK V H[SHULPHQW ZHUH IL VHFWLRQ 1R VL WR WKH GDWD 0L[HG HUR RUGHU UDWH HTXDW QHHG E\ ORZ FRHIILFL K\GURFDUERQV LQ WKH 5DWH FRQVWDQWV DQG LW RI ELRGHJUDGDWLRQ 7KH VHFRQG VHULHV RI EDWFK ELRGHJUDGD SHUIRUPHG WR DVVHVV WKH HIILFDF\ RI V HQ DGGLWLRQ WR WKH /DNH $OIUHG DTXLIHU RI WKH SUHYLRXV WUHDWPHQWV ,Q WKLV ULPHQWV DGGLWLRQDO VWHULOH FRQWUROV Z HU DVVHVV WKH ORVVHV H[KLELWHG LQ ELRG ULPHQW WUHDWPHQW ,)f ,Q DGGLWLRQ YLW\ ZDV PHDVXUHG E\ TXDQWLI\LQJ WKH P ]DQ WKL LQ LW ] LGH RI H I WLRQ H[SHULPHQW HYHUDO PHWKRGV DQG WR UHSHDW VHULHV RI HUH DGGHG WR HJUDGDWLRQ PLFURELDO LFURELDO UHGXFW W WR VHYHUDO UD QJOH PRGHO JDYH RUGHU ] HUR RUG LRQV GLG QRW PD HQWV RI PLFURFRVPV DUH UHJUHVVLRQ GDWD WR WKH V RI LRQ WH D HU WFK

PAGE 144

7DEOH f§ 7RWDO DYHUDJH K\GURFDUERQ YDOXHV XJ/f LQ WKH PLFURFRVPV RI EDWFK ELRGHJUDGDWLRQ H[SHULPHQW 7UHDWPHQW &RPSRXQG 'D\ $ % & ( ) + %HQ]HQH 7ROXHQH (WKE]

PAGE 145

7DEOH &RQWLQXHG 7UHDWPHQW &RPSRXQG 'D\ $ % & ( ) + PS;\OHQH R;\OHQH (7 70%

PAGE 146

7DEOH &RQWLQXHG 7UHDWPHQW &RPSRXQG 'D\ $ % & ( ) + (7 70% 70% 'D D GLVVROYHG R[\JHQ LQ PJ/

PAGE 147

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f DQG WKH FRQFHQWUDWLRQ RI PS[\OHQH XJ/ YV XJ/ LQ $f 7KHUH ZDV D UDSLG ORVV LQ '2 RYHU WKH ILUVW WZR GD\V LQGLFDWLQJ PLFURELDO DFWLYLW\ 7UHDWPHQW % 7KLV LV D UHSHDW RI WUHDWPHQW ,' 7KH KDOI OLYHV ZHUH JHQHUDOO\ KLJKHU UHIOHFWLQJ D GHFUHDVH LQ K\GURFDUERQ UHPRYDO 7KHUH ZDV D SURQRXQFHG ODJ SKDVH RI GD\V IRU EHQ]HQH )LJXUH f 7KH ODJ LQ GHJUDGDWLRQ IRU WROXHQH R[\OHQH PS[\OHQH DQG HWK\OWROXHQH ZDV WZR GD\V 7KH '2 SURILOH LQ WKLV WUHDWPHQW ZDV FRQVLVWHQW ZLWK WKDW RI $ LQGLFDWLQJ A UHPRYDO GXULQJ WKH ILUVW VHYHUDO GD\V +RZHYHU PLFURELDO DFWLYLW\ ZDV LQFUHDVHG RYHU WUHDWPHQW $ 7KLV PLFURELDO DFWLYLW\ GLG QRW UHVXOW LQ VLJQLILFDQW GHJUDGDWLRQ RI K\GURFDUERQV

PAGE 148

7DEOH %LRGHJUDGDWLRQ UDWH FRQVWDQWV DQG FRUUHODWLRQ FRHIILFLHQWV IRU WKH ILW RI ELRGHJUDGDWLRQ H[SHULPHQW GDWD WR D ILUVW RUGHU UDWH HTXDWLRQ 7UHDWPHQW %HQ]HQH 7ROXHQH (WKE]D PS;\OHQH R;\OHQH $ NE U % N U & N U N" U ( N U ) N U N U + N U N U

PAGE 149

7DEOH &RQWLQXHG 7UHDWPHQW (7 70% (7 70% 70% $ N U % N U & N U N U ( N U ) N U N U + N U  U D (WK\OEHQ]HQH

PAGE 150

7DEOH %LRGHJUDGDWLRQ UDWH FRQVWDQWV DQG FRUUHODWLRQ FRHIILFLHQWV IRU WKH ILW RI ELRGHJUDGDWLRQ H[SHULPHQW GDWD WR WKH 7KRPDV VORSH UDWH HTXDWLRQ 7UHDWPHQW %HQ]HQH 7ROXHQH (WKE] PS;\OHQH R;\OHQH $ ND U % N U & N U N U ( N U ) N U B U + N U N f§ B f§ U

PAGE 151

7DEOH &RQWLQXHG 7UHDWPHQW (7 70% (7 70% 70% $ N U % N U & N U N U ( N U ) N U N U + N U N U D GD\

PAGE 152

& & 2 Â’ %1= 72/ 2 (%= $ 03; [ 2; )LJXUH 5HODWLYH FRQFHQWUDWLRQV RI &A&J DURPDWLF K\GURFDUERQV YV WLPH LQ ELRGHJUDGDWLRQ WUHDWPHQW %

PAGE 153

7UHDWPHQWV DQG ( 7KHVH GDWD DVVHVVHG WKH HIIHFW RI DGGLWLRQ RQ WKH PLFURELDO FRPPXQLW\ 7KHVH ZHUH HVVHQWLDOO\ UHSHDWV RI WUHDWPHQWV & DQG ,) 7KH DGGLWLRQ RI PJ/ WUHDWPHQW 'f SURGXFHG D GD\ ODJ SKDVH IRU EHQ]HQH WROXHQH PS[\OHQH DQG HWK\OWROXHQH UHODWLYH WR QR + WUHDWPHQW )LJXUH f 7KH H[WHQW RI WUHDWPHQW ZDV FRPSDUDEOH WR WUHDWPHQW $ DLU DGGLWLRQf 7KH '2 SURILOHV DUH VKRZQ LQ )LJXUH 7KH ODJ LQ ELRDFWLYLW\ ZDV SDUDOOHOHG E\ D ODJ LQ FRQVXPSWLRQ RI '2 IRU WKH VDPH GD\ SHULRG 7KH DGGLWLRQ RI 1+A&O LQ WUHDWPHQW ( SURGXFHG D WR[LF HIIHFW DQG WKH K\GURFDUERQ GDWD ZHUH HTXLYDOHQW WR WKH VWHULOH FRQWURO ORVVHV +RZHYHU WKH '2 SURILOH )LJXUH f VKRZHG FRQVXPSWLRQ RI GLVVROYHG R[\JHQ DQG WKLV LPSOLHG VRPH PLFURELDO DFWLYLW\ 7KH ,17 GDWD DOVR GHPRQVWUDWHG LQFUHDVHG ELRDFWLYLW\ )LJXUH f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

PAGE 154

& & R Â’ %1= 72/ (%= 03; 2; )LJXUH 5HODWLYH FRQFHQWUDWLRQV RI &J&J DURPDWLF K\GURFDUERQV YV WLPH LQ ELRGHJUDGDWLRQ WUHDWPHQW

PAGE 155

D )LJXUH &RQFHQWUDWLRQ YV WLPH IRU GLVVROYHG R[\JHQ LQ ELRGHJUDGDWLRQ WUHDWPHQWV $ % DQG &

PAGE 156

XJ ,17 JUDP GU\ ZHLJKW VRLO $< 6 Â’ 757 787 ( 7.7 ) )LJXUH (OHFWURQ WUDQVSRUW DFWLYLW\ LQ ELRGHJUDGDWLRQ WUHDWPHQWV ( DQG )

PAGE 157

WKHLU KLJKHU YDSRU SUHVVXUH WRUU IRU EHQ]HQH DQG WRUU IRU WROXHQH FRPSDUHG ZLWK WRUU IRU P[\OHQH DW &f 7KH KDOI OLYHV IRU ELRGHJUDGDWLRQ XQGHU WKHVH FRQGLWLRQV ZHUH LQ WKH VDPH UDQJH DV WKRVH IRU WKH KLJKHU FRQFHQWUDWLRQV LH WUHDWPHQW $f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f 6WHULOLW\ LQ WUHDWPHQWV & ) DQG ZDV LQGLFDWHG E\ WKH ODFN RI A FRQVXPSWLRQ ORZ ,17 UHGXFWLRQ DQG WKH SHUVLVWHQFH RI DURPDWLF K\GURFDUERQV 7KH ORVVHV DVVXPHG WR UHVXOW IURP GLIIXVLRQ WKURXJK WKH WHIORQ VHSWDf ZHUH LQ WKH UDQJH RI b IRU *A&J K\GURFDUERQV DQG b IRU &+ FRPSRXQGV 6RUSWLRQ ORVVHV ZHUH DFFRXQWHG IRU LQ WKHVH GDWD E\ DGGLQJ WKH DPRXQW ORVW WR VRUSWLRQ WR WKH DTXHRXV FRQFHQWUDWLRQ GDWD 7KH GURS LQ '2 LQ WUHDWPHQW LQGLFDWHG WKDW R[\JHQ DOVR GLIIXVHV WKURXJK WKH WHIORQ

PAGE 158

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f ZHUH KLJKHVW LQ ERWK ELRGHJUDGDWLRQ H[SHULPHQWV ZLWK DLU DXJPHQWDWLRQ $ DQG $f RU ZLWK WKH DGGLWLRQ RI R[\JHQ *f $OPRVW FRPSOHWH GHJUDGDWLRQ WR EHORZ GHWHFWLRQ OLPLW RU OHVV WKDQ XJ/f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

PAGE 159

LQ WKH DTXLIHU DW WKH /DNH $OIUHG VLWH DQG WKH ORZ GLVVROYHG R[\JHQ OHYHOV LQ WKH DTXLIHU LQGLFDWH WKDW WKHUH PD\ EH VLJQLILFDQW OHYHOV RI QLWULI\LQJ EDFWHULD ZKLFK PD\ EH VWLPXODWHG E\ WKH DGGLWLRQ RI 1+ &O ,QGLUHFW HYLGHQFH IRU WKLV K\SRWKHVLV LV VHHQ LQ WKH UHVXOWV RI WKH ,17 VWXGLHV IRU WUHDWPHQWV $ DQG % 7UHDWPHQW % VKRZHG D VHYHQIROG LQFUHDVH LQ HOHFWURQ WUDQVSRUW DFWLYLW\ DOWKRXJK WKHUH ZDV QR VXEVWDQWLDO GHFUHDVH LQ K\GURFDUERQ FRQFHQWUDWLRQ )LJXUH f 7KH PLFURRUJDQLVPV LQ WKLV VWXG\ DUH DEOH WR GHJUDGH DURPDWLF K\GURFDUERQV UDSLGO\ GRZQ WR WKH XJ/ UDQJH JLYHQ VXIILFLHQW R[\JHQ 7KHVH GDWD FRQILUP WKH ZRUN RI -HQVHQ HW DO f ZKR VKRZ WKH GHJUDGDWLRQ RI DURPDWLF K\GURFDUERQV LQ SHWUROHXP FRQWDPLQDWHG JURXQGZDWHU WR XJ/ RU OHVV 7KH UDWHV RI ELRGHJUDGDWLRQ GHWHUPLQHG IURP WKHVH EDWFK ELRGHJUDGDWLRQ VWXGLHV ZHUH VLJQLILFDQWO\ IDVWHU WKDQ WKDW RI .DSSHOHU DQG :XKUPDQQ Ef ,Q WKDW VWXG\ EHQ]HQH UHTXLUHG GD\V WR GHJUDGH FRPSOHWHO\ 'HOILQR DQG 0LOHV f VKRZHG DQ HLJKW GD\ ODJ SKDVH IRU EHQ]HQH GRVHG WR FOHDQ JURXQGZDWHU ,Q WKLV VWXG\ EHQ]HQH ZDV FRPSOHWHO\ UHPRYHG LQ D PLQLPXP RI WZR GD\V LQGLFDWLQJ WKH DGDSWDWLRQ RI EDFWHULD IURP WKH /DNH $OIUHG VLWH WR GHJUDGH DURPDWLF K\GURFDUERQV +\GURJHQ 3HUR[LGH 7KH LQWURGXFWLRQ RI K\GURJHQ SHUR[LGH LQWR WKH PLFURFRVPV SURGXFHG D ODJ SKDVH 7KH PLFURELDO SRSXODWLRQV UHTXLUHG VHYHUDO GD\V WR DGDSW WR WKH FKDQJLQJ HQYLURQPHQWDO

PAGE 160

XJ c17 JUDP GU\ Y%OJKW VRLO $9 6 Â’ 757 $ 757 % R 757 & )LJXUH f (OHFWURQ WUDQVSRUW DFWLYLW\ LQ ELRGHJUDGDWLRQ WUHDWPHQWV $ % DQG &

PAGE 161

FRQGLWLRQV 7KLV ZDV UHIOHFWHG LQ WKH HOHFWURQ WUDQVSRUW DFWLYLW\ JUDSKV ZKHUH +r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r UHODWLYH WR DLU RU R[\JHQ DGGLWLRQ 7KHVH VWXGLHV GHPRQVWUDWH WKDW + GRHV QRW OLPLW WKH H[WHQW RI ELRGHJUDGDWLRQ EXW WKDW WKHUH LV DQ DGDSWLRQ SHULRG DVVRFLDWHG ZLWK LWV XVH 1R FROXPQ H[SHULPHQWV ZHUH SHUIRUPHG ZLWK K\GURJHQ SHUR[LGH 7KHVH H[SHULPHQWV ZRXOG KDYH DVVHVVHG K\GURJHQ SHUR[LGH UHDFWLYLW\ XQGHU IORZLQJ FRQGLWLRQV &ROXPQ %LRGHJUDGDWLRQ ([SHULPHQWV 6HYHUDO DXWKRUV HPSOR\HG IORZWKURXJK VRLO FROXPQV WR VWXG\ WKH GHJUDGDWLRQ RI RUJDQLF FRQWDPLQDQWV .XKQ HW DO f .XKQ HW DO f QRWHG WKDW LI RQH H[SHFWV WR

PAGE 162

DSSO\ ODERUDWRU\ GHULYHG UDWH FRQVWDQWV WR ILHOG FRQGLWLRQV WKDW LQSXW FRQFHQWUDWLRQV VKRXOG EH VLPLODU WR ILHOG FRQFHQWUDWLRQV 7KH FROXPQV XVHG LQ WKLV ZRUN ZHUH SDFNHG ZLWK VRLO IURP WKH /DNH $OIUHG ILHOG VLWH DQG ZHUH VXSSOLHG ZLWK ZHOO ZDWHU IURP /DNH $OIUHG VR WKDW ILHOG DQG ODERUDWRU\ FRQGLWLRQV ZHUH FORVHO\ PDWFKHG 7ZR IORZ UDWHV ZHUH XVHG WR EHWWHU VLPXODWH WKH YDULHG IORZ FRQGLWLRQV SUHVHQW LQ WKH /DNH $OIUHG DTXLIHU 7KH UHVXOWV RI WKH FROXPQV UXQ DW ORZ IORZ YHORFLWLHV FPPLQf DUH VKRZQ LQ )LJXUH 7KHVH GDWD ZHUH DQDO\]HG WR GHWHUPLQH UDWH FRQVWDQWV DQG WKHVH DUH VKRZQ LQ 7DEOH 7KH UDWH FRQVWDQWV ZHUH FDOFXODWHG ZLWK HTXDWLRQ >@ 7KH UDWHV RI GHJUDGDWLRQ ZHUH PXFK KLJKHU LQ WKH FROXPQ V\VWHP WKDQ LQ WKH EDWFK ELRGHJUDGDWLRQ V\VWHP 7KH UDWH FRQVWDQWV RI WKH DURPDWLF FRPSRXQGV LQ WKH FROXPQ V\VWHP ZHUH RQH WR WZR RUGHUV RI PDJQLWXGH JUHDWHU WKDQ EDWFK VWXG\ FRQVWDQWV 7KH LQFUHDVHG UDWH RI K\GURFDUERQ UHPRYDO ZDV WKH UHVXOW RI LPSURYHG WUDQVSRUW RI FDUERQ VRXUFHV QXWULHQWV DQG R[\JHQ WR WKH PLFURELDO FRPPXQLW\ LQ WKH FROXPQ V\VWHP 7KH PLFURFRVPV LQ WKH EDWFK VWXGLHV ZHUH QRW FRQWLQXRXVO\ PL[HG VR WKDW SRUWLRQV RI WKH PLFURFRVP PD\ KDYH EHHQ QXWULHQW RU R[\JHQ OLPLWHG 5HPRYDO HIILFLHQFLHV RI b ZHUH VHHQ IRU DOO FRPSRXQGV H[FHSW IRU EHQ]HQH ZKLFK ZDV GHJUDGHG PRUH VORZO\ DQG VKRZHG D b SHUFHQW UHPRYDO 7KH RUGHU RI GHJUDGDWLRQ ZDV PS[\OHQH HWK\OEHQ]HQH R[\OHQH WROXHQH EHQ]HQH 7KLV RUGHU ZDV

PAGE 163

& & R 325( 92/80(6 Â’ %1= 72/ R (%= D 03; [ 2; )LJXUH %UHDNWKURXJK FXUYHV IRU DURPDWLF FRPSRXQGV LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQWV SHUIRUPHG DW D IORZ UDWH RI P/KU

PAGE 164

7DEOH )LUVW RUGHU ELRORJLFDO UDWH FRQVWDQWV DQG KDOIOLYHV RI DURPDWLF K\GURFDUERQV IRU WKH ELRGHJUDGDWLRQ FROXPQ ZLWK IORZ DW P/KU &RPSRXQG &&R rD L GD\ GD\ %HML]HQH 7ROXHQH (WK\OEHQ]HQH PS;\OHQH ;\OHQH DFDOFXODWHG IURP WKH IROORZLQJ GDWD OHQJWK FP EXON GHQVLW\ JP/ SDUWLFOH GHQVLW\ JP/ SRUH ZDWHU YHORFLW\ FPGD\ YROXPHWULF ZDWHU FRQWHQW

PAGE 165

FRQVLVWHQW ZLWK WKH UHPRYDO RI VLGH FKDLQV SULRU WR DWWDFN RQ WKH DURPDWLF QXFOHRXV 'HJUDGDWLRQ UDWHV IRU FROXPQV UXQ DW WKH KLJKHU IORZ UDWH DUH VKRZQ LQ 7DEOH 7KH IDVWHU IORZ UDWH GHFUHDVHG WKH KDOI OLYHV RI WKH DURPDWLF FRQWDPLQDQWV 7KLV UHVXOWHG IURP LPSURYHG WUDQVSRUW RI R[\JHQ DQG VXEWUDWH 7KH IORZ UDWH XVHG LQ WKLV FROXPQ ZDV HTXLYDOHQW WR JURXQGZDWHU YHORFLWLHV LQ SRUWLRQV RI WKH /DNH $OIUHG DTXLIHU .LOODQ f DQG PD\ FORVHO\ UHIOHFW ILHOG UHPRYDOV %UHDNWKURXJK FXUYHV IRU EHQ]HQH WROXHQH DQG WULPHWK\OEHQ]HQH DUH VKRZQ LQ )LJXUHV DQG 2QO\ b RI WKH EHQ]HQH DQG b RI WKH WROXHQH ZHUH UHPRYHG DW WKLV IORZ UDWH DOWKRXJK RWKHU UHPRYDOV DUH LQ WKH UDQJH RI b 7KH GLIIHUHQFH LQ WKH GHJUDGDWLRQ IRU EHQ]HQH LV VHHQ E\ FRPSDULVRQ RI )LJXUHV ZLWK )LJXUH %HQ]HQH DOPRVW EUHDNV WKURXJK WKH FROXPQ FRPSOHWHO\ UHIOHFWLQJ WKH WLPH LQYROYHG IRU WKH PLFUREHV WR GHJUDGH WKLV VROXWH 7KH EUDQFKHG DURPDWLF FRPSRXQGV DUH PRUH UDSLGO\ GHJUDGHG ZKLFK LV FRQVLVWHQW ZLWK WKH UHVXOWV IURP WKH FPPLQ FROXPQ 7KH UDWHV RI GHJUDGDWLRQ RI WKH DURPDWLF FRPSRXQGV LQ WKH FPPLQ FROXPQV ZHUH LQ WKH RUGHU &J &J %HQ]HQH ZDV WKH PRVW UHFDOFLWUDQW ZLWK D KDOI OLIH RI GD\V KRXUVf 7KHVH GDWD DUH FRQVLVWHQW ZLWK WKH DURPDWLF GHJUDGDWLRQ SURFHVV GHVFULEHG E\ (YDQV f DQG WKH OLWHUDWXUH RQ WKH IDWH RI DURPDWLF K\GURFDUERQV LQ VRLOV %RVVHUW DQG %DUWKD f

PAGE 166

7DEOH )LUVW RUGHU ELRORJLFDO UDWH FRQVWDQWV DQG KDOIOLYHV RI DURPDWLF K\GURFDUERQV IRU WKH ELRGHJUDGDWLRQ FROXPQ ZLWK IOSZ DW P/PLQ &RPSRXQG ND GD\ GD\ %HQ]HQH 7ROXHQH (WK\OEHQ]HQH PS;\OHQH R;\OHQH ,VRSURS\OEHQ]HQH Q3URS\OEHQ]HQH RU (WK\OWROXHQH 7ULPHWK\OEHQ]HQH (WK\OWROXHQH 7ULPHWK\OEHQ]HQH 7ULPHWK\OEHQ]HQH e FDOFXODWHG ZLWK WKH IROORZLQJ GDWD OHQJWK FP SRUH ZDWHU YHORFLW\ FPPLQ SDUWLFOH GHQVLW\ JP/ EXON GHQVLW\ JP/ YROXPHWULF ZDWHU FRQWHQW

PAGE 167

325( 92/80(6 )LJXUH %UHDNWKURXJK FXUYH IRU EHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 168

325( 92/80(6 )LJXUH %UHDNWKURXJK FXUYH IRU WROXHQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 169

& & R 325( 92/80(6 )LJXUH %UHDNWKURXJK FXUYH IRU WULPHWK\OEHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 170

%DVHG RQ WKHVH GDWD LW LV HYLGHQW WKDW D ZHOO DGDSWHG VWDQGLQJ PLFURELDO SRSXODWLRQ IURP /DNH $OIUHG LV FDSDEOH RI GHJUDGLQJ DURPDWLF K\GURFDUERQV DW UHODWLYHO\ KLJK ORDGLQJV DQG VKRUW FRQWDFW WLPHV 'HJUDGDWLRQ PD\ EH DLGHG E\ WKH GHYHORSPHQW RI DQ HIILFLHQW ELRILOP %RXZHU DQG 0F&DUW\ f %HQ]HQH ZDV GHJUDGHG WR D OHVVHU H[WHQW WKDQ WKH DON\O DURPDWLFV DQG R[\OHQH ZDV PRUH UHVLVWDQW WR PLFURELDO GHJUDGDWLRQ WKDQ WKH PHWD DQG SDUD LVRPHUV .XKQ HW DO f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

PAGE 171

ELRGHJUDGDWLRQ LQ WKH ILHOG ZKHUH R[\JHQ OLPLWDWLRQ UHGXFHV WKH ELRORJLFDO UHPRYDO RI K\GURFDUERQV 7KH UDSLG ELRGHJUDGDWLRQ RI VROXWHV LQ WKH EDWFK DQG FROXPQ ELRGHJUDGDWLRQ VWXGLHV VXSSRUWV WKH K\SRWKHVLV WKDW WKH PLFURELDO FRPPXQLW\ LQ WKH /DNH $OIUHG DTXLIHU LV ZHOO DGDSWHG WR UHPRYH DURPDWLF K\GURFDUERQV IURP JDVROLQH VRXUFHV ,Q LQVWDQFHV ZKHUH DGDSWDWLRQ KDV RFFXUUHG ELRWUDQVIRUPDWLRQV PD\ EH VR UDSLG WKDW WKH\ DUH FRQVLGHUHG LQVWDQWDQHRXV UHODWLYH WR WKH UDWH RI JURXQGZDWHU IORZ 7KLV VKLIWV WKH TXDQWLWDWLYH SUHGLFWLRQ RI ELRORJLFDO DFWLYLW\ IURP D FRQVLGHUDWLRQ RI ELRORJLFDO NLQHWLFV WR D FRQVLGHUDWLRQ RI WKH H[WHQW RI XWLOL]DWLRQ :LOVRQ HW DO Ef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

PAGE 172

'LVSHUVLRQ 7KH EUHDNWKURXJK FXUYH IRU WKH 1+A&O WUDFHU DW WKH /DNH $OIUHG VLWH LV VKRZQ LQ )LJXUH 7KH GLVSHUVLRQ FRHIILFLHQW FDOFXODWHG IURP WKHVH GDWD ZDV FP PLQ &RPSDUHG ZLWK WKH GLVSHUVLRQ FRHIILFLHQWV IURP WKH FROXPQ H[SHULPHQWV SHUIRUPHG DW FPPLQ FP PLQf WKH ILHOG VFDOH GLVSHUVLRQ LV DQ RUGHU RI PDJQLWXGH ODUJHU WKDQ WKH FROXPQ GDWD 7KH FDOFXODWHG LV DSSUR[LPDWHO\ 7KLV YDOXH VKRXOG EH XVHIXO LQ WKH PRGHOLQJ RI WKH /DNH $OIUHG DTXLIHU 6ROXWH 7UDQVSRUW $Q DQDO\VLV RI VROXWH WUDQVSRUW DW WKH /DNH $OIUHG UHVHDUFK VLWH LV KDPSHUHG E\ JHRORJLF DQG PDQPDGH REVWDFOHV 7KH SUHVHQFH RI D VZDOH UXQQLQJ WKURXJK WKH VLWH DQG RI D GXDO IORZ SDWWHUQ DURXQG WKH SXPS KRXVH %XLOGLQJ f KDYH SURGXFHG SUHIHUHQWLDO IORZ LQ WKH DTXLIHU $OVR VHZHU GUDLQDJH VWHDP DQG WHOHFRPPXQLFDWLRQV OLQHV FULVVn FURVV FRQWDPLQDWHG SRUWLRQV RI WKH DTXLIHU FRPSOLFDWLQJ WKH IORZ SDWK RI GLVVROYHG K\GURFDUERQV ,W LV DOVR SUREDEOH WKDW JDVROLQH VWRUDJH WDQNV LQ EHWZHHQ %XLOGLQJV DQG DQG WUDQVIHU HTXLSPHQW VRXWK RI WKH ZDVK UDFN DGGHG XQNQRZQ TXDQWLWLHV RI JDVROLQH WR SRUWLRQV RI WKH VWXG\ DUHD .LOODQ f 7KLV VNHZV WKH GLVWULEXWLRQ RI K\GURFDUERQV LQ WKH DTXLIHU DQG PDNHV GHWHUPLQDWLRQ RI VROXWH WUDQVSRUW GLIILFXOW )LQDOO\ WKH SXPSLQJ ZHOOV 8)0 5$3 DQG 5$3f GLVWRUW WKH WUDQVSRUW RI FRQWDPLQDQWV /HVV UHWDUGHG VROXWHV DSSHDU WR EH PRUH UHWDLQHG E\ UHYHUVDO RI

PAGE 173

& & R 325( 92/80(6 )LJXUH %UHDNWKURXJK FXUYH IRU ILHOG WUDFHU 1+&,f H[SHULPHQW PHDVXUHG DW 5$3

PAGE 174

WKH K\GUDXOLF JUDGLHQW &RQYHUVHO\ VROXWHV ZKLFK DUH PRUH KLJKO\ VRUEHG PRYH PRUH TXLFNO\ WRZDUGV WKH SXPSLQJ ZHOOV DV D UHVXOW RI LQFUHDVHG FRQYHFWLYH IORZ RI WKH PRELOH SKDVH LH JURXQGZDWHUf :LWK WKHVH FDYHDWV LQ PLQG LQWHUSUHWDWLRQ RI WKH ILHOG GDWD EHFRPHV YHU\ FRPSOH[ 7KH GLVWULEXWLRQ RI EHQ]HQH DW WKH ILHOG VLWH LV KLJKHVW WRZDUG WKH VZDPS ZHOO 8):f DV LV VKRZQ LQ )LJXUH 7KH PDMRU FRQFHQWUDWLRQV RI EHQ]HQH VHHP WR KDYH PLJUDWHG VXEVWDQWLDOO\ IDVWHU WKDQ WKH RWKHU FRPSRXQGV 7KLV LV H[SHFWHG IURP WKH UHODWLYHO\ ORZ UHWDUGDWLRQ IDFWRU GHPRQVWUDWHG LQ WKH ODERUDWRU\ VWXGLHV DQG DOVR IURP WKH LQHIILFLHQW ELRGHJUDGDWLRQ RI EHQ]HQH DW KLJK IORZ DV GHWHUPLQHG LQ WKH ELRGHJUDGDWLRQ FROXPQ UXQ DW FPPLQ ,Q WKLV FROXPQ RQO\ b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f KDV D PHDVXUHG UHWDUGDWLRQ IDFWRU RI ZKLFK LV b ODUJHU WKDQ WKDW RI EHQ]HQH +RZHYHU WKH DUHDO GLVWULEXWLRQ RI R[\OHQH LV PXFK

PAGE 176

8)0 :HWODQG )LJXUH 'LVWULEXWLRQ RI R[\OHQH XJ/f DW WKH /DNH $OIUHG ILHOG VLWH

PAGE 177

GLIIHUHQW WKDQ WKDW RI EHQ]HQH %DVHG RQ D FRPSDULVRQ RI 5 YDOXHV WKH GLVWULEXWLRQ RI R[\OHQH VKRXOG EH VNHZHG WRZDUGV WKH ZHWODQGV DV LV EHQ]HQH 2QH IDFWRU ZKLFK PD\ DFFRXQW IRU WKH DSSDUHQW LQFUHDVH LQ UHWDUGDWLRQ IRU R [\OHQH LV WKH KLJKHU UDWH FRQVWDQW IRU ELRORJLFDO UHPRYDO KDOI OLIH KRXUV DW FPPLQf FRPSDUHG WR EHQ]HQH KRXUVf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f ZLWK QR VLJQLILFDQW FKDQJHV LQ WKH FRQFHQWUDWLRQV RI DQ\ RI WKH LQGLYLGXDO VROXWHV

PAGE 178

7DEOH 0LFURELDO SRSXODWLRQV LQ D VRLO FRUH WDNHQ VRXWK RI WKH SDLQW VKRS %OGJ f -XQH D &)8JGZ [ 'HSWK IHHW DYJ VWG GHY D&)8JGZ FRORQ\ IRUPLQJ XQLWV SHU JUDP GU\ ZHLJKW 7DEOH 0LFURELDO SRSXODWLRQV LQ D VRLO FRUH WDNHQ LQ WKH VSUD\ ILHOG -XQH &)8JGZD[ 'HSWK IHHW DYJ VWG GHY /2 f 2 D&)8JGZ FRORQ\ IRUPLQJ XQLWV SHU JUDP GU\ ZHLJKW

PAGE 179

7DEOH 0LFURELDO SRSXODWLRQV LQ D VRLO FRUH WDNHQ VRXWK RI WKH SXPS KRXVH %OGJ f -XO\ &)8JGZ [ 'HSWK IHHW DYJ VWG GHY &RPPHQWV 6DWXUDWHG ]RQH JDVROLQH RGRU

PAGE 180

7DEOH 0LFURELDO SRSXODWLRQV IURP VDPSOHV FROOHFWHG GXULQJ LQVWDOODWLRQ RI PRQLWRULQJ ZHOOV 5$3 DQG 5$3 6HSWHPEHU &)8JGZ [ 'HSWK 5$3 5$3 IHHW DYJ VWG GHY DYJ VWG GHY &RPPHQWV D QV QV QV QV 6DWXUDWHG ]RQH D QR VDPSOH

PAGE 181

7DEOH :DWHU FKHPLVWU\ SDUDPHWHUV IURP VHOHFWHG PRQLWRULQJ ZHOOV DW /DNH $OIUHG &5(& :HOO &KORULGH PJ/ &RQGXFWLYLW\ XPKRV S+ 'LVVROYHG 2[\JHQ PJ/ 7RWDO 3KRVSKDWH PJ/ 1LWUDWH PJ/ 2+0 2+0 2+0 2+0 3 3 3 8)( 8)0 8): 5$3 5$3 5$3 5$3 5$3

PAGE 182

7KH RSSRVLWH DSSHDUV WR EH WUXH LQ GDWD IURP ZHOO 3 7KLV ZHOO VKRZV VLJQLILFDQW GHFUHDVHV LQ VRPH DURPDWLF K\GURFDUERQV DQG WKH GLVVROYHG R[\JHQ OHYHOV VWDUW WR LQFUHDVH DIWHU 1RYHPEHU 7KLV PD\ EH WKH UHVXOW RI WKH LQFUHDVHG UHFKDUJH RI DHUDWHG ZDWHU DQG FKDQJH LQ SXPSLQJ FRQGLWLRQV HVWDEOLVKHG E\ .LOODQ f 'HFUHDVHV LQ K\GURFDUERQ FRQFHQWUDWLRQV FRQFRPLWDQW ZLWK LQFUHDVLQJ '2 DUH DOVR QRWHG XS JUDGLHQW RI 3 SULRU WR 1RYHPEHU :HOOV 5$3 DQG 5$3 H[KLELW UDSLG UHPRYDOV RI K\GURFDUERQV IROORZLQJ WKH VWDUW RI LQFUHDVHG IOXVKLQJ ZLWK DHUDWHG ZDWHU 2FWREHU f +RZHYHU WKH GDWD DUH LQVXIILFLHQW WR FRQFOXGH ZKHWKHU WKLV FKDQJH UHVXOWV IURP WKH LQFUHDVHG VXSSO\ RI R[\JHQDWHG ZDWHU DQG VXEVHTXHQW ELRGHJUDGDWLRQ RU LI LW LV FDXVHG E\ WKH PRUH UDSLG VROXWH WUDQVSRUW RZLQJ WR LQFUHDVLQJ WKH IORZ YHORFLW\ RI WKH DTXLIHU

PAGE 183

&+$37(5 9, 6800$5< $1' &21&/86,216 6XPPDU\ +\GURO\VLV VRUSWLRQ DQG ELRGHJUDGDWLRQ UHDFWLRQV RI DURPDWLF K\GURFDUERQV DOO LVRPHUV RI &A+&+ff XQGHU ZDWHU VDWXUDWHG VRLO FRQGLWLRQV ZHUH LQYHVWLJDWHG 6HYHUDO WUHDWPHQW WHFKQLTXHV ArU r JDV DQG 1+& f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bf RI WKH DTXLIHU PDWHULDO 7KH DTXLIHU ZDV FRPSRVHG SULPDULO\ RI PHGLXP WR ILQH JUDLQHG VDQGV &RQWDPLQDWHG ZHOO ZDWHU IURP WKH VXUILFLDO DTXLIHU ZDV HPSOR\HG DV WKH VRXUFH RI VROXWHV IRU WKH PDMRULW\ RI H[SHULPHQWV 7KH PDMRU FRPSRQHQWV RI WKLV ZDWHU ZHUH WKH K\GURFDUERQV &A+A&A+f XVHG LQ WKLV VWXG\

PAGE 184

+\GURO\VLV VWXGLHV +\GURO\VLV GLG QRW DFFRXQW IRU VXEVWDQWLDO ORVVHV RI WKH DURPDWLF K\GURFDUERQV LQ WKLV VWXG\ 7KHVH VROXWHV ZHUH UHVLVWDQW WR K\GURO\VLV HYHQ XQGHU H[WUHPH UHODWLYH WR WKH HQYLURQPHQWf FRQGLWLRQV RI S+ f RU WHPSHUDWXUH &f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f IRU WKH WZR OLQHDU PRGHOV ZHUH HTXLYDOHQW DQG WKH )UHXQGOLFK PRGHO JDYH VLPLODU VRUSWLRQ FRHIILFLHQWV .Af YDOXHV IURP WKH OLQHDU PRGHOV UDQJHG

PAGE 185

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f ZDV FORVH WR VHHSDJH YHORFLWLHV PHDVXUHG DW WKH ILHOG VLWH FPPLQf 7KH FROXPQ EUHDNWKURXJK FXUYHV %7&f H[KLELWHG VRPH QRQHTXLOLEULD DV D UHVXOW RI VORZ VRUSWLRQ NLQHWLFV DQG WKLV SURFHVV PD\ DOVR DIIHFW WKH WUDQVSRUW RI VROXWHV LQ WKH ILHOG 7KH LQIOXHQFH RI FRPSHWLQJ VROXWHV ZDV LQYHVWLJDWHG E\ FRPSDULQJ UHWDUGDWLRQ YDOXHV IRU EHQ]HQH LQ D VLQJOH VROXWH V\VWHP ZLWK WKH EUHDNWKURXJK FXUYH IRU EHQ]HQH LQ WKH PXOWLFRPSRQHQW V\VWHP 7KH UHWDUGDWLRQ IDFWRUV IRU EHQ]HQH LQ ERWK FROXPQ V\VWHPV ZHUH VLPLODU YV f 6ROXWH FRPSHWLWLRQ IRU VRUELQJ VLWHV ZDV QRW D VLJQLILFDQW IDFWRU

PAGE 186

LQ WKLV VWXG\ 7KLV ZDV OLNHO\ WKH UHVXOW RI WKH XVH RI ORZ FRQFHQWUDWLRQV OHVV WKDQ b RI WKH ZDWHU VROXELOLW\f 6RUSWLRQ PHFKDQLVPV ZHUH HYDOXDWHG E\ FRPSDULVRQ RI .TF GDWD IURP FROXPQ VWXGLHV LQ WKLV VWXG\ ZLWK SDUWLWLRQLQJ DQG PROHFXODU WRSRORJ\ PRGHOV 5HJUHVVLRQ DQDO\VLV RI .TF GDWD YHUVXV OLWHUDWXUH YDOXHV IRU GHPRQVWUDWHG WKDW RZ SDUWLWLRQLQJ DORQH GLG QRW DGHTXDWHO\ GHVFULEH WKH VRUSWLRQ SURFHVV U f 5HJUHVVLRQ DQDO\VLV RI .TF GDWD ZLWK ILUVW RUGHU PROHFXODU FRQQHFWLYLW\ LQGLFHV LQGLFDWHG WKDW VRUSWLRQ PD\ EH SDUWLDOO\ GHVFULEHG DV D VXUIDFH DUHD GHSHQGHQW SKHQRPHQD U f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f ZDV HTXLYDOHQW WR VHHSDJH

PAGE 187

YHORFLWLHV DW WKH ILHOG VLWH DQG VXJJHVWHG WKDW WKH FRQWDFW WLPH ZDV VXLWDEOH IRU FRPSOHWH GHJUDGDWLRQ RI DURPDWLF VROXWHV XQGHU QRQOLPLWLQJ FRQGLWLRQV 7KLV LQGLFDWHG WKH QHHG IRU R[\JHQ DXJPHQWDWLRQ DW WKH ILHOG VLWH WR LQFUHDVH WKH ELRGHJUDGDWLRQ UDWHV RI DURPDWLF FRQWDPLQDQWV %DWFK ELRGHJUDGDWLRQ H[SHULPHQWV ZHUH SHUIRUPHG WR DVVHVV WKH HIILFDF\ RI YDULRXV PHWKRGV WR LQFUHDVH WKH b ELRORJLFDO GHJUDGDWLRQ RI GLVVROYHG DURPDWLF K\GURFDUERQV DW WKH /DNH $OIUHG ILHOG VLWH /DERUDWRU\ H[SHULPHQWV ZLWK K\GURJHQ SHUR[LGH LQGLFDWHG WKH DELOLW\ RI WKH PLFURELDO FRPPXQLW\ DQG WKH DTXLIHU PDWHULDOV WR FDWDO\]H WKH UHGXFWLRQ RI K\GURJHQ SHUR[LGH WR \LHOG R[\JHQ JDV 1R K\GURFDUERQ R[LGDWLRQ ZDV DSSDUHQW DV D UHVXOW RI WKH K\GURJHQ SHUR[LGH GHFRPSRVLWLRQ 7KH KDOI OLYHV IRU ELRORJLFDO UHPRYDO RI WKH VHOHFWHG DURPDWLF K\GURFDUERQV ZLWK WKH DGGLWLRQ RI DLU PJ/ &Af LQ WKH EDWFK ELRGHJUDGDWLRQ VWXGLHV 7UHDWPHQW $ 7KRPDV VORSH UDWH HTXDWLRQf UDQJHG IURP GD\V IRU WROXHQH WR GD\V IRU WULPHWK\,EHQ]HQH %HQ]HQH WROXHQH DQG WULPHWK\OEHQ]HQH ZHUH GHJUDGHG PRVW UDSLGO\ $XJPHQWDWLRQ RI R[\JHQ LQ WKH IRUP RI DLU RU R[\JHQ JDV ZDV PRVW HIIHFWLYH IRU LQFUHDVLQJ WKH ELRGHJUDGDWLRQ RI DURPDWLF K\GURFDUERQV 7KHVH GDWD LQGLFDWHG WKDW WKH PLFUREHV IURP WKH /DNH $OIUHG VLWH ZHUH ZHOO DGDSWHG WR DURPDWLF JDVROLQH K\GURFDUERQV DQG ZHUH OLPLWHG RQO\ E\ WKH DYDLODELOLW\ RI R[\JHQ 7UHDWPHQW ZLWK K\GURJHQ SHUR[LGH PJ/ WR PJ/f LQFUHDVHG WKH GLVVROYHG R[\JHQ OHYHOV LQ WKH

PAGE 188

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

PAGE 189

FRQILUPHG E\ WKH ODERUDWRU\ ELRGHJUDGDWLRQ H[SHULPHQWV ZKHUH WKH PLFUREHV IURP WKH ILHOG VLWH ZHUH ZHOO DGDSWHG DQG ZHUH DEOH WR UDSLGO\ GHJUDGH WKH DURPDWLF VROXWHV WR OHVV WKDQ XJ/ 0LFURELDO SRSXODWLRQV DW WKH ILHOG VLWH ZHUH GHWHUPLQHG WR EH LQ WKH UDQJH RI WR RUJDQLVPV SHU JUDP GU\ ZHLJKW RI VRLO )LHOG 6FDOH 6ROXWH 7UDQVSRUW 7KH GLVWULEXWLRQ RI FRQWDPLQDQWV DW WKH /DNH $OIUHG ILHOG VLWH ZDV FRPSOLFDWHG E\ SK\VLFDO VWUXFWXUHV QXPHURXV VSLOOV DQG XQGHUJURXQG XWLOLWLHV 7KLV PDGH WKH LQWHUSUHWDWLRQ RI ILHOG GDWD GLIILFXOW 7KH PDMRU FRQFHQWUDWLRQV RI EHQ]HQH ZHUH IRXQG DW WKH ZHVWHUQ ERXQGDU\ RI WKH ILHOG VLWH GRZQ JUDGLHQW IURP WKH VSLOO DUHD 7KLV GLVWULEXWLRQ RI EHQ]HQH GHPRQVWUDWHV WKDW WKH FRPELQDWLRQ RI ORZ UHWDUGDWLRQ DQG LQHIILFLHQW ELRGHJUDGDWLRQ FDQ UHVXOW LQ LQFUHDVHG PLJUDWLRQ UHODWLYH WR VROXWHV ZKLFK ZHUH PRUH UHWDUGHG DQG PRUH HDVLO\ GHJUDGHG

PAGE 190

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

PAGE 191

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f DQG K\GURJHQ SHUR[LGH PJ/f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

PAGE 192

0LFURELDO SRSXODWLRQV DW WKH /DNH $OIUHG VLWH ZHUH R[\JHQ OLPLWHG EXW QRW SKRVSKRUXV RU QLWURJHQ OLPLWHG +RUL]RQWDO GLVSHUVLRQ DW WKH ILHOG VLWH ZDV FDOFXODWHG WR EH FP PLQ /RZ UHWDUGDWLRQ f KLJK IORZ YHORFLW\ FPPLQf DQG D GHJUDGDWLRQ UDWH RI XJ/GD\ H[SODLQ WKH GLVWULEXWLRQ RI EHQ]HQH DW WKH ILHOG VLWH

PAGE 193

$33(1',&(6

PAGE 194

$33(1',; $ &+520$72*5$3+,& &21',7,216 $1' 48$/,7< &21752/ 3$5$0(7(56 )25 7+( $1$/<6,6 2) $520$7,& +<'52&$5%216 7KLV DSSHQGL[ OLVWV WKH FKURPDWRJUDSKLF FRQGLWLRQV XVHG LQ WKH JDV FKURPDWRJUDSKLF DQDO\VLV RI DURPDWLF K\GURFDUERQV RQ WKH 3HUNLQ (OPHU JDV FKURPDWRJUDSK )ROORZLQJ WKH *& SDUDPHWHUV VXPPDU\ JXDOLW\ FRQWURO GDWD LV SUHVHQWHG IRU FKURPDWRJUDSKLF DQDO\VHV SHUIRUPHG GXULQJ WKH FRXUVH RI WKHVH VWXGLHV

PAGE 195

0(7+2' $1*/(< '$7( /$67 :5,77(1 6(&7,21 *2 &21752/ 28(1 7(03 '(* &f ,62 7,0( 0,1f 5$03 5$7( %(* &0,1f ),' 6(16 +,*+ (7 =(52 21 '(7 7(03 )/2: $ 0/0,1 &$55,(5 *$6 +( (*8,/,% 7,0( 0,1 727$/ 581 7,0( 0,1 6(&7,21 7,0(' (8(17 7,0( (8(17 :,'7+ 6(7 =(52 ,17(* 2)) 6(&7,21 '$7$ +$1'/,1* '$7$ $&48,6 ,7,21 5(3257 67$57 7,0( 0,1 &$/& 7<3( ,17 67' (1' 7,0( 0,1 $5($+7 &$/& $5($ 35,17 72/ :,'7+ 287387 6.,0 6(16 6&5((1 12 %$6(/,1( &253 %% 35,17(5 <(6 $5($ 6(16 %$6( 6(16 3($. ,'(17,),&$7,21 48$17,7$7,21 &$/ ,( $8* 815(7' 3($. 7,0( 0,1 6&$/,1* )$&725 $5($+7 5(-(&7 5) )25 81.12:16 5() 3. 7,0( 0,1 67' &20317 1$0( &+/252%1= 7,0( 72/ 0,1 603 $02817 67' $02817 &20317 72/ $%6 72/ &20321(17 /, 67 57 5) 67' $07 1$0( *53 6 %(1=(1( 72/8(1( &+/252%1= (7+
PAGE 196

3UHFLVLRQ DQG DFFXUDF\ GDWD IRU WKH DQDO\VLV RI DURPDWLF K\GURFDUERQV LQ JURXQGZDWHU E\ (3$ PHWKRG PRGLILHGf &RPSRXQG 3UHFLVLRQ b 56' VG $FFXUDF\ b 5 VG %HQ]HQH 7ROXHQH (WK\OEHQ]HQH P US;\OHQH R;\OHQH ,VRSURS\OEHQ]HQH .' f Q3URS\EHQ]HQH (WK\OWROXHQH 7ULPHWK\OEHQ]HQH (WK\OWROXHQH 7ULPHWK\OEHQ]HQH 7ULPHWK\OEHQ]HQH

PAGE 197

$33(1',; % ),(/' 6$03/,1* 352&('85(6 7KH VDPSOLQJ SURFHGXUHV HPSOR\HG GXULQJ WKLV UHVHDUFK ZHUH GHVFULEHG LQ WKH /DNH $OIUHG 4XDOLW\ $VVXUDQFH4XDOLW\ &RQWURO 4$4&f SODQ .LOODQ f 6HFWLRQ VL[ RI WKH 4$4& SODQ LV SUHVHQWHG LQ WKH IROORZLQJ SDJHV

PAGE 198

6$03/,1* 352&('85(6 &OHDQLQJ 3URFHGXUHV 9RODWLOH 2UJDQLFV %RWWOH W\SH ZDWHU P/ JODVV YLDO ZLWK WHIORQ OLQHG VHSWXP FDSV VRLO TXDUW PDVRQ MDUV 6RDS $OFRQR[ f :DVK FDSV OLQHUV DQG YLDOV LQ KRW VRDS\ ZDWHU f 5LQVH OLEHUDOO\ ZLWK WDS DQG ', ZDWHU f 5LQVH ZLWK SHVWLFLGH JUDGH PHWKDQRO f 'U\ FDSV VHSWD DQG YLDOV LQ RYHQ DW & IRU QR PRUH WKDQ PLQXWHV f &RRO LQ LQYHUWHG SRVLWLRQ DQG FDS LPPHGLDWHO\ ZKHQ ERWWOHV DUH FRRO HQRXJK WR KDQGOH /DEHOV f$IWHU FOHDQLQJ WKH DSSURSULDWH ODEHO LV DWWDFKHG WR HDFK ERWWOH DQG WKH GDWH FOHDQHG LV HQWHUHG )LHOG 'RFXPHQWV DQG 5HFRUGV )LHOG VKHHWV 7KH ILHOG VKHHW VHH DWWDFKPHQWVf LV ILOOHG LQ ZLWK WKH IROORZLQJ LQIRUPDWLRQ XSRQ VDPSOLQJ f GDWH f WLPH f VDPSOH W\SH f SUHVHUYDWLRQ f ZHOO QXPEHU IRU ZHOO VDPSOHVf f ZHOO FDVLQJ DQG GLDPHWHU f GHSWK RI ZDWHU DW WLPH RI VDPSOLQJ f GHSWK RI FRUH LI DSSOLFDEOH VRLO VDPSOHVf f QRWH VSHFLDO FKDUDFWHULVWLFV RI VDPSOH fILHOG QXPEHU $OO ILHOG PHDVXUHPHQWV DUH UHFRUGHG LQ WKH ERXQG ILHOG QRWHERRN RU RQ WKH GDWD VKHHWV

PAGE 199

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

PAGE 200

ZLOO EH WLJKWO\ SDFNHG WR UHGXFH KHDGVSDFH LQ WKH VDPSOH FRQWDLQHU 6DPSOHV DUH WUDQVSRUWHG RQ LFH DQG VWRUHG DW & LQ WKH GDU N %LRORJLFDO $QDO\VLV 6RLO VDPSOHV IRU ELRORJLFDO DQDO\VLV ZLOO EH FROOHFWHG ZLWK VWHULOL]HG SSP FKORULQH VROXWLRQf VWDLQOHVV VWHHO DXJHU 6DPSOHV ZLOO EH SODFHG LQ D RQH TXDUW PDVRQ MDU FOHDQHG LQ WKH VDPH PDQQHU DV WKH GHVFULEHG LQ VHFWLRQ 6DPSOHV ZLOO EH VWRUHG DW & LQ WKH GDUN 0HDVXUHPHQW RI ILHOG SDUDPHWHUV 7HPSHUDWXUH 7HPSHUDWXUH ZLOO EH PHDVXUHG LQ WKH ZHOOV XVLQJ D WKHUPRPHWHU FDOLEUDWHG DJDLQVW DQ 1%6 VWDQGDUG WKHUPRPHWHU S+ 7KH S+ RI WKH ZHOO ZDWHU ZLOO EH PHDVXUHG XVLQJ D SRUWDEOH S+ PHWHU 2ULRQ 5HVHDUFK PRGHO f FRQQHFWHG WR D )LVKHU $FFXS+DVW PLFURSUREH FRPELQDWLRQ HOHFWURGH 'LVVROYHG 2[\JHQ '2 ZLOO EH PHDVXUHG XVLQJ D SRUWDEOH GLVVROYHG R[\JHQ PHWHU <6, $ f ZLWK D <6, R[\JHQ SUREH

PAGE 201

$33(1',; & ,627+(50 '$7$ )25 7+( 62537,21 2) 678'< &203281'6 72 /$.( $/)5(' $48,)(5 0$7(5,$/ %DWFK LVRWKHUP GDWD LV SUHVHQWHG IRU HDFK FRPSRXQG LQ WKLV VWXG\ )UHXQGOLFK LVRWKHUPV IRU HDFK FRPSRXQG DUH DOVR VKRZQ

PAGE 202

%HQ]HQH 6RUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D DPRXQW VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDW LRQ D Q O

PAGE 203

%HQ]HQH 'HVRUSWLRQ 'DWD &V XJ/f DYJ &Z VWG XJ/f DYJ VWG DPRXQW VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDWLRQ D D D Q O

PAGE 204

/22 $02817 625%(' /22 62/87,21 &21&(175$7,21 Â’ 62537,21 R '(62537,21 )UHXQGOLFK VRUSWLRQGHVRUSWLRQ LVRWKHUP IRU EHQ]HQH DW HTXLOLEULXP

PAGE 205

7ROXHQH 6RUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D D D D D D D DPRXQ W VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDW LRQ D Q

PAGE 206

7ROXHQH 'HVRUSWLRQ 'DWD DPRXQW XJ/f &Z XJ/f VRUEHG DYJ VWG DYJ VWG XJ/f D D D D D D Q D ORJ ORJ DPRXQW DPRXQW VROXWLRQ VRUEHG VRUEHG FRQFHQWU QJJf ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, ,,

PAGE 207

/22 $02817 625%(' /22 62/87,21 &21&(175$7,21 Â’ 62537,21 R '(62537,21 )UHXQGOLFK VRUSWLRQGHVRUSWLRQ LVRWKHUP IRU WROXHQH DW HTXLOLEULXP

PAGE 208

UD3B;\OHQH 6RUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D D D D D D D D D DPRXQW VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDWLRQ D Q

PAGE 209

LQS;\OHQH 'HVRUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D D D D DPRXQW VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDWLRQ D Q O

PAGE 210

/22 $02897 625%(' )UHXQGOLFK VRUSWLRQGHVRUSWLRQ LVRWKHUP IRU PS;\OHQH DW HTXLOLEULXP

PAGE 211

R;\OHQH 6RUSWLRQ 'DWD DPRXQW &V XJ/f &Z XJ/f VRUEHG DYJ VWG DYJ VWG XJ/f D D D D D D ORJ ORJ DPRXQW DPRXQW VROXWLRQ VRUEHG VRUEHG FRQFHQWUDW LRQ QJJf ,, ,, ,, ,, ,, ,, ,, ,, ,, LL LL LL LL LL LL LL LL LL LL LL LL LL

PAGE 212

R;\OHQH 'HVRUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D D D D DPRXQ W VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDWLRQ D Q O

PAGE 213

/22 $02817 625%(' )UHXQGOLFK VRUSWLRQGHVRUSWLRQ LVRWKHUP IRU R;\OHQH DW HTXLOLEULXP

PAGE 214

(WK\OWR XHQH 6RUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D D D D DPRXQW VRUEHG XJ/f DPRXQ W VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDW LRQ D Q O

PAGE 215

(WK\OWROXHQH 'HVRUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D D DPRXQW VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDWLRQ D Q O

PAGE 216

/22 $02817 625%(' /22 62/87,21 &21&(175$7,21 Â’ 62537,21 R '(62I37,21 )UHXQGOLFK VRUSWLRQGHVRUSWLRQ LVRWKHUP IRU (WK\OWROXHQH DW HTXLOLEULXP

PAGE 217

7ULPHWK\OEHQ]HQH 6RUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D D D DPRXQW VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDWLRQ D Q

PAGE 218

7ULPHWK\OEHQ]HQH 'HVRUSWLRQ 'DWD DPRXQW &V XJ/f &Z XJ/f VRUEHG DYJ VWG DYJ VWG XJ/f D D Q D DPRXQW VRUEHG QJJf ORJ ORJ DPRXQW VROXWLRQ VRUEHG FRQFHQWUDWLRQ

PAGE 219

/22 $02817 625%(' /22 62/87,21 &21&(175$7,21 D 62537,21 R '(62537,21 )UHXQGOLFK VRUSWLRQGHVRUSWLRQ LVRWKHUP IRU 7ULPHWK\OEHQ]HQH DW HTXLOLEULXP

PAGE 220

(WK\OWROXHQH 6RUSWLRQ 'DWD &V XJ/f &Z DYJ VWG DPRXQW XJ/f VRUEHG DYJ VWG XJ/f D D D D D Q D ORJ ORJ DPRXQW DPRXQW VROXW LRQ VRUEHG VRUEHG FRQFHQWUDWLRQ QJJf LL LL LL LL LL LL Q LL LL LL LL Q Q LL LL LL Q LL LL LL LL LL

PAGE 221

(WK\OWROXHQH 'HVRUSWLRQ 'DWD DPRXQ W &V XJ/f &Z XJ/f VRUEHG DYJ VWG DYJ VWG XJ/f D D D D Q D ORJ ORJ DPRXQW DPRXQW VROXWLRQ VRUEHG VRUEHG FRQFHQWUDWLRQ QJJf LW Q LL Q LL Q LL LL ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, ,, r

PAGE 222

/22 $02817 625%(' /22 62/87,21 &21&(175$7,21 Â’ 62537,21 R '(62537,21 )UHXQGOLFK VRUSWLRQGHVRUSWLRQ LVRWKHUP IRU (WK\OWROXHQH DW HTXLOLEULXP

PAGE 223

7ULPHWK\OEHQ]HQH 6RUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D D D D DPRXQW VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDWLRQ D Q

PAGE 224

7ULPHWK\OEHQ]HQH 'HVRUSWLRQ 'DWD &V XJ/f DYJ VWG &Z XJ/f DYJ VWG D D D D DPRXQW VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDWLRQ D Q

PAGE 225

/22 $02817 625%(' /2* 62/87,21 &21&(175$7,21 D 62537,21 R '(62537,21 )UHXQGOLFK VRUSWLRQGHVRUSWLRQ LVRWKHUP IRU 7ULPHWK\OEHQ]HQH DW HTXLOLEULXP

PAGE 226

7ULPHWK\OEHQ]HQH 6RUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D D D D DPRXQW VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDWLRQ D Q O

PAGE 227

7ULPHWK\OEHQ]HQH 'HVRUSWLRQ 'DWD &V XJ/f &Z XJ/f DYJ VWG DYJ VWG D D D DPRXQW VRUEHG XJ/f DPRXQW VRUEHG QJJf ORJ DPRXQW VRUEHG ORJ VROXWLRQ FRQFHQWUDW LRQ D Q

PAGE 228

/22 $02817 625%(' /22 62/87,21 &21&(175$7,21 Â’ 62537,21 R '(62537,21 )UHXQGOLFK VRUSWLRQGHVRUSWLRQ LVRWKHUP IRU 7ULPHWK\OEHQ]HQH DW HTXLOLEULXP

PAGE 229

$33(1',; %5($.7+528*+ &859( '$7$ )25 7+( 62537,21 2) 678'< &203281'6 72 /$.( $/)5(' $48,)(5 0$7(5,$/ 7KLV DSSHQGL[ SUHVHQWV WKH EUHDNWKURXJK GDWD IRU WKH DURPDWLF VROXWHV XVHG LQ WKLV VWXG\ 7KH GDWD LV SUHVHQWHG DV FRQFHQWUDWLRQV XJ/f DQG DV &&T HIIOXHQW FRQFHQWUDWLRQ LQIOXHQW FRQFHQWUDWLRQf )ROORZLQJ WKHVH GDWD SORWV RI &&T YV SRUH YROXPHV DUH SUHVHQWHG IRU WKRVH FRPSRXQGV QRW VKRZQ JUDSKLFDOO\ LQ WKH ERG\ RI WKH GLVVHUWDWLRQ 7KH ILQDO SDJH RI WKLV DSSHQGL[ SUHVHQWV WKH GDWD IRU WKH VLQJOH VROXWH EUHDNWKURXJK RI EHQ]HQH

PAGE 230

&ROXPQ 6RUSWLRQ 'DWD / FP Y FPPLQ SY P/ 9DOXHV DUH DV XJ/ P/ %1= 72/ (7+%= PS;
PAGE 231

&ROXPQ 6RUSWLRQ 'DWD / FP Y FPPLQ SY P/ 9DOXHV DUH DV XJ/ L VS%= QS%= (7 70% (7 70% 70%

PAGE 232

&ROXPQ 6RUSWLRQ 'DWD DV &&R 39 %1= 72/ (WK\O %] PS;
PAGE 233

&ROXPQ 6RUSWLRQ 'DWD DV &&R LVS%= QS%= (7 70% ,, 1,, ,, 0 LL LD LL LL Q LL LL 70% 70%

PAGE 234

R 2 ? 2 325( 92/80(6 Â’ &+/25,'( (7+
PAGE 235

R 2 ? R 8 24 $ I +f§%at6f§+ I $a g U -I g I L L L W Le/U 7 325( 92/80(6 D &+/25,'( 03;9/(1( 7a

PAGE 236

R 2 ? 2 325( 92/80(6 Q &+/25,'( 2;9/(1(

PAGE 237

& & R X Y 24 2$ 2I 6 Â’ W n g 3 r % Â’ &+/25,'( 7 7 325( 92/80(6 ,623523
PAGE 238

R 2 ? 2 6 26 RD RV 26 RV 2R g L $ I $ $ \ \ $ n D &+/25,'( 7a 325( 92/80(6 (7 K7/7 2/8( 1(

PAGE 239

R R ? R Â’ &+/25,'( 325( 92/80(6 ,75,0(7+
PAGE 240

& & R 325( 92/80(6 Â’ &+/25,'( (7WU/(2/8(1(

PAGE 241

& & R Â’ &+/25,'( 325( 92/80(6 7 50(7 I7/%(1=(1(

PAGE 242

2 R R ’ &+/25,'( 325( 92/80(6 7 5-. I(7 I/%(1=( 1(

PAGE 243

6LQJOH 6ROXWH %UHDNWKURXJK 'DWD )RU %HQ]HQH / FP 9ROXPH FX FP %XON 'HQVLW\ JFX FP 39 P/ Y FPPLQ %HQ]HQH P/ 39 XJ/f &&R

PAGE 244

$33(1',; ( %$7&+ %,2'(*5$'$7,21 '$7$ 7KLV DSSHQGL[ SUHVHQWV GDWD IURP EDWFK ELRGHJUDGDWLRQ H[SHULPHQWV RQH DQG WZR $OO K\GURFDUERQ FRQFHQWUDWLRQ YDOXHV DUH LQ XQLWV RI XJ/ =HUR YDOXHV LQGLFDWH WKDW WKH FRQFHQWUDWLRQ RI K\GURFDUERQV ZDV EHORZ XJ/ 'LVVROYHG R[\JHP YDOXHV DUH LQ XQLWV RI PJ/

PAGE 245

7UHDWPHQW $ 'D\ %HQ]HQH 7ROXHQH UDS[\O R;\O (7 DYJ VWG bYDU DYJ VWG bYDU DYJ VWG bYDU 70% (7 70% 70% '2 PJ/

PAGE 246

7UHDWPHQW $ 'D\ %HQ]HQH 7ROXHQH P3a[\O R;\O (7 DYJ VWG bYDU DYJ VWG bYDU '2 70% (7 70% 70% PJ/

PAGE 247

7UHDWPHQW ,% 'D\ %HQ]HQH 7ROXHQH DYJ VWG bYDU DYJ VWG bYDU DYJ VWG bYDU ;\O R;\O (7 n @ (7 / 70% 70% '2 PJ/

PAGE 248

7UHDWPHQW ,% 'D\ %HQ]HQH 7ROXHQH UD3[\O R;\O (7 DYJ VWG bYDU DYJ VWG bYDU 70% (7 } 70% 70% '2 PJ/

PAGE 249

7UHDWPHQW & 'D\ %HQ]HQH 7ROXHQH UDS[\O R;\O (7 DYJ VWG bYDU DYJ VWG bYDU DYJ VWG bYDU 70% (7 70% '2 70% PJ/

PAGE 250

7UHDWPHQW & '2 'D\ %HQ]HQH 7ROXHQH P3;\O R;\O (7 70% (7 70% 70% PJ/ DYJ VWG bYDU DYJ VWG bYDU

PAGE 251

7UHDWPHQW ,' 'D\ %HQ]HQH 7ROXHQH DYJ VWG bYDU DYJ VWG bYDU DYJ VWG bYDU f;\O R;\O (7 70% (7 70% 70% '2 PJ/

PAGE 252

7UHDWPHQW ,' '2 'D\ %HQ]HQH 7ROXHQH PS;\O R;\O (7 70% (7 70% 70% PJ/ DYJ VWG bYDU DYJ VWG bYDU

PAGE 253

7UHDWPHQW 'D\ ,( %HQ]HQH 7ROXHQH Q!3;\O R;\O (7 70% (7 70% 70% >'2@ PJ/ DYJ VWG bYDU DYJ VWG bYDU DYJ VWG bYDU

PAGE 254

7UHDWPHQW ,( 'D\ %HQ]HQH 7ROXHQH PS;\O R;\O (7 DYJ VWG bYDU DYJ VWG bYDU 70% (7 70% 70% >'2@ PJ/

PAGE 255

7UHDWPHQW ,) 'D\ %HQ]HQH 7ROXHQH PS;\O R;\O (7 DYJ VWG bYDU DYJ VWG bYDU DYJ VWG bYDU 70% (7 70% 70% >'2@ PJ/

PAGE 256

7UHDWPHQW ,) >'2@ 'D\ %HQ]HQH 7ROXHQH PS;\O R ;\O (7 70% (7 70% 70% PJ/ DYJ VWG bYDU DYJ VWG bYDU

PAGE 257

7UHDWPHQW 'D\ %HQ]HQH 7ROXHQH PS;\O R;\O (7 DYJ VWG bYDU DYJ VWG bYDU DYJ VWG bYDU 70% (7 70% 70% >'2@ PJ/

PAGE 258

7UHDWPHQW 'D\ %HQ]HQH 7ROXHQH PS;\O R;\O (7 DYJ VWG bYDU DYJ VWG bYDU L (7 70% 70% >'2@ PJ/

PAGE 259

75($70(17 $ WUHDWPHQW $ '$< %1= 72/ (7+ %= PS;'2@ DYJ VWG bYDULDQFH WUHDWPHQW $ '$< %1= 72/ (7+ %= PS;'2@ DYJ VWG bYDULDQFH

PAGE 260

7UHDWPHQW $ '$< %1= 72/ (7+ %= PS;'2@ DYJ VWG bYDULDQFH WUHDWPHQW $ '$< %1= 72/ (7+ %= PS;'2@ DYJ VWG bYDULDQFH

PAGE 261

WUHDWPHQW $ '$< %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 262

75($70(17 % '$< %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 263

7UHDWPHQW % '$< %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@ 1!

PAGE 264

7UHDWPHQW % '$< %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 265

75($70(17 & '$< %1= 72/ (7+ %= PS;'2@ DYJ 6WG bYDULDQFH 7UHDWPHQW & '$< %1= 72/ (7+ %= PS;'2@ DYJ VWG bYDULDQFH

PAGE 266

7UHDWPHQW & '$< %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 267

7UHDWPHQW & '$< %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 268

75($70(17 WUHDWPHQW GD\ %1= 72/ (7+ %= PS;'2@ n (7 70% (7 70% 70% >'2@

PAGE 269

WUHDWPHQW GD\ %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 270

WUHDWPHQW GD\ %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 271

WUHDWPHQW ( GD\ %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 272

WUHDWPHQW ( GD\ %1= 72/ (7+ %= PS;'2@ DYJ VWG bYDULDQFH WUHDWPHQW GD\ ( %1= 72/ (7+ %= PS;'2@ DYJ VWG bYDULDQFH

PAGE 273

WUHDWPHQW ( GD\ %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 274

7UHDWPHQW ) WUHDWPHQW ) GD\ %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 275

7UHDWPHQW ( WUHDWPHQW ( GD\ %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 276

WUHDWPHQW ) '$< %1= 72/ (7+ %= PIS;'2@ (7 70% (7 70% 70% >'2@

PAGE 277

WUHDWPHQW ) '$< %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 278

75($70(17 WUHDWPHQW GD\ %1= 72/ (7+ %= PS;'2@ QD (7 70% (7 70% 70% >'2@

PAGE 279

WUHDWPHQW GD\ %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@

PAGE 280

WUHDWPHQW GD\ %1= 72/ (7+ %= PS;'2@ DYJ VWG bYDULDQFH (55 (55 WUHDWPHQW GD\ %1= 72/ (7+ %= PS;'2@ DYJ VWG bYDULDQFH (55

PAGE 281

75($70(17 + WUHDWPHQW + GD\ %1= 72/ (7+ %= PS;'2@ QD (7 70% (7 70% 70% >'2@

PAGE 282

WUHDWPHQW + GD\ %1= 72/ (7+ %= PS;'2@ (7 70% (7 70% 70% >'2@ (55 (55 (55

PAGE 283

WUHDWPHQW + GD\ %1= 72/ (7+ %= PS;'2@ DYJ VWG bYDULDQFH WUHDWPHQW + GD\ %1= 72/ (7+ %= PIS;'2@ DYJ VWG bYDULDQFH

PAGE 284

75($70(17 WUHDWPHQW GD\ %1= 72/ (7+ %= PS;'2@ QD (7 70% (7 70% 70% >'2@

PAGE 285

WUHDWPHQW GD\ %1= 72/ (7+ %= PS;'2@ (55 (55 (7 70% (7 70% 70% >'2@

PAGE 286

WUHDWPHQW GD\ %1= 72/ (7+ %= PS;'2@ (55 (55 (7 70% (7 70% 70% >'2@

PAGE 287

$33(1',; ) &2/801 %5($.7+528*+ '$7$ )25 %,2'(*5$'$7,21 &2/8016 %UHDNWKURXJK GDWD IRU FROXPQV ZLWK IORZ UDWHV RI P/PLQ DQG P/KU DUH SUHVHQWHG LQ WDEXODU IRUP %UHDNWKURXJK FXUYHV IRU HDFK FRPSRXQG IRU WKH P/PLQ FROXPQ DUH SUHVHQWHG IROORZLQJ WKH WDEXODU GDWD

PAGE 288

&ROXPQ %LRGHJUDGDWLRQ 'DWD YDOXHV DV XJ/ &800 0/ %1= 72/ (%= 03; 2; &R / Y FP FPPLQ

PAGE 289

&ROXPQ %LRGHJUDGDWLRQ 'DWD 39 9DOXHV DUH &&R %= 72/ (%= 03; 2; / FP Y FUQPLQ SRUH ZDWHU YHORFLW\ EXON GHQVLW\ SDUWLFOH GHQVLW\ FPGD\ JPO JPO

PAGE 290

/ FP Y FPPLQ SRUH YROXPH 0/ 9DOXHV DUH DV XJ/ &800 0/ %1= 72/ (%= 03; 2;
PAGE 291

9DOXHV DUH DV XJ/ ,63%= 13%= (7 70% (7 70% 70% &R

PAGE 292

&ROXPQ %LRGHJUDGDWLRQ 'DWD 39 &&R %1 = &&R 72/ &&R (%= &&R 03; &&R R;
PAGE 293

&ROXPQ %LRGHJUDGDWLRQ 'DWD &&R ,63%= &&R 13%= &&R (7 &&R 70% &&R (7 &&R 70% &&R 70%

PAGE 294

325( 92/80(6 %UHDNWKURXJK FXUYH IRU EHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 295

R 2 ? 2 325( 92/80(6 %UHDNWKURXJK FXUYH IRU WROXHQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQWV SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 296

325( 92/80(6 %UHDNWKURXJK FXUYH IRU HWK\OEHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PL

PAGE 297

R 2 ? &R $ 325( 92/80(6 %UHDNWKURXJK FXUYH IRU PS[\OHQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 298

2 $ %UHDNWKURXJK FXUYH IRU R[\OHQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 299

R 2 ? 2 Dt 2$ 22%%%(MW 325( 92/80(6 %UHDNWKURXJK FXUYH IRU QSURS\OEHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 300

325( 92/80(6 %UHDNWKURXJK FXUYH IRU QSURS\OEHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 301

325( 92/80(6 %UHDNWKURXJK FXUYH IRU DQG HWK\OWROXHQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 302

325( 92/80(6 %UHDNWKURXJK FXUYH IRU WULPHWK\OEHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 303

R ? M 2$ %UHDNWKURXJK FXUYH IRU HWK\OWROXHQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 304

325( 92/80(6 %UHDNWKURXJK FXUYH IRU WULPHWK\OEHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 305

X R 2 ? 2 2$ f§ 325( 92/80(6 %UHDNWKURXJK FXUYH IRU WULPHWK\OEHQ]HQH LQ FROXPQ ELRGHJUDGDWLRQ H[SHULPHQW SHUIRUPHG DW D IORZ UDWH RI P/PLQ

PAGE 306

$33(1',; +<'52&$5%21 &21&(175$7,216 ,1 021,725,1* :(//6 $7 7+( /$.( $/)5(' &,7586 5(6($5&+ $1' ('8&$7,21 &(17(5 $OO FRQFHQWUDWLRQ YDOXHV DUH LQ XQLWV RI XJ/ %ODQN VSDFHV ZLWKLQ WKH ERG\ RI HDFK WDEOH LQGLFDWH WKDW WKH FRQFHQWUDWLRQ ZDV EHORZ WKH OLPLW RI GHWHFWLRQ R XJ/f RI WKH DQDO\WLFDO V\VWHP )LJXUH VKRZV WKH ORFDWLRQ RI HDFK ZHOO

PAGE 307

:(// 2+0 (0( &$<6 %(1=(1( 7&/8(1( (,+%= 03;
PAGE 308

:(// 2+0 40' &IW<6 %(1=(1( 72/ (,+%= 03;
PAGE 309

:(// 2 (5,( '$<6 %( 7; (,+%= 03;63%= Q)%= (7 70 (7 70% 70 D

PAGE 310

:(// 2+0 (0( &06 %(1=(1( 72/8(1( (,+%= 03;
PAGE 311

:(// 3 (0( '06 ((1= 7&/ HWK%] PS;g/ R;
PAGE 312

:(// 3 '27( '276 %(1=(0 7; (,+(1= 03;
PAGE 313

:(// 3 (0( ,06 (66( 7&/ (,+(1= 03;
PAGE 314

:(// 5$3 &$7( '06 %6( 7&/ (,+%= 03;
PAGE 315

:(// 5$3 &$7( '0 (1= 7&/ (WK%= PS;
PAGE 316

:(// 5$3 &$7( &$<6 %(,n((1( 72-8(1( (,+(W( PS;
PAGE 317

:(// 5$3 '$,( &$76 %( 7&/ (WK%= PS;
PAGE 318

:(// 8)( &$7( 2:6 %Q] 7W!O (WK%] PS;\O LVR)%= Q3%= (7 7)% (7 ,70% 7&% O

PAGE 319

:(// 8)0 (0( (06 %HQ]HQH 7ROXHQH (WUWR] PS;\O R;\O b b LVR3%= Q3%= (7 70 (7 0 7k b b

PAGE 320

&$7( &$<6 %HQ]HUH 7EOXVUH (WE%= PS;
PAGE 321

5()(5(1&(6 $EGXO $6 7& *LEVRQ DQG '1 5DL f 7KH (IIHFW RI 2UJDQLF &DUERQ RQ WKH $GVRUSWLRQ RI )OXRUHQH E\ $TXLIHU 0DWHULDOV +D]DUGRXV :DVWH DQG +D]DUGRXV 0DWHULDOV f $OH[DQGHU 0 f %LRGHJUDGDWLRQ RI 2UJDQLF &KHPLFDOV (QYLURQ 6FL 7HFKQRO f $QGHUVRQ 03 f 8VLQJ 0RGHOV WR 6LPXODWH WKH 0RYHPHQW RI &RQWDPLQDQWV WKURXJK *URXQGZDWHU )ORZ 6\VWHPV ,Q &5& &ULWLFDO 5HYLHZV LQ (QYLURQPHQWDO &RQWURO %RFD 5DWRQ )/ &5& 3UHVV SS \ $WODV 50 f (QXPHUDWLRQ DQG (VWLPDWLRQ RI 0LFURELDO %LRPDVV ,Q ([SHULPHQWDO 0LFURELDO (FRORJ\ 5, %XUQV DQG +6ODWHU HGVf %RVWRQ 0$7 %ODFNZHOO 6FLHQWLILF &R SS %DLOH\ *: DQG -/ :KLWH f )DFWRUV ,QIOXHQFLQJ WKH $GVRUSWLRQ 'HVRUSWLRQ DQG 0RYHPHQW RI 3HVWLFLGHV LQ 6RLO 5HVLGXH 5HYLHZ %DUEDVK DQG 39 5REHUWV f 9RODWLOH 2UJDQLF &KHPLFDO &RQWDPLQDWLRQ RI *URXQGZDWHU 5HVRXUFHV LQ WKH 86 -RXUQDO :DWHU 3ROOXWLRQ &RQWURO )HGHUDWLRQ f %DUNHU -) DQG *& 3DWULFN f 1DWXUDO $WWHQXDWLRQ RI $URPDWLF +\GURFDUERQV LQ D 6KDOORZ 6DQG $TXLIHU ,Q 3URFHHGLQJV RI 1::$$3, &RQIHUHQFH RQ 3HWUROHXP +\GURFDUERQV DQG 2UJDQLF &KHPLFDOV LQ *URXQG :DWHU +RXVWRQ 7; 1DWLRQDO :DWHU :HOO $VVRF SS %HDU f +\GUDXOLFV RI *URXQGZDWHU 1HZ
PAGE 322

%HGLHQW 3% 5& %RUGHQ DQG ', /HLE f %DVLF &RQFHSWV IRU *URXQG :DWHU 7UDQVSRUW 0RGHOLQJ ,Q *URXQG :DWHU 4XDOLW\ &+ :DUG : *LJHU DQG 3/ 0F&DUW\ HGVf 1HZ
PAGE 323

%URRNPDQ *7 0 )ODQDJDQ DQG -2 .HEH f /LWHUDWXUH 6XUYH\ +\GURFDUERQ 6ROXELOLWLHV DQG $WWHQXDWLRQ 0HFKDQLVPV :DVKLQJWRQ '& $PHULFDQ 3HWUROHXP ,QVWLWXWH 3XEOLFDWLRQ 1R %URZQ += '5 %LVKRS DQG &$ 5RZDQ f 7KH 5ROH RI 6NLQ $EVRUSWLRQ DV D 5RXWH RI ([SRVXUH IRU 9RODWLOH 2UJDQLF &RPSRXQGV 92&Vf LQ 'ULQNLQJ :DWHU $PHULFDQ -RXUQDO RI 3XEOLF +HDOWK f &DUULQJHU 5' -% :HEHU DQG 70RQDFR f $GVRUSWLRQ'HVRUSWLRQ RI 6HOHFWHG 3HVWLFLGHV E\ 2UJDQLF 0DWWHU DQG 0RQWPRUL,RQLWH $JULH )RRG &KHP f &KLRX &7 /3HWHUV DQG 9+ )UHHG f $ 3K\VLFDO &RQFHSW RI 6RLO:DWHU (TXLOLEULD IRU 1RQLRQLF 2UJDQLF &RPSRXQGV 6FLHQFH &KLRX &7 3( 3RUWHU DQG ': 6FKPHGGLQJ f 3DUWLWLRQ (TXLOLEULD RI 1RQLRQLF 2UJDQLF &RPSRXQGV %HWZHHQ 2UJDQLF 0DWWHU DQG :DWHU (QYLURQ 6FL 7HFKQRO &ROHPDQ :( -: 0XQFK -3 6WUHLFKHU +3 5LQJKDQG DQG )& .RSIOHU f 7KH ,GHQWLILFDWLRQ DQG 0HDVXUHPHQW RI &RPSRQHQWV LQ *DVROLQH .HURVHQH DQG 1R )XHO 2LO WKDW 3DUWLWLRQ LQWR WKH $TXHRXV 3KDVH DIWHU 0L[LQJ $UFK (QYLURQ &RQWDP 7R[LFRO &5& +DQGERRN RI &KHPLVWU\ DQG 3K\VLFV f %RFD 5DWRQ ), &5& 3UHVV ,QF &XUWLV *3 39 5REHUWV DQG 0 5HLQKDUG f $ 1DWXUDO *UDGLHQW ([SHULPHQW RQ 6ROXWH 7UDQVSRUW LQ D 6DQG $TXLIHU ,9 6RUSWLRQ RI 2UJDQLF 6ROXWHV DQG LWV ,QIOXHQFH RQ 0RELOLW\ XQSXEOLVKHG 'DJOH\ 6 f $ %LRFKHPLFDO $SSURDFK WR 6RPH 3UREOHPV RI (QYLURQPHQWDO 3ROOXWLRQ ,Q (VVD\V LQ %LRFKHPLVWU\ 31 &DPSEHOO DQG :1 $GOULGJH HGVf 1HZ
PAGE 324

'DYLGVRQ -0 36& 5DR DQG 3 1NHGL.L]]D f 3K\VLFDO 3URFHVVHV ,QIOXHQFLQJ :DWHU DQG 6ROXWH 7UDQVSRUW LQ 6RLOV ,Q &KHPLFDO 0RELOLW\ DQG 5HDFWLYLW\ LQ 6RLO 6\VWHPV 0DGLVRQ :LVFRQVLQ 6RLO 6FLHQFH 6RFLHW\ RI $PHULFD SS 'HOILQR -DQG &0LOHV f $HURELF DQG $QDHURELF 'HJUDGDWLRQ RI 2UJDQLF &RQWDPLQDQWV LQ )ORULGD *URXQGZDWHU 6RLO t &URS 6FL 6RF )OD 3URF 'L7RUR '0 DQG /0 +RU]HPSD f 5HYHUVLEOH DQG 5HVLVWDQW &RPSRQHQWV RI 3&% $GVRUSWLRQ'HVRUSWLRQ ,VRWKHUPV (QYLURQ 6FL 7HFKQROA f 'RZG 50 f /HDNLQJ 8QGHUJRXQG 6WRUDJH 7DQNV (QYLURQ 6FL 7HFKQRO f 'XSRQW f +\GURJHQ 3HUR[LGH 6ROXWLRQ 6WRUDJH DQG +DQGOLQJ :LOPLQJWRQ '( (, 'XSRQW GH 1HPRXUV t &R SS ( (YDQV :& f %LRFKHPLVWU\ RI WKH %DFWHULDO &DWDEROLVP RI $URPDWLF &RPSRXQGV LQ $QDHURELF (QYLURQPHQWV 1DWXUH )HUQDOG ($ DQG '3DWWRQ f :DWHU 5HVRXUFHV $WODV RI )ORULGD 7DOODKDVVHH )/ ,QVWLWXWH RI 6FLHQFH DQG 3XEOLF $IIDLUV )ORULGD 6WDWH 8QLYHUVLW\ )HWWHU *: f $SSOLHG +\GURJHRORJ\ &ROXPEXV 2+ &KDUOHV ( 0HUULOO &R )/'(5 f )ORULGD 6LWHV /LVW 3HWUROHXP &RQWDPLQDWLRQ ,QFLGHQWVA 7DOODKDVVHH )/ 'HSW RI (QYLURQPHQWDO 5HJXODWLRQ )UHH]H 5$ DQG -$ &KHUU\ f *URXQGZDWHU (QJOHZRRG &OLIIV 13UHQWLFH+DOO ,QF *KLRUVH :& DQG '/ %DONZLOO f (QXPHUDWLRQ DQG 0RUSKRORJLFDO &KDUDFWHUL]DWLRQ RI %DFWHULD ,QGLJHQRXV WR 6XEVXUIDFH (QYLURQPHQWV 'HY ,QG 0LFURE

PAGE 325

*KLRUVH :& DQG '/ %DONZLOO f 0LFURELRORJLFDO &KDUDFWHUL]DWLRQ RI 6XEVXUIDFH (QYLURQPHQWV ,Q *URXQG :DWHU 4XDOLW\ &+ :DUG : *LJHU DQG 3/ 0F&DUW\ HGVf 1HZ
PAGE 326

.DULFNKRII 6: '6 %URZQ DQG 7$ 6FRWW f 6RUSWLRQ RI +\GURSKRELF 3ROOXWDQWV RQ 1DWXUDO 6HGLPHQWV :DWHU 5HVHDUFK .HQDJD (( DQG &$ *RULQJ f 5HODWLRQVKLS EHWZHHQ :DWHU 6ROXELOLW\ 6RLO 6RUSWLRQ 2FWDQRO:DWHU 3DUWLWLRQLQJ DQG %LRFRQFHQWUDWLRQ RI &KHPLFDOV LQ %LRWD ,Q $TXDWLF 7R[LFRORJ\ -* (DWRQ 35 3DULVK DQG $& +HQGULFNV HGVf 1HZ
PAGE 327

/LWFKILHOG & f $Q 2YHUYLHZ RI 7KH ,Q 6LWX %LRUHFODPDWLRQ RI *URXQG :DWHU 3ULQFLSOHV 3UDFWLFHV DQG 3RWHQWLDO 1HZDUN 'O (, GXSRQW GH 1HPRXUV DQG &RPSDQ\ /LWFKILHOG & DQG / &ODUN f %DFWHULDO $FWLYLW\ LQ *URXQG :DWHUV &RQWDLQLQJ 3HWUROHXP 3URGXFWV :DVKLQJWRQ '& $PHULFDQ 3HWUROHXP ,QVWLWXWH 0DF.D\ '0 39 5REHUWV DQG -$ &KHUU\ f 7UDQVSRUW RI 2UTDQLF &RQWDPLQDQWV LQ *URXQGZDWHU (QYLURQ 6FL 7HFKQRO f 0F&DUW\ 3/ f $SSOLFDWLRQ RI %LRORJLFDO 7UDQVIRUPDWLRQ LQ *URXQG :DWHU 3URFHHGLQJV RI 6HFRQG ,QWHUQDWLRQDO &RQIHUHQFH RQ *URXQG :DWHU 4XDOLW\ 5HVHDUFK 0DUFK 7XOVD 2. :RUWKLQJWRQ 2+ 1DWLRQDO :HOO :DWHU $VVRFLDWLRQ 0F.HH -( )% /DYHUW\ DQG 50 +HUWHO f *DVROLQH LQ *URXQGZDWHU -RXUQDO :DWHU 3ROOXWLRQ &RQWURO )HGHUDWLRQ 0F.HQQD (DQG 5' +HDWK f %LRGHJUDGDWLRQ RI 3RO\QXFOHDU $URPDWLF +\GURFDUERQ 3ROOXWDQWV E\ 6RLO DQG :DWHU 0LFURRUJDQLVPV 8QLYHUVLW\ RI ,OOLQRLV &KDPSDLJQ 8UEDQD 5HVHDUFK 5HSRUW 1R 0HDQV -& 6* :RRG -+DVVHWW DQG :/ %DQZDUW f 6RUSWLRQ RI $PLQRDQG &DUER[\6XEVWLWXWHG $URPDWLF +\GURFDUERQV E\ 6HGLPHQWV DQG 6RLOV (QYLURQ 6FL 7HFKQRO 0LOJHOJULQ 8 DQG = *HUVWO f 5HHYDOXDWLRQ RI 3DUWLWLRQLQJ DV D 0HFKDQLVP RI 1RQLRQLF &KHPLFDOV $GVRUSWLRQ LQ 6RLOV (QYLURQ 4XDO f 0LOOHU &7 DQG ::HEHU f 0RGHOLQJ 2UJDQLF &RQWDPLQDQW 3DUWLWLRQLQJ LQ *URXQG:DWHU 6\VWHPV *URXQG :DWHU 0LWFKHOO 5 f ,QWURGXFWLRQ WR (QYLURQPHQWDO 0LFURELRORJ\ (QJOHZRRG &OLIIV 13UHQWLFH+DOO ,QF

PAGE 328

0RRUH -: DQG ($ 0RRUH f (QYLURQPHQWDO &KHPLVWU\ 1HZ
PAGE 329

5DR 36& $* +RUQVE\ '3 .LOFUHDVH DQG 3 1NHGL.L]]D f 6RUSWLRQ DQG 7UDQVSRUW RI +\GURSKRELF 2UJDQLF &KHPLFDOV LQ $TXHRXV DQG 0L[HG 6ROYHQW 6\VWHPV 0RGHO 'HYHORSPHQW DQG 3UHOLPLQDU\ (YDOXDWLRQ (QYLURQ 4XDO 5DR 36& DQG 5( -HVVXS f 6RUSWLRQ DQG 0RYHPHQW RI 3HVWLFLGHV DQG 2WKHU 7R[LF 2UJDQLF 6XEVWDQFHV LQ 6RLOV ,Q &KHPLFDO 0RELOLW\ DQG 5HDFWLYLW\ LQ 6RLO 6\VWHPV 0DGLVRQ :, 6RLO 6FLHQFH 6RF RI $PHULFD S, &K 75D\PRQG 5/ 9: -DPLVRQ DQG -2 +XGVRQ Df %HQHILFLDO 6WLPXODWLRQ RI %DFWHULDO $FWLYLW\ LQ *URXQGZDWHUV &RQWDLQLQJ 3HWUROHXP 3URGXFWV $,&K( 6\PSRVLXP 6HULHV SS 5D\PRQG 5/ 9: -DPLVRQ DQG -2 +XGVRQ Ef )LQDO 5HSRUW RQ %HQHILFLDO 6WLPXODWLRQ RI %DFWHULDO $FWLYLW\ LQ *URXQGZDWHUV &RQWDLQLQJ 3HWUROHXP 3URGXFWV :DVKLQJWRQ '& $PHULFDQ 3HWUROHXP ,QVWLWXWH $3, 3URMHFW 26 5D\PRQG 5/ 9: -DPLVRQ DQG -2 +XGVRQ f %DFWHULDO *URZWK LQ DQG 3HQHWUDWLRQ RI &RQVROLGDWHG DQG 8QFRQVROLGDWHG 6DQGV &RQWDLQLQJ *DVROLQH :DVKLQJWRQ '& $PHULFDQ 3HWUROHXP ,QVWLWXWH $3, 3URMHFW 5REHUWV 39 0 5HLQKDUG *' +RSNLQV DQG 56 6XPPHUV f $GYHFWLRQ'LVSHUVLRQ6RUSWLRQ 0RGHOV IRU 6LPXODWLQJ WKH 7UDQVSRUW RI 2UJDQLF &RQWDPLQDQWV ,Q *URXQG :DWHU 4XDOLW\ &+ :DUG : *LJHU DQG 3/ 0F&DUW\ HGVf 1HZ
PAGE 330

6DEOML& $ f 2Q WKH 3UHGLFWLRQ RI 6RLO 6RUSWLRQ &RHIILFLHQWV RI 2UJDQLF 3ROOXWDQWV IURP 0ROHFXODU 6WUXFWXUH $SSOLFDWLRQ RI 0ROHFXODU 7RSRORJ\ 0RGHO (QYLURQ 6FL 7HFKQRO f 6DQGHUV :1 DQG -% 0D\QDUG f &DSLOODU\ *DV &KURPDWRJUDSKLF 0HWKRG IRU 'HWHUPLQLQJ WKH && +\GURFDUERQV LQ )XOO 5DQJH 0RWRU *DVROLQHV $QDO &KHP f 6FKZDU]HQEDFK 53 : *LJHU ( +RHKQ DQG -. 6FKQHLGHU f %HKDYLRU RI 2UJDQLF &RPSRXQGV 'XULQJ ,QILOWUDWLRQ RI 5LYHU :DWHU WR *URXQGZDWHU )LHOG 6WXGLHV (QYLURQ 6FL 7HFKQRO 6FKZDU]HQEDFK 53 DQG :HVWDOO f 7UDQVSRUW RI 1RQSRODU 2UJDQLF &RPSRXQGV IURP 6XUIDFH :DWHU WR *URXQG :DWHU (QYLURQ 6FL 7HFKQRO 6KHKDWD $ f $ 0XOWL5RXWH ([SRVXUH $VVHVVPHQW WR &KHPLFDOO\ &RQWDPLQDWHG 'ULQNLQJ :DWHU DQG +HDOWK 6LJQLILFDQFH ZLWK (PSKDVLV RQ *DVROLQH $XJXVWD 0( 0DLQH 'HSW RI +XPDQ 6HUYLFHV 6PLWK / DQG ): 6FKZDUW] f 0DVV 7UDQVSRUW $ 6WRFKDVWLF $QDO\VLV RI 0DFURVFRSLF 'LVSHUVLRQ :DWHU 5HVRXU 5HV 6SDQJOHU f +\GURJHRORJLF 6WXG\ RI 8QLYHUVLW\ RI )ORULGD $JULFXOWXUDO 5HVHDUFK DQG (GXFDWLRQ &HQWHU /DNH $OIUHG )ORULGD XQSXEOLVKHG UHSRUW 6WDQGDUG 0HWKRGV IRU WKH ([DPLQDWLRQ RI :DWHU DQG :DVWHZDWHU WK (GLWLRQ f :DVKLQJWRQ '& $PHULFDQ 3XEOLF +HDOWK $VVRF 6ZRNRZVNL ($ f &DOFXOXV :LWK $QDO\WLFDO *HRPHWU\ %RVWRQ 3ULQGOH :HEHU DQG 6FKPLGW S 7KRPDV +$ f *UDSKLFDO 'HWHUPLQDWLRQ RI %2' &XUYH &RQVWDQWV :DWHU DQG 6HZDJH :RUNV

PAGE 331

7UHYRUV -7 f (IIHFW RI 3HQWDFKORURSKHQRO RQ (OHFWURQ 7UDQVSRUW 6\VWHP $FWLYLW\ LQ 6RLO %XOO (QYLURQ &RQWDP 7R[LFRO 7UHYRUV -7 &, 0D\ILHOG DQG :( ,QQLVV f 0HDVXUHPHQW RI (OHFWURQ 7UDQVSRUW 6\VWHP (76f $FWLYLW\ LQ 6RLO 0LFURE (FRORJ\ 75, f (QKDQFLQJ WKH 0LFURELDO 'HJUDGDWLRQ RI 8QGHUJURXQG *DVROLQH E\ ,QFUHDVLQJ WKH $YDLODEOH 2[\JHQ $XVWLQ 7; 7H[DV 5HVHDUFK ,QVWLWXWH 863+6 f 6HFRQG $QQXDO 5HSRUW RQ &DUFLQRJHQV 5HVHDUFK 7ULDQJOH 3DUN 1& 8QLWHG 6WDWHV 3XEOLF +HDOWK 6HUYLFH 9DQ *HQXFKWHQ 07 DQG -& 3DUNHU f %RXQGDU\ &RQGLWLRQV IRU 'LVSODFHPHQW ([SHULPHQWV WKURXJK 6KRUW /DERUDWRU\ 6RLO &ROXPQV 6RLO 6FL 6RF $P 9RLFH 7& DQG ::HEHU f 6RUSWLRQ RI +\GURSKRELF &RPSRXQGV E\ 6HGLPHQWV 6RLOV DQG 6XVSHQGHG 6ROLGV 7KHRU\ DQG %DFNJURXQG :DWHU 5HVHDUFK :DNVPDQ 6$ f %DFWHULDO 1XPEHUV LQ 6RLO DW 'LIIHUHQW 'HSWKV DQG LQ 'LIIHUHQW 6HDVRQV RI WKH
PAGE 332

:LOVRQ %+ DQG -) 5HHV f %LRWUDQVIRUPDWLRQ RI *DVROLQH +\GURFDUERQV LQ 0HWKDQRJHQLF $TXLIHU 0DWHULDO ,Q 3URFHHGLQJV RI 1::$$3, &RQIHUHQFH RQ 3HWUROHXP +\GURFDUERQV DQG 2UJDQLF &KHPLFDOV LQ *URXQG :DWHU +RXVWRQ 7; :RUWKLQJWRQ 2+ 1DWLRQDO :DWHU :HOO $VVRF SS :LOVRQ -7 &* (QILHOG :'XQODS 5/ &URVE\ '$ )RVWHU DQG /% %DVNLQ f 7UDQVSRUW DQG )DWH RI 6HOHFWHG 2UJDQLF 3ROOXWDQWV LQ D 6DQG\ 6RLO (QYLURQ 4XDLO :LOVRQ -7 /( /HDFK 0 +HQVRQ DQG -1 -RQHV f ,Q 6LWX %LRUHVWRUDWLRQ DV D *URXQG :DWHU 5HPHGLDWLRQ 7HFKQLTXH *URXQG :DWHU 0RQLWRULQJ 5HYLHZ f :LOVRQ -7 DQG -) 0F1DEE f %LRORJLFDO 7UDQVIRUPDWLRQ RI 2UJDQLF 3ROOXWDQWV LQ *URXQGZDWHU (26 f :LOVRQ -7 -) 0F1DEE '/ %DONZLOO DQG :& *KLRU]H Df (QXPHUDWLRQ DQG &KDUDFWHUL]DWLRQ RI %DFWHULD ,QGLJHQRXV WR D 6KDOORZ :DWHU 7DEOH $TXLIHU *URXQG :DWHU :LOVRQ -7 -) 0F1DEE -: &RFKUDQ 7+ :DQJ 0% 7RPVRQ DQG 3% %HGLHQW Ef $GDSWLRQ RI *URXQG :DWHU 0LFURRUJDQLVPV DW D &UHRVRWH :DVWH 'LVSRVDO 6LWH 3UHVHQWHG %HIRUH WKH 'LYLVLRQ RI (QYLURQPHQWDO &KHPLVWU\ :DVKLQJWRQ '& $PHULFDQ &KHPLFDO 6RFLHW\ :LOVRQ 6% f ,Q 6LWX %LRVXUIDFWDQW 3URGXFWLRQ $Q $LG WR WKH %LRGHJUDGDWLRQ RI 2UJDQLF *URXQG :DWHU &RQWDPLQDQWV ,Q 3URFHHGLQJV RI 7KH 3HWUROHXP +\GURFDUERQV DQG 2UJDQLF &KHPLFDOV LQ *URXQG :DWHU 3UHYHQWLRQ 'HWHFWLRQ DQG 5HVWRUDWLRQ +RXVWRQ 7; :RUWKLQJWRQ 2+ 1DWLRQDO :DWHU :HOO $VVRF SSn

PAGE 333

:LQGKRO] 0 f 7KH 0HUFN ,QGH[ WK (GLWLRQ 5DKZD\ 10HUFN &R :RRGEXUQ f 7KHUPRG\QDPLFV DQG 0HFKDQVLPV RI 6RUSWLRQ IRU +\GURSKRELF 2UJDQLF &RPSRXQGV RQ 1DWXUDO DQG $UWLILFLDO 6RUEHQW 0DWHULDOV 3K' 'LVVHUWDWLRQ 8QLYHUVLW\ RI )ORULGD

PAGE 334

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

PAGE 335

, FHUWLI\ WKDW RSLQLRQ LW FRQIRUPV SUHVHQWDWLRQ DQG LV D GLVVHUWDWLRQ IRU FHUWLI\ WKDW RSLQLRQ LW FRQIRUPV SUHVHQWDWLRQ DQG LV D GLVVHUWDWLRQ IRU FHUWLI\ WKDW RSLQLRQ LW FRQIRUPV SUHVHQWDWLRQ DQG LV D GLVVHUWDWLRQ IRU FHUWLI\ WKDW RSLQLRQ LW FRQIRUPV SUHVHQWDWLRQ DQG LV D GLVVHUWDWLRQ IRU KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ n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

PAGE 336

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


u
o
O
\
O
1 -
0.9 -
OA3 -
0.7 -
0.6 -
05 -
0.4 -
05 -
05 -
0J -
0
0 2 4 6
PORE VOLUMES
Breakthrough curve for 1,2,3-trimethylbenzene in column
biodegradation experiment performed at a flow rate of 1 mL/min.
290


TREATMENT #2H
treatment #2H
day 0
BNZ
TOL
ETH BZ m,p-XYL
o-XYL
237
460
2006
1303
230
397
80
1367
1017
193
386
123
1348
1044
avg
220
414
102
1574
1121
std
19
33
21
306
129
%variance
9
8
21
19
11
treatment #2H
day 2
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
136
56
0
4
628
181
164
0
184
809
193
181
0
151
826
avg
170
134
0
113
754
std
25
55
0
78
90
%variance
14
41
ERR
69
12
3,4ET
135TMB
2ET
12 4 TMB
123TMB
[DO]
432
181
170
773
333
20.00
433
161
198
583
363
523
181
231
617
396
463
174
200
658
364
20.00
43
9
25
83
26
0.00
9
5
12
13
7
n/a
3,4ET
135TMB
2ET
124TMB
12 3 TMB
[DO]
23
55
66
1
152
4.20
72
92
95
41
218
8.00
69
92
94
26
217
7.00
55
80
85
23
196
6.40
22
17
13
16
31
1.61
41
22
16
73
16
25.13
266


Figure 4-1. Site plan of the field research site at the Citrus Research and
Education Center, Lake Alfred, FL. w
cn


123
solutes. The main feature of these plots is the eight day
lag phase in the removal of benzene, toluene and o-xylene.
However, with time, degradation of these compounds was
essentially complete. The compounds also displayed a
lag up to eight days in length. The half lives were
slightly increased over treatment 1A, indicating the time
involved in the adaption of the microorganisms to the
hydrogen peroxide.
5.9.3 Treatment 1C
The effects of increasing the concentration of to
68 mg/L was
shown in t
his treatment.
There was
no apparent
increase in
toxicity over the 17 mg/L
treatment.
Ben zene,
toluene and
m,p-xylene
were completel
y removed.
Again,
1,2,4-trimethylbenzene
exhibited the
most rapid
degradation
of the CgH12
compounds
. The initial
DO in these
microcosms
was 10.5 mg/L. The increased half lives of the study
compounds reflect the adaptation to hydrogen peroxide noted
in treatment 2B. Dissolved oxygen concentrations are shown
in Figure 5-15.
5.9.4 Treatment ID
Ammonium chloride (18mg/L) was added to these vials.
This concentration was chosen based on the calculated amount
of nitrogen required to completely degrade the aromatic
solutes assuming a C:N ratio of 10:1. The initial DO
concentration was 9 mg/L. Oxygen consumption appeared rapid
but fell after seven days. Addition of ammonium chloride
significantly reduced the rate of microbial degradation of


treatment #2E
day 7
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
710
3490
46
2651
1510
426
159
152
573
260
5.10
613
3031
38
2369
1288
393
143
135
528
227
5.10
642
3216
41
2493
1390
417
159
149
562
254
3.70
avg
655
3246
42
2504
1396
412
154
145
554
247
4.63
std
41
189
3
115
91
14
8
7
19
14
0.66
%variance
6
6
8
5
6
3
5
5
3
6
14.24
treatment
day 14
#2E
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
782
3296
44
2552
1441
423
158
151
592
250
6.00
760
2918
40
2148
1249
355
132
130
478
224
4.90
652
3140
22
2238
1290
215
139
131
462
224
5.20
avg
731
3118
35
2313
1327
331
143
137
511
233
5.37
std
57
155
10
173
83
87
11
10
58
12
0.46
%variance
8
5
27
7
6
26
8
7
11
5
8.65
257


216
Column Sorption Data
L = 5 cm
v = 0.204 cm/min
pv = 6.9 mL
Values are as ug/L
i spBZ
npBZ
3,4 ET 135 TMB
2 ET
12 4 TMB
12 3 TMB
2
1
4
0
2
2
2
1
1
3
0
2
1
3
2
2
4
1
5
1
2
5
2
7
2
9
4
12
34
7
38
11
47
23
72
90
22
101
33
113
61
168
189
53
225
72
218
127
309
271
85
359
112
314
188
431
337
117
462
145
380
236
511
509
198
695
229
542
357
721
571
226
784
257
594
395
767
616
254
838
282
637
431
821
661
276
926
306
695
461
893
706
302
990
331
730
499
941
767
337
1109
368
799
555
1030
845
370
1164
398
854
589
1085
876
404
1281
431
894
636
1136
922
420
1291
442
917
646
1152
925
423
1306
448
932
654
1179
937
439
1404
461
960
683
1224
883
406
1270
435
909
642
1173
1072
511
1561
532
1079
773
1350
1229
579
1774
617
1270
907
1618
1127
523
1586
562
1156
822
1478
1233
581
1743
617
1258
897
1596
1125
534
1662
580
1196
859
1552
1121
539
1639
579
1178
845
1513


LOO AMOUNT SORBED
LOO SOLUTION CONCENTRATION
SORPTION o DESOfPTION
Freundlich sorption-desorption isotherm for 3,4-Ethyltoluene
at equilibrium.
201


Treatment IB
Day
Benzene Toluene
0
664
1971
623
1605
615
1631
avg
634
1735
std
22
167
%var
3
10
3
881
1959
567
1219
559
866
avg
669
1348
std
150
456
%var
22
34
7
723
1613
639
1219
avg
681
1416
std
42
197
%var
6
14
-Xyl
o-Xyl
3,4 ET
3962
2369
701
3266
1934
623
3417
2030
653
3548
2111
659
299
187
32
8
9
5
2951
2202
601
1310
1274
' 309
565
1668
129
1609
1715
346
997
381
194
62
22
56
2281
2134
473
1373
2087
347
1827
2111
410
454
23
63
25
1
15
,5
5
]
2 ET
L,2,4 1
TMB
,2,3
TMB
DO
mg/L
289
253
1447
604
8.8
261
232
1027
468
9.1
258
239
892
408
9.2
269
241
1122
493
9.0
14
9
237
82
0.2
5
4
21
17
1.9
269
239
692
402
1.5
143
136
296
229
202
188
177
290
1.5
205
188
388
307
1.5
51
42
220
72
0.0
25
22
57
23
0.0
228
205
469
365
2.6
219
226
260
358
1.6
224
216
365
362
2.1
4
11
105
3
0.5
2
5
29
1
23.8
232


176
11. Addition of air or oxygen gas was the most
effective method for stimulating microbial degradation of
the solutes in this study.
12. Hydrogen peroxide was effective in increasing the
dissolved oxygen level in the microcosms.
13. Hydrogen peroxide addition to the microcosms did
not increase the rate or extent of aromatic hydrocarbon
removal.
14. Ammonium chloride addition to the microcosms caused
nitrification, resulting in oxygen consumption in the
microcosms without hydrocarbon removal.
15. The combination of ammonium chloride (18 mg/L) and
hydrogen peroxide (17 mg/L) additions to biodegradation
microcosms produced toxic conditions.
16. Column biodegradation studies yielded higher rate
constants than the batch studies, reflecting improved
transport of nutrients and oxygen to bacteria.
17. Rates of biodegradation for aromatic compounds were
in the order C0 > Cn > C_ > Qr. Benzene was the most
9 8 7 6
recalcitrant solute in the column studies.
18. Benzene, toluene, m,p-xylene and 1,2,4-
trimethylbenzene showed the most rapid biodegradation in the
batch studies.
19. Microbial communities in the Lake Alfred aquifer
5 6
were in the range of 10 -10 colony forming units per gram
dry weight of aquifer material.


277
Column Biodegradation Data
PV
C/Co
BN Z
C/Co
TOL
C/Co
EBZ
C/Co
MPX
C/Co
o-XYL
0.256
0.000
0.001
0.000
0.001
0.001
0.545
0.000
0.002
0.000
0.001
0.001
0.689
0.000
0.003
0.000
0.001
0.001
0.836
0.011
0.005
0.001
0.001
0.002
0.980
0.093
0.043
0.011
0.011
0.018
1.124
0.269
0.139
0.050
0.051
0.075
1.268
0.446
0.269
0.135
0.120
0.173
1.412
0.621
0.414
0.248
0.226
0.291
1.556
0.694
0.480
0.316
0.292
0.359
1.700
0.764
0.542
0.376
0.348
0.417
1.988
0.841
0.608
0.442
0.418
0.477
2.277
0.872
0.647
0.479
0.455
0.509
2.421
0.880
0.645
0.478
0.459
0.515
2.565
0.926
0.681
0.506
0.481
0.540
2.709
0.883
0.671
0.516
0.496
0.546
2.853
1.005
0.731
0.536
0.512
0.568
2.997
0.955
0.736
0.561
0.547
0.582
3.141
0.860
0.663
0.508
0.486
0.534
3.285
0.915
0.688
0.517
0.495
0.540
3.718
0.933
0.718
0.548
0.524
0.573
3.862
0.928
0.711
0.539
0.520
0.563
4.006
0.877
0.660
0.492
0.471
0.530
4.150
0.926
0.703
0.534
0.510
0.559
4.294
0.908
0.721
0.566
0.548
0.591
4.438
0.875
0.632
0.441
0.430
0.489
4.582
0.946
0.751
0.587
0.570
0.610
4.726
0.916
0.722
0.565
0.542
0.583
4.870
0.929
0.740
0.581
0.561
0.599
5.014
0.983
0.783
0.618
0.591
0.635


treatment #2F
DAY 7
BNZ
TOL
ETH BZ
mfp-XYL
o-XYL
600
2946
26
2536
1388
687
3294
27
2834
1519
428
2374
19
2000
1133
avg
572
2871
24
2457
1347
std
108
379
4
345
160
%variance
19
13
16
14
12
treatment #2F
DAY 14
BNZ
TOL ETH BZ m,p-XYL
o-XYL
701
3320
30
2651
1502
776
3713
34
2968
1666
730
3578
36
2998
1667
avg
736
3537
33
2872
1612
std
31
163
2
157
78
%variance
4
5
7
5
5
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
457
156
146
600
261
8.00
508
186
168
680
290
8.60
385
138
127
498
237
8.10
450
160
147
593
263
8.23
50
20
17
74
22
0.26
11
12
11
13
8
3.19
3,4ET
135TMB
2ET
124TMB
12 3 TMB
[DO]
436
167
160
596
279
7.90
498
184
173
663
289
8.10
515
196
179
702
302
7.20
483
182
171
654
290
7.73
34
12
8
44
9
0.39
7
7
5
7
3
4.99
261


APPENDIX F
COLUMN BREAKTHROUGH DATA FOR
BIODEGRADATION COLUMNS
Breakthrough data for columns with flow rates of
1 mL/min and 0.9 mL/hr are presented in tabular form.
Breakthrough curves for each compound for the 1 mL/min
column are presented following the tabular data.
272


o
O
\
O
1S -
1J -
1
0.9 -
OS -
0.7 -
o.a -
os
0.4 -|
OS
os -|
OJ
o
Â¥
i
A
f
A
A
y
y

/
/
0
A
/'
a CHLORIDE
"T~
2
PORE VOLUMES
+ 3.4-ET hT/LT OLUE NE
223


TI
Figure 5-17.
Concentration vs. time for dissolved oxygen in biodegradation
treatments ID, IE, IF and 1G.
126


WELL P- 6
DOTE
DOTS
BENZEM
TX
EIHENZ
M,P-XYL
0-X7L
02-01-86
0
5
53
39
33
02-27-86
26
22
66
149
03-07-86
34
35
16
62
03-20-86
47
438
40
302
1%
03-27-86
54
372
44
287
268
04-25-86
82
37
87
05-23-86
111
13
32
88
06-25-86
144
17
485
183
89
79
07-18-86
167
78
106
61
36
09-19-86
229
14
21
11
21
55
10-22-86
262
1
39
25
32
79
10-25-86
265
1
11
5
3
10-28-86
268
1
23
5
2
1
11-04-86
275
2
13
4
112
171
11-07-86
278
1
39
33
119
129
11-19-86
290
1
33
700
246
11-23-86
294
2
26
2
10
51
12-10-86
311
4
1
01-27-87
359
02-20-87
383
19
20
16
29
15
03-17-87
408
15
6
7
04-29-87
451
41
33
12
32
05-29-87
481
1
33
m
379
223
06-23-87
506
0
5
2
1
isoEBZ
n-PBZ
3,4ET
135U4B
2ET
124TPB
1231?
1619
651
584
2283
621
232
273
168
494
238
221
191
125
452
147
2902
930
615
3094
608
2079
701
478
2176
471
918
655
270
1660
206
849
645
107
789
45
113
102
27
90
42
13
31
22
28.5
13
20
40
23
35
521
3
13
36
48
35
89
60
8
3
14
2
3
50
130
113
29
177
3
6
46
32
31
64
46
81
72
58
75
102
2
2
5
14
11
2
25
1
2
1
14
16
27
14
25
11
10
13
38
32
17
23
20
21
10
24
184
83
59
236
88
1
1
1
297


79
or linear models/ and this model is more convenient for the
application of equation [3.10].
5.5 Breakthrough Curves for Aromatic Solutes
5.5.1 Measurement of Column Dispersion
Breakthrough curves (BTCs) for a non-retained solute
were determined for each column used in these experiments.
Analysis of these data allowed the determination of the
Peclet number used to model the breakthrough of the aromatic
solutes. Evaluation of these data also allowed the
calculation of dispersion in the column. Chloride and
tritiated water were used in these experiments.
Dispersion (D^) was calculated from the slope of a plot
of C/Co vs pore volumes (pv) at pv = 1 according to the
equation (Rao/ 1985):
Dh = C v L/ 4 pi B2]
[5.1]
where D,
h
is the hydrodynamic dispersion coefficient
v is the flow velocity (cm/min), L is the length
of the column (cm) and B is the slope of the BTC at C/Co =1.
This assumes a sigmoidal shaped curve/ and this assumption
was valid for these breakthrough curves. A typical
breakthrough curve is shown in Figure 5-4. Some values of
D^ are presented in Table 5-9. Columns with flow rates of 1
ml/min exhibited higher values of since dispersion


68
Table 5-4. Regression parameters for the analysis of
average values of equilibrium batch isotherm
data with the Freundlich model.
Compound
N3
c b
(ug?L)
log
Kf,
lo9r
std
d
n
stde
2
r
Benzene
14
950
-0.857,
0.217
0.901,
0.071
0.952
Toluene
14
4200
-0.783,
0.260
0.876,
0.076
0.917
m,p-Xylene
16
4300
-0.758,
0.110
0.916,
0.031
0.984
o-Xylene
16
2500
-0.873,
0.098
0.966,
0.026
0.990
3 or 4 ETf
11
935
-0.702,
0.158
Q.904,
0.054
0.958
1,3,5-TMB9
11
460
-0.605,
0.081
0.921,
0.029
0.991
2-ETh
11
373
-0.951,
0.255
0.993,
0.088
0.934
1,2,4-TMB1
10
1600
-0.641,
0.099
0.937,
0.035
0.989
1,2,3TMB9
9
558
-0.623,
0.078
0.918,
0.028
0.995
anumber of data points
b . .
maximum concentration
Q
log standard deviation of values
^Freundlich exponent
0
standard deviation of Freundlich exponent
^3 or 4 Ethyltoluene
^1/3/5-Trimethylbenzene
V_
n2-Ethyltoluene
1l,2,4-Trimethylbenzene
-^1,2,3-Trimethylbenzene


2-Ethyltoluene Desorption Data
amoun t
Cs (ug/L)
Cw
(ug/L)
sorbed
avg
std
avg
std
(ug/L)
131
4.22
306
31
175
64
20.4
143
25
79
12
0.72
24
1
12
2
0.06
8
1
6
2
0.59
4
0
2
11
a
37.3
a
26.3
2.4
a
7 .7
a
5.3
n= 1
a
log
log
amount
amount
solution
sorbed
sorbed
concentration
(ng/g)
it
n
ii
n
ii
n
ii
ii
II
II
II
II
II
II
II
II
II
II
II
II
II
60.4
1.78
2.49
27.3
1.44
2.16
4.1
0.62*
1.38
2.1
0.32
0.90
0.7
-0.16
0.60
9.1
0.96
1.57
1.8
0.26
0.89
206


180
METHOD 6 ANGLEY 2
DATE LAST WRITTEN 87/05/12
SECTION 1 GO CONTROL
1
OUEN TEMP (DEG C) 50
ISO TIME (MIN) 5.0
RAMP RATE (BEG C/MIN) 3.0
2 3 4
70 94 200
7.0 0.0 0.0
3.0 30.6
FID SENS HIGH
0ET ZERO ON
DET TEMP 300
FLOW A 55 ML/MIN
CARRIER GAS HE
EGUILIB TIME 0.5 MIN
TOTAL RUN TIME 30.1 MIN
SECTION 2 TIMED EUENT3
TIME
EUENT
0.01
WIDTH
5
8.02
SET ZERO
29.00
INTEG
OFF
SECTION 3 DATA HANDLING
DATA ACQUIS
ITION
REPORT
START TIME 0.
00 MIN
CALC TYPE
INT STD
END TIME 30.
19 MIN
AREA/HT CALC
AREA
PRINT TOL
0.0000
WIDTH
5
OUTPUT
SKIM SENS
100
SCREEN
NO
BASELINE CORP
B-B
PRINTER
YES
AREA SENS
119
BASE SENS
6
PEAK IDENTIFICATION
QUANTITATION (CAL IE
AUG
UNRETD PEAK TIME
0.00 MIN
SCALING FACTOR
1.0000
AREA/HT REJECT
0.0000
RF FOR UNKNOWNS
10.0000
REF PK: TIME
13.19 MIN
STD COMPNT NAME
CHLOROBNZ
TIME TOL
0.05 MIN
SMP AMOUNT
1.0000
STD AMOUNT
62.0000
COMPNT: TOL ABS
0.05
TOL
0.50
COMPONENT LI
ST
RT
RF
STD AMT
NAME
GRP
5.S3
7.4916
7.1424
BENZENE
1
9.63
7.5224
4.8768
TOLUENE
1
13.56
10.0000
62.0000
CHLOROBNZ
0
14.32
7.8000
5.4360
ETHYL BENZENE
1
15. 43
7.6960
5.5030
M.P XYLENE
1
17.25
7.9963
5.6328
0 XYLENE
1
20.25
7.3722
5.6040
ISOPROPYL BNZ
2
22.60
7.5404
4. 1806
N PROPYL BNZ
2
23.38
6.7646
11.0616
3,4 ETHYLTOL
2
24.00
8.7483
3.2520
1,3,5 T M BNZ
2
24. 70
6.7756
5. ¡312
2,ETHYLTOLUENE
2
25.80
7.467
4. 1664
1,2.4 TMBNZ
2
27.44
7.9088
5.2440
1,2,3 TMENZ
2
OF 1 2 >


PORE VOLUMES
Breakthrough curve for n-propylbenzene in column biodegradation
experiment performed at a flow rate of 1 mL/min.
285


5-8 Regression parameters for the analysis of
average values of equilibrium batch
desorption data with the Freundlich model 78
5-9 Values of Dispersion calculated from the
breakthrough curves of unretained solutes in
laboratory columns 81
5-10 Calculated values of R, K and K from
analysis of solute breakthrough curves 87
5-11 Retardation factors calculated from leaching
column and equilibrium batch isotherm data 88
5-12 An empirical index of sorption nonequilibrium
(ISNE) for 12 selected aromatic solutes leaching
through Lake Alfred aquifer material 90
5-13 Regression coefficients for plots of log Koc
vs. log Kow and log Koc vs log WS 98
5-14 Comparison of relationships to predict Koc
from Kow values 99
5-15 Regression coefficients for the relationship
between log Koc and X 104
5-16 Total average hydrocarbon values (ug/L) in the
microcosms of batch biodegradation
experiment #1. 113
5-17 Biodegradation rate constants, half lives and
correlation coefficients for the fit of
biodegradation experiment #1 data to a first
order rate equation 116
5-18 Biodegradation rate constants, half lives
and correlation coefficients for the fit of
biodegradation experiment #1 data to the
Thomas-slope rate equation 118
5-19 Total average hydrocarbon values (ug/L) in
the microcosms of batch biodegradation
experiment #2 129
5-20 Biodegradation rate constants, half lives and
correlation coefficients for the fit of
biodegradation experiment #2 data to a first
order rate equation 133
viii


C / C o
13
13
1J
1
0.9
03
0.7
0.6
03
0.4
03
03
0.1
0
Figure 5-6. Breakthrough curve for toluene from Lake Alfred
water (C = 2600 ug/L).
o ^
Â¥
B& S-qQ
f
f
i
I /
/ /
.it
T~
2
PORE VOLUMES
CHLORIDE + TOLUENE
oo


treatment #2D
day 7
BNZ
TOL
ETH BZ
m,p-XYL
O-XYL
41
73
5
27
654
703
3602
55
2794
1584
735
3724
56
2895
1701
avg
493
2466
39
1905
1313
std
320
1693
24
1329
468
%variance
65
69
61
70
36
treatment #2D
day 14
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
73
175
73
71
216
1118
18
881
673
137
820
11
711
504
avg
142
704
15
555
416
std
59
394
3
348
254
%variance
41
56
23
63
61
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
23
92
143
6
246
4.30
478
192
172
656
292
2.20
509
196
179
656
309
2.20
337
160
165
439
282
2.90
222
48
16
306
27
0.99
66
30
9
70
9
34.14
3,4ET
135TMB
2ET
15
14
26
174
89
86
98
134
80
96
79
64
65
49
27
68
63
42
124TMB
123TMB
[DO]
10
21
4.30
187
164
4.10
121
203
2.80
106
129
3.73
73
78
0.66
69
60
17.81
254


BIOGRAPHICAL SKETCH
Joseph Timothy Angley was born on November 15/ 1958/ in
Boston/ Massachusetts. He prepared for college at Silver
Lake Regional High School in Kingston/ Massachusetts/ and
graduated in 1976. He attended Bowdoin College in
Brunswick/ Maine/ where he graduated with a Bachelor of Arts
degree in biology/ cum laude/ in 1980. He was accepted for
graduate study at the University of Florida/ Department of
environmental engineering sciences/ in January 1981 and
completed the Master of Science degree in 1984 with a study
of the mutagenicity of chlorinated sewage effluents. He is
currently a candidate for the Doctor of Philosophy degree in
Environmental Engineering Sciences.
His related work experience has included employment as
a graduate teaching assistant for several water chemistry
courses/ and as a graduate research associate on several
grants and projects.
In 1986 he was one of 22 graduate students nationwide
to receive an American Chemical Society Division of
Environmental Chemistry Graduate Student Award. He is a
member of the American Chemical Society and the Water
Pollution Control Federation.
He was married to Elizabeth Euliano in August/ 1985 and
together they have one child/ David/ 1 year old.
319


56
Average C/Cq values were calculated from the regions of the
solute breakthrough curves where 3C/St = 0. This derivation
assumes that microbial degradation occurs only from the
aqueous phase, and that dispersion is negligible.
4.12 Field Studies
4.12.1 Aquifer Characterization
A tracer experiment was conducted to measure seepage
velocities and obtain better estimates of aquifer hydraulic
conductivity and field scale dispersion. RAP-9 was used as
the dosing well. The following steps outline the
experimental procedure:
1. A tracer solution was prepared by dissolving
50 lb (23 kg) of technical grade ammonium chloride in 55 gal
(208 L) of tap water. The resulting concentration was
109,000 mg/L ammonium chloride.
2. The ammonium chloride solution was injected
into the dosing well and simultaneously diluted with tap
water at a metered rate of 1 gallon per minute (gpm).
Dosing continued for 15.8 hours, resulting in a total dose
volume of 1,035 gallons of tracer solution.
3. Detection of the tracer was monitored in
wells RAP-10 and RAP-11 using a conductivity meter with a
field probe. Measurements were obtained at one half- to
one-hour intervals for the first 24-hour period. Wells P-


CHAPTER VI
SUMMARY AND CONCLUSIONS
6.1 Summary
Hydrolysis, sorption and biodegradation reactions of
aromatic hydrocarbons (all isomers of C^H,--C0H,) under
6 6 9 12
water saturated soil conditions were investigated. Several
treatment techniques (^22r 2 gas and NH4C1 ) were evaluated
to enhance the microbial degradation of the aromatic
compounds. These studies were performed with a
multicomponent solute system of aromatic hydrocarbons,
resulting from the partial solubilization of gasoline into
groundwater, obtained from a field site where a gasoline
spill had occurred. The sorbent used in these studies was
collected from the field site in a non-contaminated portion
of the aquifer. This site was typical of sandy surficial
aquifers in Florida, and was characterized by the low
organic carbon content (0.015%) of the aquifer material.
The aquifer was composed primarily of medium to fine grained
sands.
Contaminated well water from the surficial aquifer was
employed as the source of solutes for the majority of
experiments. The major components of this water were the
hydrocarbons (C^H^-C^H) used in this study.
168


PORE VOLUMES
Breakthrough curve for 3 and 4 ethyltoluene in column
biodegradation experiment performed at a flow rate of 1 mL/min.
286


5-27 Breakthrough curve for field tracer (NH cl)
experiment measured at RAP-10 158
5-28 Distribution of benzene (ug/L) at the
Lake Alfred field site 160
5-29 Distribution of o-xylene (ug/L) at the
Lake Alfred field site.. 162
xii


Treatment 2F
treatment #2F
day 0
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
1238
7083
227
6498
3185
1826
10286
330
9320
4225
1350
7355
226
6903
3353
1155
6310
91
6246
3048
avg
1392
7759
219
7242
3453
std
260
1509
85
1223
459
%variance
19
19
39
17
13
treatment #2F
DAY 2
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
799
3996
38
3568
1929
518
2596
23
2203
1221
640
3415
32
3259
1770
avg
652
3336
31
3010
1640
std
115
574
6
584
303
%variance
18
17
20
19
18
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
1443
509
415
1899
689
7.50
2153
769
624
2805
1036
1576
569
462
2031
765
1432
527
428
1941
758
1651
594
482
2169
812
7.50
295
104
84
370
133
0.00
18
17
17
17
16
0.00
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
695
254
239
972
396
9.00
403
146
135
539
227
8.10
664
252
224
944
253
8.50
587
217
199
818
292
8.53
131
50
46
198
74
0.37
22
23
23
24
25
4.31
259


treatment #2H
day 7
BNZ
TOL
ETH BZ
m,p-XYL
O-XYL
101
54
0
12
225
25
21
0
6
43
105
74
3
5
164
avg
77
50
1
8
144
std
37
22
1
3
76
%variance
48
44
141
40
53
treatment #2H
day 14
BNZ
TOL
ETH BZ
m,p-XYL
O-XYL
24
29
0
23
59
26
29
2
22
69
14
3
0
0
13
14
3
0
1
24
avg
20
16
1
11
41
std
6
13
1
11
23
%variance
28
81
153
97
57
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
8
19
33
5
64
5.00
0
6
20
0
21
5.20
9
13
33
0
53
5.00
6
13
29
2
46
5.07
4
5
6
2
18
0.09
71
41
21
141
40
1.86
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
5
7
15
7
36
6
7
24
4
27
1
5
2
1
27
1
5
3
1
22
3
6
11
3
28
ERR
2
1
9
3
5
ERR
65
17
83
82
18
ERR
267


Table 5-16
Continued
Treatment
Compound
Day
1A
IB
1C
ID
IE
IF
1G
0
560.37
493.07
518.50
493.60
436.00
436.00
479.33
3
309.30
306.93
291.23
315.47
306.00
241.33
264.00
7
200.80
361.85
271.25
283.50
243.00 '
230.00
310.67
15
12.70
169.60
73.27
219.13
243.00
184.25
222.00
31
0.00
9.60
8.50
155.45
75.67
130.67
194.67
0
7.30
9.03
10.40
8.90
10.20
10.20
8.63
3
1.50
1.50
3.03
2.20
2.10
9.80
7.87
7
1.80
2.10
2.63
5.20
4.13
2.80
8.20
15
2.70
2.40
3.77
4.00
5.40
5.43
7.95
31
4.10
2.40
3.60
5.20
5.47
6.57
7.80
a3,4-Ethyltoluene
^1,3,5-Trimethylbenzene
C2-Ethyltoluene
^1,2,4-Trimethylbenzene
0
1,2,3-Trimethylbenzene
^Dissolved oxygen, in mg/L
115


32
and is more soluble in water than air or molecular oxygen.
However, it is also cytotoxic and may be chemically reduced,
especially in the presence of iron salts. The biological
decomposition of hydrogen peroxide is enzymatic:
catalase
2H22 > 2H2 + 2 [3.18]
peroxidase
H202 + XH2 > 2H20 + X [3.19]
where X is a biological reducing agent. Non-enzymatic
decomposition occurs most frequently in the presence of iron
salts:
Fe++ + H202 > Fe+++ + OH- + OH* [3.20]
OH* + H202 > H20 + H+ + 02*_ [3.21]
Britton (1985) reported that hydrogen peroxide was
relatively stable in combination with phosphates, even in
the presence of moderate iron concentrations, and that
bacterial populations can tolerate H2C>2 concentrations up to
500 mg/L. Hydrogen peroxide was shown (Britton, 1985) to
2
increase microbial counts by 10 but there was no reported
increase in hydrocarbon removal.
3.5.4 Measurement of Microbial Activity
The reduction of INT (2-p-iodophenol-3-p-nitrophenyl-5-
phenyl tetrazolium chloride) to INT-formazan by the electron
transport system is a function of cell respiration, and is
widely used as a general measure of microbial activity.


164
Table 5-26. Microbial populations in a soil core
taken south of the pump house (Bldg. 12),
July, 1986.
CFU/gdw x 106
Depth,
feet avg. std. dev. Comments
0.5
3.6
0.73
1.0
4.6
1.21
1.5
6.0
2.25
2.0
2.6
0.36
2.5
2.1
0.91
4.0
4.5
2.16
5.0
1.6
0.16
6.0
3.3
0.60
Saturated zone
gasoline odor


Table 5-21.
Continued.
136
Treatment
3,4-ET 1,3,5-TMB 2-ET
1,2,4-TMB 1,2,3-TMB
2A
k
0.216
0.152
0.130
0.228
0.162
r2
0.909
0.960
0.961
0.914
0.915
2B
k
0.156
0.161
0.144
0.172
0.138
r2
0.942
0.890
0.863
0.961
0.843
2C
k
0.162
0.177
0.154
0.173
0.157
r2
0.858
0.850
0.813
0.852
0.754
2D
k2
0.116
0.129
0.079
0.140
0.153
r2
0.987
0.986
0.910
0.999
0.880
2E
k
0.223
0.255
0.254
0.216
0.255
r2
0.832
0.881
0.858
0.801
0.856
2F
k
0.222
0.234
0.235
0.230
0.254
r2
0.852
0.859
0.786
0.846
0.704
2G
k
0.225
0.177
0.211
0.227
0.206
r2
0.940
0.961
0.943
0.940
0.935
2H
k
0.240
0.149
0.165
0.251
0.096
r2
0.946
0.968
0.989
0.934
0.718
21
k
0.211
0.217
0.193
0.206
0.195
r2
0.905
0.898
0.841
0.886
0.871
a -1
day


C / C o
CHLORIDE
PORE
+
VOLUMES
124T R1MET fT/LBENZENE


Table 3-1. Selected physical properties of study compounds.
ci Id ci
Molecular Water Boiling
*-' 3. O
Weight, Solubility, Point, Density, log ,
Compound AMU mg/L C g/ml Kqw 1Xa
Benzene
78.11
1740-
1791
80.1
0.8675
1.56-2.28 3.000
Toluene
92.13
515-
724
110.6
0.8669
2.11-2.73 3.394
Ethylbenzene
106.2
131-
208
136.2
0.8670
3.15 3.932
m,p-Xylene
106.7
134-
196
139.1
138.4
0.8642
0.8611
3.18 3.788
o-Xylene
106.7
142-
213
144.4
0.8802
2.77-3.13 3.805
3,4-Ethyltoluene
120.2
40
161.3
162.5
0.8645
0.8616
4.326
1,3,5-Trimethylbenzene
120.2
48-
92
164.7
0.8652
3.42-3.60 4.182
2-Ethyltoluene
120.2
40
165.2
0.8807
4.343
1,2,4-Trimethylbenzene
120.2
52-
59
169.3
0.8758
4.198
1,2,3-Trimethylbenzene
120.2
75
176.1
0.8944
3.60 4.215
Isopropylbenzene
120.2
48-
73
165.4
0.9106
3.60 4.305
n-Propylbenzene
120.2
55
159.2
0.8620
3.57-3.68 4.432
aCRC Handbook of Chemistry and Physics, 1980.
^Brookman et al., 1985.
CLeo et al., 1971.
dSabljic, 1987.
kD


43
4.7 Batch Sorption Studies
Sorption batch studies were performed in 40 mL VOA
vials with
Teflon
coated septa
(Fisher
Scientific ) .
Vials
were first
filled
with 60 g of
aquifer
material and
then
autoclaved
at 120
C for 1 hour
on each
of three consecutive
days .
Water
from w
ell OHM-4, con
taining
a mixture of
dissolved aromatic hydrocarbons/ was used in the batch
sorption experiments. As a result/ all these experiments
are multisolute/ at concentrations representative of those
found across the aquifer at Lake Alfred.
4.7.1 Sorption Experiments
Water used in the sorption experiments was filter
sterilized through 0.2 urn membrane filters (Gelman Metricel)
and then added to each vial. The range of solute
concentrations was achieved by dilution of Well OHM-4 water
with Well RAP-2 water at ratios between 1:1 to 1:1000. Each
dilution was performed in triplicate. Non-soil controls
(solute water with no soil) were also set up in triplicate.
To minimize headspace/ the vials were premixed on a rotary
tumbler for approximately 1 hour to remove interstitial air
and to disperse the foam that formed during mixing. The
vials were then opened/ completely filled with sample and
recapped. A high solids to solution ratio (2.9 g/ g ) was
used to maximize the fractional decrease in solution


184
All samples are assigned a consecutive field
number and this is recorded in the field
notebook, the field data sheet and on the
sample bottle.
6.3 Water Sample collection Field procedures.
6.3.1 Well preparation.
The volume of water in each well is
determined. The well is bailed for three
times the calculated volume. This is done
using a PVC bailer, or a battery operated
pump. The bailed volume is measured in a
calibrated container. Glass tubing is
attached to the end of tygon tubing to
present a glass surface to the water in the
well. Tygon tubing is attached directly to
the pump. Each well is supplied with a
dedicated piece of tygon tubing and a
dedicated glass insert.
6.3.2 Volatile Organic Samples
An unopened field blank is taken into the
field .
Wells are bailed as above.
Vials are filled by lowering the container
directly into the well. The vial is filled to
overflowing. The teflon side of the septum is
placed on the meniscus,and capped tightly.
The sample is inverted and examined for air
bubbles .
If air is present the sample is discarded,
and the well resampled.
Samples are taken in duplicate and chilled
immediately and placed in the dark. Blanks
are stored with the samples.
No preservation of the samples other than
cooling is performed.
6.4 Soil Sample Collection
6.4.1 Chemical Analysis
Soil samples destined for chemical analysis
for gasoline will be collected with a
stainless steel auger. Samples will be
placed into a one quart mason jar. Samples


PORE VOLUMES
Breakthrough curve for ethylbenzene in column biodegradation
experiment performed at a flow rate of 1 mL/mi.
281


218
Column Sorption Data as C/Co
ispBZ
npBZ
3,4 ET
135 TMB
II NJ
II
II M
ii i-a
ii
ii
n
ii
ii
124 TMB
123 TMB
0.002
0.002
0.002
0.000
0.002
0.002
0.001
0.001
0.002
0.002
0.000
0.002
0.001
0.003
0.001
0.003
0.002
0.002
0.005
0.002
0.002
0.005
0.003
0.004
0.003
0.009
0.005
0.010
0.034
0.013
0.023
0.021
0.047
0.029
0.059
0.089
0.038
0.062
0.061
0.114
0.079
0.137
0.188
0.094
0.138
0.135
0.219
0.16 6
0.253
0.269
0.151
0.220
0.211
0.316
0.245
0.352
0.335
0.207
0.283
0.273
0.382
0.308
0.418
0.506
0.350
0.426
0.431
0.545
0.466
0.590
0.568
0.402
0.481
0.483
0.598
0.516
0.627
0.612
0.450
0.514
0.531
0.641
0.563
0.671
0.657
0.490
0.568
0.575
0.699
0.602
0.730
0.702
0.535
0.607
0.623
0.734
0.651
0.769
0.762
0.597
0.681
0.691
0.804
0.725
0.842
0.840
0.656
0.714
0.747
0.859
0.769
0.887
0.871
0.717
0.786
0.810
0.899
0.830
0.929
0.916
0.744
0.792
0.831
0.923
0.843
0.942
0.919
0.749
0.801
0.841
0.938
0.854
0.964
0.932
0.777
0.861
0.867
0.966
0.892
1.001
0.878
0.720
0.779
0.817
0.914
0.838
0.959
1.065
0.906
0.958
1.000
1.086
1.009
1.104
1.222
1.027
1.088
1.160
1.278
1.184
1.323
1.120
0.927
0.973
1.056
1.163
1.073
1.209
1.226
1.030
1.069
1.160
1.266
1.171
1.305
1.118
0.947
1.020
1.090
1.203
1.121
1.269
1.114
0.956
1.006
1.088
1.185
1.103
1.237


TREATMENT #2A
treatment #2A
DAY 0
BNZ
TOL
ETH BZ
m,p-XYL o-
-XYL
3,4ET
135TMB 2ET
124TMB
123TMB
[DO]
1238
7083
227
6498
3185
1443
509
415
1899
689
7.50
1826
10286
330
9320
4225
2153
769
624
2805
1036
1350
7355
226
6903
3353
1576
569
462
2031
765
1155
6310
91
6246
3048
1432
527
428
1941
758
avg
1392
7759
219
7242
3453
1651
594
482
2169
812
7.50
std
260
1509
85
1223
459
295
104
84
370
133
0.00
%variance
19
19
39
17
13
18
17
17
17
16
0
treatment #2A
DAY 2 BNZ
TOL
ETH BZ
m,p-XYL o-
-XYL
3,4ET
135TMB 2ET
124TMB
123TMB
[DO]
110
206
22
1273
1340
368
221
198
412
335
3.80
47
84
31
201
1403
129
257
233
56
97
2.20
228
302
21
1447
2145
402
305
284
312
473
2.20
avg
128
197
25
974
1629
300
261
238
260
302
2.73
std
75
89
4
551
366
121
34
35
150
155
0.75
%variance
58
45
17
57
22
41
13
15
58
51
27.59
244


94
5.6 Evaluation of Sorption Models
The actual mechanisms through which sorption retards
the movement of solutes are not well known. Various
conceptual models are available to help describe these
sorption process. These include the partitioning between
organic matter on the aquifer matrix (Chiou et al., 1979/
Karickhoff et al., 1979), interactions with the mineral
surfaces (Sabljic, 1987), and solvophobic theory (Rao et
al. 1985 ). To assess the significance of these models,
sorption data from the column experiments were compared to
several theoretical models. The column data were normalized
to the organic carbon content of the Lake Alfred aquifer.
These values of K are shown in Table 5-10.
oc
5.6.1 Relationship between K and K
i ere
Several authors cite the linearity of the sorption
isotherms as evidence of the dominance of the partitioning
mechanism (Chiou et al., 1979, Chiou et al., 1983). However
this evidence may be suspect, if the range of concentrations
is far removed from the maximum solubility of the compounds.
In addition, many sorption models are indistinguishable over
sufficiently small concentration ranges (Curtis et al.,
1986). In this study, solute concentrations are far below
the solubility limits. The least soluble compounds in this
work are 3 ethyltoluene and 4-ethyltoluene with aqueous
solubilities of 40 mg/L. However, the maximum concentration
employed in this study is 935 ug/L,
which is only 2% of the


5.5 Breakthrough Curves for Aromatic Solutes 79
5.6 Evaluation of Sorption Models 93
5.7 Comparison of Mixed Solute and Single
Solute Retardation.... 106
5.8 Evaluation of Hydrogen Peroxide
Reactivity 108
5.9 Batch Biodegradation Experiment #1 Ill
5.10 Batch Biodegradation Experiment #2 128
5.11 Column Biodegradation Experiments 146
5.12 Comparison of Field and Laboratory data. 156
VI SUMMARY AND CONCLUSIONS 168
6.1 Summary 168
6.2 Conclusions 175
APPENDICES
A CHROMATOGRAPHIC CONDITIONS AND QUALITY
CONTROL PARAMETERS FOR THE ANALYSIS OF
AROMATIC HYDROCARBONS 179
B FIELD SAMPLING PROCEDURES 182
C ISOTHERM DATA FOR THE SORPTION OF
STUDY COMPOUNDS TO AQUIFER MATERIALS 186
D BREAKTHROUGH CURVE DATA FOR SORPTION OF
STUDY COMPOUNDS TO AQUIFER MATERIALS 214
E BATCH BIODEGRADATION DATA 229
F COLUMN BREAKTHROUGH DATA FOR
BIODEGRADATION COLUMNS 272
G HYDROCARBON CONCENTRATIONS IN MONITORING
WELLS AT THE LAKE ALFRED CITRUS RESEARCH
AND EDUCATION CENTER 291
REFERENCES......... 306
BIOGRAPHICAL SKETCH 318
vi


LOO AMOUNT SORBED
LOO SOLUTION CONCENTRATION
SORPTION o DESORPTION
Freundlich sorption-desorption isotherm for 1,2,3-Trimethylbenzene
at equilibrium.
213


120
below, each treatment is discussed individually, prior to an
overall analysis of these experiments.
5.9.1 Treatment 1A.
Data are plotted in Figures 5-14 and 5-15. The
dissolved oxygen in these microcosms was not artificially
increased, other than by aeration during the transfer and
filling of the solute containing water into the
biodegradation vials. The DO of these vials at time = 0 was
7.3 mg/L. An examination of the half lives of these solutes
showed that benzene (3.1 days) and toluene (2.9 days) were
readily removed from the microcosm compared to a half life
of 4.96 for 1,3,5-trimethylbenzene This is in
contradiction to studies which note the recalcitrance of
these compounds to biodegradation (Bossert and Bartha,
1984). The ortho isomer of xylene was more resistant to
microbial attack than were the meta and para isomers. This
confirmed the data of Kappeler and Wuhrmann (1978a, 1978b).
Complete degradation of all solutes was achieved by 31 days
(detection limit 0.5 ug/L) and in many cases degradation was
complete in 15 days. Toluene was degraded particularly
rapidly. The depletion of oxygen in these microcosms
suggested that this loss was microbially mediated (Figure 5-
16) .
5.9.2 Treatment IB.
Data for this treatment are shown in Appendix E .
These data demonstrate the effect of 17 mg/L hydrogen
peroxide treatment on the degradation of the aromatic


15
3.4.2 Sorption Equilibria
Two experimental techniques are widely used to evaluate
the aS/ 3t term in equation [1.1], These are batch
equilibrium and soil column methods. Batch studies allow
the evaluation of the linearity of the sorption isotherm and
their use is well documented (Schwarzenbach and Westall,
1981, Chiou et al., 1979). The most widely used models to
describe sorption equilibria in groundwater systems are the
linear [3.3] and Freundlich models [3.4] (Miller and Weber,
1984):
S = Kd C [3.3]
S=Kf*Cn (n < 1) [3.4]
where S (ug/g) and C (ug/L) are the adsorbed phase and
solution phase concentrations respectively at equilibrium,
(L/g) is the linear sorption coefficient, (L/g) is the
Freundlich sorption coefficient (both and indicating
sorption capacity) and n is an empirical constant
(indicating sorption intensity). The linear model is in
effect, a special case of the Freundlich model where n=l.
The Freundlich equation is often linearized (log
transformed) to facilitate calculation of variables and n
in batch studies:
log S = n log C + Log [3.5]
In column studies is evaluated through the retardation
factor (R). The mass transport equation for reactive
solutes under steady flow is described by equation [3.6]:


C / C o
1J
Figure 5
1 -
0.9 -
0.3 -
0.7 -
0.6 -
PORE VOLUMES
CHLORIDE
-4. Breakthrough curve for chloride for a 5 cm sorption column,
co
o


I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
Peter Nkedi-Kizza
Assistant Professor of
Soil Science
This dissertation was submitted to the Graduate Faculty of
the College of Engineering and to the Graduate School and
was accepted as partial fulfillment of the requirements for
the degree of Doctor of Philosophy.
Dean, Graduate School


WELL RAP-5
CATE
CAYS
BEI'EENE
TOJUENE
EIHEtE
m.p-XYL
o-XYL
iso-PBZ
n-PBZ
3,4ET
135TM3
2ET
124TM3
123T
10-22-86
262
54
208
213
692
499
54
346
674
231
327
5
10-25-86
265
11
38
38
18
10-28-86
268
5
42
18
26
16
64
11-04-86
275
11-07-86
278
3
14
21
73
40
2
5
39
19
15
41
20
11-19-86
290
4
10
21
66
43
2
4
32
18
14
37
21
11-23-86
294
20
30
51
237
128
4
7
132
55
46
122
70
12-10-86
311
2
02-20-87
383
6
5
3
5
2
3
3
4
2
2
1
1
03-17-87
408
14
145
174
362
103
46
25
348
146
66
164
183
04-29-87
451
0
1.4
0.3
1.2
0.5
0.2
0.9
0.3
0.7
0.8
0.2
05-29-87
481
0.2
1.3
4
16
3.4
0.4
0.8
3.5
3
3
9
4.3
06-23-87
506
25
48
80
618
108
3.5
6.8
255
113
79
301
130
301


317
Wilson, B.H., and J.F. Rees. (1985). Biotransformation of
Gasoline Hydrocarbons in Methanogenic Aquifer Material.
In Proceedings of NWWA/API Conference on Petroleum
Hydrocarbons and Organic Chemicals in Ground Water,
Houston, TX. Worthington, OH: National Water Well Assoc.,
pp. 128-139.
Wilson, J.T., C.G. Enfield, W.J. Dunlap, R.L. Crosby, D.A.
Foster, and L.B. Baskin. (1981). Transport and Fate of
Selected Organic Pollutants in a Sandy Soil. J. Environ.
Quail 10: 501-506.
Wilson, J.T., L.E. Leach, M. Henson, and J.N. Jones. (1986).
In Situ Biorestoration as a Ground Water Remediation
Technique. Ground Water Monitoring Review 6(4): 56-64.
Wilson, J.T., and J.F. McNabb. (1983). Biological
Transformation of Organic Pollutants in Groundwater. EOS
64(33): 505-508.
Wilson, J.T., J.F. McNabb, D.L. Balkwill, and W.C. Ghiorze.
(1983a). Enumeration and Characterization of Bacteria
Indigenous to a Shallow Water Table Aquifer. Ground Water
21: 134-142.
Wilson, J.T., J.F McNabb, J.W. Cochran, T.H. Wang, M.B.
Tomson, and P.B. Bedient. (1983b). Adaption of Ground-
Water Microorganisms at a Creosote Waste Disposal Site.
Presented Before the Division of Environmental Chemistry.
Washington, D.C.: American Chemical Society.
Wilson, S.B. (1985). In Situ Biosurfactant Production: An Aid
to the Biodegradation of Organic Ground Water
Contaminants. In Proceedings of The Petroleum
Hydrocarbons and Organic Chemicals in Ground Water -
Prevention, Detection and Restoration, Houston, TX.
Worthington, OH: National Water Well Assoc., pp'. 43 6-
444.


Q
*
O
o
J
Figure 5-11. Log Kqc vs. iX for aromatic solutes in (a) this study and from
(b) Sabijic (1987) .
103


Treatment #2B
DAY 7
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
667
2771
55
1857
1245
704
2835
52
1469
1214
592
2419
50
1357
1117
avg
654
2675
52
1561
1192
std
47
183
2
214
55
%variance
7
7
4
14
5
Treatment #2B
DAY 15
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
289
887
19
856
916
695
1700
37
469
824
avg
492
1294
28
663
870
std
203
407
9
194
46
%variance
41
31
31
29
5
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
380
137
135
390
239
2.30
323
131
127
250
229
2.10
279
108
118
245
200
2.20
327
125
127
295
223
2.20
41
12
7
67
17
0.08
13
10
5
23
7
3.71
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
198
99
107
159
190
3.10
116
102
109
69
175
2.70
157
101
108
114
183
2.90
41
2
1
45
8
0.20
26
1
1
39
4
6.90
N>
00


303
Brookman, G.T., M. Flanagan, and J.O. Kebe. (1985). Literature
Survey: Hydrocarbon Solubilities and Attenuation
Mechanisms. Washington, D.C.: American Petroleum
Institute Publication No. 4414.
Brown, H.Z., D.R. Bishop, and C.A. Rowan. (1984). The Role of
Skin Absorption as a Route of Exposure for Volatile
Organic Compounds (VOCs) in Drinking Water. American
Journal of Public Health 74(5): 479-484.
Carringer, R.D., J.B. Weber, and T.J. Monaco. (1975).
Adsorption-Desorption of Selected Pesticides by Organic
Matter and Montmori1Ionite. J. Agrie. Food Chem. 23(3):
568-572.
Chiou, C.T., L.J. Peters, and V.H. Freed. (1979). A Physical
Concept of Soil-Water Equilibria for Nonionic Organic
Compounds. Science 206: 831-832.
Chiou, C.T., P.E. Porter, and D.W. Schmedding. (1983).
Partition Equilibria of Non-ionic Organic Compounds
Between Organic Matter and Water. Environ. Sci. Technol.
17: 227-231.
Coleman, W.E., J.W. Munch, J.P. Streicher, H.P. Ringhand, and
F.C. Kopfler. (1984). The Identification and Measurement
of Components in Gasoline, Kerosene, and No. 2 Fuel Oil
that Partition into the Aqueous Phase after Mixing.
Arch. Environ. Contam. Toxicol. 13: 171-178.
CRC Handbook of Chemistry and Physics. (1980). Boca Raton,
FI.: CRC Press, Inc.
Curtis, G.P., P.V. Roberts, and M. Reinhard. (1986). A Natural
Gradient Experiment on Solute Transport in a Sand Aquifer
IV. Sorption of Organic Solutes and its Influence on
Mobility, unpublished.
Dagley, S. (1975). A Biochemical Approach to Some Problems of
Environmental Pollution. In Essays in Biochemistry.
P.N. Campbell and W.N. Adlridge (eds): New York: Academic
Press, p. 81.


90
Table 5-12. An empirical index of sorption nonequilibrium
(ISNE) for 12 selected aromatic solutes
leaching through Lake Alfred aquifer material
Compound
ISNE
Benzene
0.20
Toluene
0.23
Ethylbenzene
0.14
m,p-Xylene
0.17
o-Xylene
0.17
Isopropylbenzene
0.13
n-Propylbenzene
0.10
3 or 4 Ethyltoluene
0.12
1/3,5-Trimethylbenzene
0.11
2-Ethyltoluene
0.10
1,2,4-Trimethylbenzene 0.13
1/2,3-Trimethylbenzene 0.13


CHAPTER V
RESULTS AND DISCUSSION
5.1 Introduction
This chapter will review the results of all experiments
performed as part of this dissertation research. The
presentation of results and the interpretation of the data
for each major experimental section are grouped together to
avoid loss of continuity. Hydrolysis of aromatics in
groundwater is discussed first, followed by the results and
discussion of the batch and column sorption experiments.
Batch and column biodegradation experiments are addressed
next', followed by the presentation of field data, and the
correlation of field data with laboratory experiments.
5.2 Hydrolysis of Aromatic Hydrocarbons
The results of initial measurements (time = 0) of the
hydrolysis ampules were inconclusive, resulting from over
dilution of the samples. Several analytes were below the
limit of detection of the GCMS analytical system, therefore
no conclusive statements may be made relative to the rates
of aromatic hydrolysis.
Statistical analysis of data from ampules after 60 days
of temperature controlled storage indicated that for a given
temperature, there was no significant (student's t-test,
59


149
Table 5-22. First order biological rate constants and
half-lives of aromatic hydrocarbons for the
biodegradation column with flow at 0.90 mL/hr.
Compound
C/Co
*a -i
day
day
Bejizene
0.36
5.80
0.120
Toluene
0.144
11.01
0.063
Ethylbenzene
0.086
13.94
0.050
m,p-Xylene
0.051
16.82
0.041
0-Xylene
0.128
11.69
0.059
acalculated from the following data:
length = 2.5 cm
bulk density = 1.8 g/mL
particle density = 2.6 g/mL
pore water velocity = 14.21 cm/day
volumetric water content = 0.31


o
O
\
O
PORE VOLUMES
n CHLORIDE + O-XVLENE
221


1,2,4-Trimethylbenzene Desorption Data
Cs (ug/L)
avg
std
Cw (ug/L)
avg
std
479
14.27
1072
140
203
17.5
531
62
43
3.78
107
0
8
0.79
13
6
637
80.56
1565.2
a
24
22.12
156.5
a
5
4.91
31 4
a
3.8
0.25
15.7
a
amount
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentration
593
204.6
2.31
3.03
328
113.2
2.05
2.73
64
22.1
1.34
2.03
5
1.7
0.24
1.11
928.2
320.2
2.51
3.19
132.5
45.7
1.66
2.19
26.4
9.1
0.96
1.50
11.9
4.1
0.61
1.20
a
n= 1
209


o-Xylene Sorption Data
amount
Cs (ug/L)
Cw (ug/L)
sorbed
avg
std
avg
std
(ug/L)
1 .49
0.11
2.61
0.53
1.12
6.32
0.22
11.03
0.24
4.706666
19.70
3.63
23.07
2.15
3.366666
45.53
5.88
105.45
1.56
59.91666
819.02
158.39
1153.58
a
334.5633
2.02
0.13
3.41
a
1.39
3.10
0.20
6.83
a
3.73
7.95
0.45
17 .10
a
9.15
16.80
0.00
34 20
a
17.4
81.23
3.64
170.80
a
89.56666
1274.80
17.77
1708.27
74.22
433.4666
1786.50
74.72
2316.25
257.84
529.75
657.67
20.76
1245.67
137 .16
588
176.33
4.64
231.60
0.00
55.26666
56.50
11 .50
62.33
3.30
5.833333
19.00
0 .82
27.00
0.82
8
log
log
amount
amount
solution
sorbed
sorbed
concentrat ion
(ng/g)
II
II
II
II
II
II
II
II
II
ii
ii
ii
ii
ii
ii
ii
ii
ii
ii
ii
ii
ii
0.4
-0.41
0.42
1.6
0.21
1.04
1.2
0.07
1.36
20.7
1.32
2.02
115.4
2.06
3.06
0.5
-0.32
0.53
1.3
0.11
0.83
3.2
0.50
1.23
6.0
0.78
1.53
30.9
1.49
2.23
149.5
2.17
3.23
182.8
2.26
3.36
202.9
2.31
3.10
19.1
1.28
2.36
2.0
0.30
1.79
2.8
0.44
1.43
196


treatment #2G
day 7
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
0
9
0
3
4
0
4
0
40
105
0
11
0
9
70
avg
0
8
0
17
60
std
0
3
0
16
42
%varianee
ERR
37
ERR
94
70
treatment #2G
day 14
BNZ
TOL
ETH BZ
m,p-XYL
o-XYL
5
60
7
64
61
3
39
8
59
37
0
15
0
57
101
0
4
0
37
83
avg
2
29
4
54
70
std
2
21
4
10
24
%variance
107
73
101
19
34
3,4ET
135TMB
2ET
124TMB
123TMB
[DO]
2
0
9
0
5
5.00
15
0
18
21
43
2.90
5
10
17
3
25
4.40
7
3
15
8
24
4.10
5
4
4
9
16
0.88
73
141
28
116
65
21.54
3,4ET
135 TMB
2ET
124TMB
123TMB
[DO]
12
7
18
15
21
3.20
12
5
10
13
14
4.00
17
14
21
22
33
2.50
11
12
26
12
23
13
9
19
15
23
3.23
2
3
6
4
7
0.61
18
37
30
25
30
18.95
264


24
studies of a soil with low organic carbon (0.0015 gQC/g
soil) are shown in Table 3-3.
As may be noted from this short review, most of the
above studies involve data from individual components or
from oil based products. Given the differences in
composition among these petroleum products and gasoline,
extrapolation may be insufficient to provide accurate data
(Brookman et al., 1985).
3.5 Biodegradation of Aromatic Hydrocarbons in Groundwater
Biological activity is an important process in the
attenuation of gasoline hydrocarbons in the subsurface
environment. This realization is only recent. Early
techniques for the enumeration of microbes in the subsurface
(Waksman, 1916) underrepresented the numbers of microbes in
the subsurface, showing a decline in population with depth.
These data resulted from the use of nutrient rich growth
media, inappropriate for the enumeration of groundwater
bacteria (Wilson and McNabb, 1983).
Recent work shows that more substantial populations of
heterotrophic organisms exist in shallow water table
aquifers than were previously thought. Wilson et al .
(1983a) demonstrated that the numbers of organisms were
relatively constant to a depth of six meters in a shallow
water table aquifer. The populations of heterotrophic
bacteria were estimated to be approximately 10^
organisms/gram dry weight soil (Ghiorse and Balkwill, 1985).


1J
1 -
0.9 -
O A -
Breakthrough curve for o-xylene in column biodegradation
experiment performed at a flow rate of 1 mL/min.
283


in,p-Xylene Desorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
2055
45.02
4232
609
837
52.88
1893
80
152
20
423
a
27
0.81
137
a
26
3.5
48
1
1800
220.02
4287
a
55
50.59
429
18.4
19
4.14
86
a
13
0.439
43
a
amount
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentration
2177
751.1
2.88
3.63
1056
364.3
2.56
3.28
271
93.5
1.97
2.63
110
37.9
1.58
2.14
22
7.6
0.88
1.68
2487
858.0
2.93
3.63
374
129.0
2.11
2.63
67
23.1
1.36
1.93
30
10.4
1.01
1.63
a
n = l
194


228
Single Solute Breakthrough Data
For Benzene
L = 5.0 cm
Volume = 24.5 cu. cm.
Bulk Density = 1.82 g/cu. cm.
1 PV = 6.96 mL
v = 0.204 cm/min.
Benzene
mL
PV
(ug/L)
C/Co
1.43
0.205
9
0.009
3.43
0.493
12
0.013
4.43
0.636
25
0.027
5.43
0.780
35
0.038
6.43
0.924
84
0.092
7.43
1.068
250
0.272
8.43
1.211
409
0.446
9.43
1.355
529
0.576
10.43
1.499
656
0.714
11.43
1.642
734
0.800
12.43
1.786
779
0.848
13.43
1.930
784
0.854
14.43
2.073
825
0.899
15.43
2.217
853
0.929
16.43
2.361
820
0.893
17.43
2.504
918
1.000
23.43
3.366
909
0.990
24.43
3.510
917
0.999
25.43
3.654
887
0.966
26.43
3.797
748
0.815
27.43
3.941
578
0.629
28.43
4.085
408
0.445
29.43
4.228
298
0.325
30.43
4.372
240
0.261
31.43
4.516
181
0.197
32.43
4.659
143
0.156
33.43
4.803
113
0.123
35.43
5.091
88
0.095
37.43
5.378
81
0.089
39.43
5.665
63
0.068
49.43
7.102
33
0.036


Treatment IE
Day
Benzene Toluene m,p-Xyl o-Xyl
3,4 ET
15
26
30
24
901
22
245
162
38
1302
30
9
30
25
986
10
avg
93
74
29
1063
21
std
107
62
6
173
8
%var
115
84
22
16
40
31
2
6
9
263
5
4
1
2
178
2
15
4
4
192
3
avg
7
4
5
211
3
std
6
2
3
37
1
%var
82
56
59
18
37
,3,5
TMB
2 ET
1,2,4
TMB
1,2,3
TMB
[DO]
mg/L
150
139
8
255
6.1
123
132
8
242
4.1
104
122
7
232
6.0
126
131
8
243
5.4
19
7
0
9
0.9
15
5
6
4
17.0
65
41
4
99
5.0
48
26
4
66
3.7
24
24
2
62
7.7
46
30
3
76
5.5
17
8
1
17
1.7
37
25
28
22
30.5
239


WELL RAP-4
CATE
DM3
ENZ
TCL
EthBZ
m,p-XYL
O-XYL
iso-EBZ
n-PBZ
3,4ET
135TM3
2ET
124TMB
123TMB
10-22-86
262
224
313
944
325
117
1167
774
485
952
426
11-23-86
294
34
84
415
187
296
166
379
297
104
12-10-86
311
8
39
13
48
167
02-20-87
383
133
152
100
189
97
107
115
106
147
68
85
03-17-87
408
65
231
130
190
1%
157
67
163
04-29-87
451
0.8
0.1
0.1
0.8
05-29-87
481
0.4
0.2
0.7
0.5
0.1
0.1
0.5
0.3
0.6
0.3
0.1
06-23-87
506
2
12
114
515
180
10
27
226
95
69
268
109
WELL RAP-6
CATE
IMS
BE
TX
EthBZ
m,p-XYL
o-XYL
isoiBZ
rt-FEZ
3,4ET
135TM3
2ET
124TM3
123HB
10-22-86
262
113
170
242
324
142
11-23-86
294
5
2
2
4
3
15
4
10
3
5
69
12-10-86
311
1
01-27-87
359
2
1
4
5
46
02-20-87
383
03-17-87
408
3
25
995
255
2748
5785
04-29-87
451
0.1
0.3
0.2
0.4
0.2
0.2
0.2
0.8
0.1
0.4
0.2
0.2
05-29-87
481
0.1
3
1.5
3
3
0.1
0.3
1.5
0.8
1
1.3
1
06-23-87
506
0
0
0
0
0
0
0
0
0
300


WELL UF-1E
CATE
OWS
Bnz
Tt>l
EthBz
m,p-Xyl
02-01-86
0
1
1
02-27-86
26
365
525
03-07-86
34
03-20-86
47
03-27-86
54
04-25-86
82
05-23-86
111
1
06-25-86
144
07-28-86
167
2
1
08-28-86
208
08-19-86
229
1
1
1
10-22-86
262
11-23-86
294
12-10-86
311
02-20-87
383
03-17-87
408
05-29-87
481
0.2
0.5
1.8
1.4
06-23-87
506
1
0
5
3
isoFBZ n-PBZ 3,4ET 135TFB
2ET I24TMB 123TCB
1
l
0.4 0.7 1.2 4.6 3.4 3.8 1.4
1 1 2 6 7 3 3
303


Benzene Desorption Data
Cs (ug/L)
avg
Cw
std
(ug/L)
avg
std
amount
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentration
3
1
0.2
0.08
2.8
0.97
-0.015
0.48
92.5
4.4
1.7
1.1
90.3
31.1
1.49
1.96
8.6
1
5.1
0.5
3.6
1.2
0.09
0.93
338
a
106
27
282
97.3
1.99
2.59
865
128
238
a
627
216
2.34
2.94
a
n = l
188


12
The physical and mathematical relationships of water and
solute transport were reviewed by Davidson et al. (1983).
Solute dispersion was noted to occur because of macroscale
spatial changes in the direction and magnitude of water
flow. The continuum approach to mathematically describe
water and solute transport in laboratory soil columns was
shown to be reasonably successful.
In practice, laboratory measurements and theory may be
of little value in predicting dispersion in natural
aquifers. Laboratory columns give dispersivity estimates on
the order of centimeters, whereas field scale dispersion is
usually in meters (Bedient et al., 1985). This is a result
of the greater heterogeneity of a field site versus a small
homogeneous laboratory column. A solution for equation
[3.1] for a finite column using dimensionless variables was
presented by Brenner (1962). The dimensionless Peclet
number (P ) was used as a measure of dispersion:
Pe = vL/4Dh [3.2]
where v is pore water velocity (cm/min), L is the length
(cm) of the soil column and is the hydrodynamic
2
dispersion coefficient (cm /min). For values of Pg > 100
dispersion is assumed negligible. Values of P^ < 10
generally indicate complete mixing. Boundary conditions for
displacement experiments through short laboratory columns
were reviewed by van Genuchten and Parker (1984). The
solution of Brenner (1962) was shown to correctly conserve
mass in finite laboratory soil columns, based on mass


Benzene Sorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
0 4
0.1
1.5
0.5
2.11
0.14
2.7
0.42
1.1
0.08
1.5
0.69
1.8
0.14
2.5
0.45
4.4
a
7.4
0.39
8.7
0.3
15
15.5
30.9
0.92
73
3.4
46.19
4.6
90
9
66
1.6
92
4.4
254
4.2
338
a
594
12
728
34.3
771
26
865
111
873
135
900
90
amount
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentrat ion
1.1
0.38
-0.42
0.18
0.54
0.19
-0.73
0.42
0.35
0.12
-0.91
0.16
0.7
0.24
-6.17
0.4
3
1
0.013
0.87
66.1
2.1
0.32
1.17
41.9
14.5
1.16
1.86
43.8
15.1
1.18
1.95
24.5
9.1
0.96
1.97
84
29
1.46
2.53
133
46
1.66
2.86
94
32.3
1.51
2.94
27
9.5
0.98
2.95
a
n = l
187


162
different than that of benzene. Based on a comparison of R
values, the distribution of o-xylene should be skewed
towards the wetlands, as is benzene. One factor which may
account for the apparent increase in retardation for o-
xylene is the higher rate constant for biological removal
(half life = 0.144 hours at 0.680 cm/min) compared to
benzene (0.940 hours). This results in improved removal of
o-xylene as it moves through the aquifer, so that the solute
front appears retarded, relative to benzene. These type of
analysis, although somewhat crude, indicates the importance
of biological data in the interpretation of solute transport
under field conditions.
5.12,3 Microbial Enumeration and biodegradation
Microbial populations at the field site are given in
5 6
Tables 5-24 to 5-27. Generally they range from 10 to 10
organisms/gram dry weight soil. Given sufficient oxygen,
this population is sufficient for complete biodegradation as
shown in the batch laboratory studies; no additional
nutrients are necessary. The extent of oxygen limitation is
noted in Table 5-28, where the range in concentrations of DO
over the study period are presented. Wells which exhibit
low DO also exhibit high concentrations of hydrocarbons. An
example of the apparent lack of significant bioactivity is
seen in an examination of well data from OHM-3. This well
shows consistently low DO (0.4 mg/L), with no significant
changes in the concentrations of any of the individual
solutes.


Treatment 1C
1,3,5 1,2,4 1,2,3 DO
Day
Benzene
Toluene
m,P-Xyl
o-Xyl
3,4 ET
TMB
2 ET
TMB
TMB
mg/L
15
14
35
75
252
12
100
51
11
177
3.2
4
30
53
34
16
7
14
10
15
4.0
9
42
44
86
19
9
37
9
28
4.1
avg
9
36
57
124
16
39
34
10
73
3.8
std
4
5
13
93
3
43
15
1
74
0.4
%var
48
14
22
75
19
113
45
8
101
10.7
31
0
0
0
0
0
0
5
1
1
2.6
0
0
0
1
0
35
2
1
17
4.8
avg
0
0
0
0
0
18
4
1
9
3.7
std
0
0
0
0
0
18
2
0
8
1.1
%var
0
0
0
100
0
100
47
6
94
29.7


1,2,3-Trimethylbenzene Sorption Data
Cs (ug/L) Cw (ug/L)
avg
std
avg
std
284
30
429
82
115
4
257
44
31
1
43
1
11
6
15
2
361.4
2.4
558
32.1
23.1
1.17
55.8
a
4.3
0.07
11.2
a
1.9
0.14
5.6
a
0 .89
0.17
2.23
a
0.45
0.05
1.11
a
amount
sorbed
(ug/L)
amount
sorbed
(ng/g)
log
amount
sorbed
log
solution
concentration
145
50.0
1.70
2.63
142
49.0
1.69
2.41
12
4.1
0.62
1.63
4
1.4
0.14
1.18
196.6
67.8
1.83
2.75
32.7
11.3
1.05
1.75
6 .9
2.4
0.38
1.05
3.7
1.3
0.11
0.75
1.34
0.5
-0.34
0.35
0.66
0.2
-0.64
0.05
a
n = l
211


LOO AMOU/VT SORBED
Freundlich sorption-desorption isotherm for m,p-Xylene
at equilibrium
195


150
consistent with the removal of side chains prior to attack
on the aromatic nucleous.
Degradation rates for columns run at the higher flow
rate are shown in Table 5-23. The faster flow rate
decreased the half lives of the aromatic contaminants. This
resulted from improved transport of oxygen and subtrate.
The flow rate used in this column was equivalent to
groundwater velocities in portions of the Lake Alfred
aquifer (Killan, 1987) and may closely reflect field
removals. Breakthrough curves for benzene, toluene and
1,2,4-trimethylbenzene are shown in Figures 5-24 ,5-25 and
5-26. Only 10% of the benzene and 30% of the toluene were
removed at this flow rate although other removals are in the
range of 50-60%. The difference in the degradation for
benzene is seen by comparison of Figures 5-24 with Figure 5-
26. Benzene almost breaks through the column completely,
reflecting the time involved for the microbes to degrade
this solute. The branched aromatic compounds are more
rapidly degraded, which is consistent with the results from
the 0.680 cm/min column. The rates of degradation of the
aromatic compounds in the 0.01 cm/min columns were in the
order Cg > Cg > Benzene was the most recalcitrant
with a half life of 0.12 days (2.88 hours). These data are
consistent with the aromatic degradation process described
by Evans (1977), and the literature on the fate of aromatic
hydrocarbons in soils (Bossert and Bartha, 1984).


Table 5-16. Continued
Treatment
Compound
Day
1A
IB
1C
ID
IE
IF
1G
3,4-ETa
1,3,5-TMBb
2-ETC
l,2,4-TMBd
0
915.59
659.17
867.00
858.30
675.33
675.33
717.67
3
264.60
346.40
319.73
249.63
410.00
383.33
353.67
7
168.37
409.85
46.30
60.20
69.00
66.00
414.33
15
14.60
182.20
15.80
41.90
20.67
47.75
312.33
31
0.00
4.83
0.00
4.13
3.33
8.67
224.00
0
389.89
269.07
378.90
347.75
280.00
280.00
320.67
3
218.30
204.73
188.93
214.47
185.33
130.33
165.33
7
136.93
223.50
128.40
153.50
134.67
122.67
189.33
15
3.80
83.55
38.50
132.37
125.67
94.75
129.33
31
0.00
3.23
17.65
99.70
45.67
56.00
104.33
0
410.43
241.47
317.90
299.50
256.33
256.33
285.33
3
167.60
187.80
178.93
212.07
175.67
145.00
146.33
7
131.70
215.75
145.95
179.05
151.67
147.67
172.00
15
33.15
100.50
33.90
137.73
131.00
128.00
126.00
31
0.00
10.83
3.60
54.05
30.33
68.33
101.00
0
1334.60
1121.87
1103.30
1113.70
980.00
980.00
1046.33
3
442.55
388.13
422.70
89.90
349.33
548.33
537.67
7
189.60
364.70
7.58
4.75
5.33
7.33
618.33
15
14.90
181.20
9.63
4.90
7.67
9.00
414.67
31
0.00
2.10
0.85
1.70
3.33
2.33
335.67
114


o O / O
1
OJO
OjB
0.7
OS
OJO
OA
OJO
02
03
O
O 4 a 12 10 20 84 26 32
DAYS
130TMB + 2ET o 124TMB A 123TMB
Figure 5-15. Relative concentration vs. time for four CgH-j^ compounds
in biodegradation treatment 1A.
122