<%BANNER%>

Investigation of Stiffness Gain Mechanism in Florida Limestone Base Course Material

Permanent Link: http://ufdc.ufl.edu/UFE0021855/00001

Material Information

Title: Investigation of Stiffness Gain Mechanism in Florida Limestone Base Course Material
Physical Description: 1 online resource (79 p.)
Language: english
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2008

Subjects

Subjects / Keywords: base, cementation, geotechnical, limestone, stiffness, suction
Civil and Coastal Engineering -- Dissertations, Academic -- UF
Genre: Civil Engineering thesis, M.E.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: The Florida Department of Transportation (FDOT) has observed stiffness increases over time in limestone base course materials. It is a goal of the FDOT to understand the mechanism involved so that it may implement design procedures to account for the stiffness increase. Past studies have credited calcium carbonate cementation as providing the stiffness increase. The objective of this study was to test the hypothesis that cementation can occur if there are pressure gradients adjacent to grain contacts. Laboratory investigation involved compacting three Florida limestones and curing in chambers with high, medium and low relative humidities, which would induce various degrees of such pressure gradients. Modulus values were obtained over time by performing free-free resonant column tests on all materials. Compacted materials were later looked at with a scanning electron microscope to search for crystal growth in the materials. It was found that no cementation had occurred during the 30-day test period and that the observed stiffness gains were a result of capillary suction within the nano and micro-pores. SEM imagery for an aged field core paired with porosity data suggests that cementation occurs, but at a much slower rate than observed in the compacted laboratory specimens. Image analysis of the field core showed the presence of calcite crystals and much less fine void space than the compacted specimen of similar material. Porosity measurements were compared between the three compacted materials and the field core to help clarify what processes are involved with the stiffness increases.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Thesis: Thesis (M.E.)--University of Florida, 2008.
Local: Adviser: McVay, Michael C.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2008
System ID: UFE0021855:00001

Permanent Link: http://ufdc.ufl.edu/UFE0021855/00001

Material Information

Title: Investigation of Stiffness Gain Mechanism in Florida Limestone Base Course Material
Physical Description: 1 online resource (79 p.)
Language: english
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2008

Subjects

Subjects / Keywords: base, cementation, geotechnical, limestone, stiffness, suction
Civil and Coastal Engineering -- Dissertations, Academic -- UF
Genre: Civil Engineering thesis, M.E.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: The Florida Department of Transportation (FDOT) has observed stiffness increases over time in limestone base course materials. It is a goal of the FDOT to understand the mechanism involved so that it may implement design procedures to account for the stiffness increase. Past studies have credited calcium carbonate cementation as providing the stiffness increase. The objective of this study was to test the hypothesis that cementation can occur if there are pressure gradients adjacent to grain contacts. Laboratory investigation involved compacting three Florida limestones and curing in chambers with high, medium and low relative humidities, which would induce various degrees of such pressure gradients. Modulus values were obtained over time by performing free-free resonant column tests on all materials. Compacted materials were later looked at with a scanning electron microscope to search for crystal growth in the materials. It was found that no cementation had occurred during the 30-day test period and that the observed stiffness gains were a result of capillary suction within the nano and micro-pores. SEM imagery for an aged field core paired with porosity data suggests that cementation occurs, but at a much slower rate than observed in the compacted laboratory specimens. Image analysis of the field core showed the presence of calcite crystals and much less fine void space than the compacted specimen of similar material. Porosity measurements were compared between the three compacted materials and the field core to help clarify what processes are involved with the stiffness increases.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Thesis: Thesis (M.E.)--University of Florida, 2008.
Local: Adviser: McVay, Michael C.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2008
System ID: UFE0021855:00001


This item has the following downloads:


Full Text





INVESTIGATION OF STIFFNESS GAIN
MECHANISM IN FLORIDA LIMESTONE
BASE COURSE MATERIAL





















By

LUIS ALFONSO CAMPOS


A THESIS PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF ENGINEERING

UNIVERSITY OF FLORIDA


2008

































2008 Luis Alfonso Campos


































To my Parents and Sisters and to Carrie















ACKNOWLEDGMENTS

I would like to thank Dr. Bjorn Birgisson for giving me the opportunity to work on

this research project with which most of the work was completed under. I would also like

to thank Dr. Michael C. McVay for taking this research to completion and for his

seemingly limitless knowledge and fascination in geotechnical engineering. I would also

like to thank Dr. Philip S. Neuhoff of the Department of Geology who helped shape this

project and give it a new direction. I would also like to thank Dr. Dennis R. Hiltunen and

Dr. Reynaldo Roque for serving on my supervisory committee.

I appreciate my former boss, the late M. Fred Rwebyogo, and Dr. Frank C.

Townsend's guidance which steered me towards my career in graduate school. I would

also like to thank Dr. David Bloomquist for giving me the opportunity to work on a

separate project which took me around the world to a place I would never have had a

chance to see.

I appreciate the patience and knowledge of Tanya Reidhammer with all of my

chemistry and microscopy questions. I also appreciate the cooperation from the FDOT

State Materials Office. Without their aid and experience this research would not have

been possible.

Finally, I would like to thank my family for their support throughout the years. I

also thank my friends for being such fantastic distractions and entertainment in my life.









TABLE OF CONTENTS

page

A C K N O W L E D G M E N T S ............................................................................................................. iv

LIST OF TA BLES ............................. ... .............. .. .... ........... ......... .... ............ vii

LIST OF FIGURES ................ ................................. ................. .......... viii

A B S T R A C T ................................ .................. .......................... ................ .. x

CHAPTER

1 INTRODUCTION ............... ................. ........... ................... ...............

1.1 B ack g rou n d ................................................................................................... . 1
1.2 Purpose and Scope ...................... .... .............. .............................. .2
1.3 M eth odology ................................................................... ................................ . 2

2 L ITER A TU R E R E V IEW .................................................................. ..... .........................

2.1 Introduction ..................................... .......................... ..... ..... ......... 4
2 .2 B ase C ourse M materials .................................................. ........................... ...........4
2.2 Chem istry of Carbonate Cem entation....................................... ......................... 5
2.3 K elvin's Equation ....................... .................................. .......... .... ....
2.4 Com action Issues ...................... .................... ..... .. .............. ....

3 M ATERIALS AND M ETHOD S ............................................................ .......11

3.1 Selection of M materials .................. ..................................... .. ........ .... 11
3 .2 M material P rep aration ............................................................................ ................... 12
3.3 C om action P procedures ....................................................................... ..................13
3.4 Curing Procedures .................. ............................ ............ .. .. ............ 13
3.5 R esonant C olum n T testing ............................................................................. ...... 14
3.6 Scanning E lectron M icroscopy ........................................................................ .. .... 15
3.6.1 Sample Preparation ............... .......................... ............. ............. 15
3.6.2 Scanning Electron Microscopy Analysis.........................................................15
3.6.3 Im aging Softw are ......................................... ........ ........ .. .......... 16
3.7 P orosity M easurem ents ....................................................................... ........ .......... 16
3.8 X -R ay D iffraction ................................................. ...... .............. .. 17

4 RESULTS AND D ISCU SSION .................................................. ............................... 25

4.1 R esonant Colum n R results ................................................... ........ ............... .25
4.2 Scanning Electron M microscope Analysis .......................................... ............... 26
4.3 Porosity M easurem ents ........................................................................... 27
4.4 Discussion ..................................... .................. ................ .......... 29









5 CONCLUSIONS AND RECOMMENDATIONS ............ ........................................51

5 .1 C o n clu sio n s ......................................................... .............. ................ 5 1
5.2 R ecom m endations for Future W ork.................................................................. ......52

APPENDIX

A M odified Proctor and LB R R results ............................................................... ....................54

B Resonant Colum n Testing D ata......................................................................... 57

C C alcu nation s .................................................................................6 5

L IST O F R E F E R E N C E S ...................................................................................... ....................66

B IO G R A PH IC A L SK E T C H ............................................................................... .....................68






































vi









LIST OF TABLES


Table page

3-1 Descriptive data for three limestone base course materials ......................................21

3-2 Equilibrium relative humidity values for saturated aqueous salt solutions .....................21

4-1 Summary of Ocala limestone under different curing conditions................. ................31

4-2 Summary of Miami limestone under different curing conditions...................................31

4-3 Summary of Loxahatchee shell rock under different curing conditions............................32

4-4 Average bulk properties of base course materials .................................. ............... 42

4-5 Summary statistics for pore sizes from ImageJ analysis ............................................. 42

4-6 Comparison of porosity values from different methods ..............................................42

4-7 Theoretical suction pressures for different relative humidities..............................50

B-1 Data for Ocala limestone after compaction ............................................ ............... 57

B-2 D ata for Ocala lim estone after curing ...................................................... .............. 58

B-3 Data for M iami limestone after compaction ..................................... ........ ............... 59

B-4 D ata for M iam i lim estone after curing........................................ ........................... 60

B-5 Data for Loxahatchee shell rock after compaction ................................. ................61

B-6 Data for Loxahatchee shell rock after curing.................................. ....................... 62

C-1 Summary of values used for calculating precipitated calcite ...........................................65









LIST OF FIGURES

Figure page

2-1 Schematic of pavement layers showing concept of structural numbers ............................9

2-2 General relationship between pore diameter and relative humidity ..................................9

2-3 General relationship between total suction and relative humidity................................. 10

3-1 Map of Florida showing approximate locations of aggregate source mines ...................19

3-2 Grain size distribution curves for limestone materials ............................................... 20

3-3 M ercury Porosim eter specim en set-up....................................................................... ...22

3-4 X-Ray diffraction plot for untreated Ocala limestone ................................................. 23

3-5 X-Ray diffraction plot for untreated Miami limestone .............. ...................................23

3-6 X-Ray diffraction plot for untreated Loxahatchee limestone ........................................24

4-1 Ocala lim estone stiffness gain versus tim e ............................................. ............... 33

4-2 M iami limestone stiffness gain versus time.................................................................... 33

4-3 Loxahatchee shell rock stiffness gain versus time ......................................................34

4-4 Ocala limestone stiffness gain versus decrease in initial moisture.............. .................34

4-5 Miami limestone stiffness gain versus decrease in initial moisture...............................35

4-6 Loxahatchee shell rock stiffness gain versus decrease in initial moisture.........................35

4-7 O cala lim stone typical im age 1 ............................................... ............................. 36

4-8 Ocala lim estone typical im age 2 ..................................................................... 36

4-9 M iam i lim estone typical im age 1............................................................ .....................37

4-10 M iam i lim estone typical im age 2 ............................................................ .....................37

4-11 Loxahatchee shell rock typical im age 1 ........................................ ......................... 38

4-12 Loxahatchee shell rock image 2 showing zone of possible calcite crystal growth............38

4-13 Loxahatchee shell rock close-up of highlighted region in Fig. 4-12 .............................39

4-14 G lades core typical im age 1 ...................................................................... ...................39









4-15 Glades core typical image 2 showing zone of calcite crystal growth ............................40

4-16 Glades core close-up of highlighted region in Fig. 4-15 ......................................40

4-17 Glades core typical image 3 showing zone of calcite crystal growth.............................41

4-18 Glades core close-up of highlighted region in Fig. 4-17 ......................................41

4-19 Relative humidity values and corresponding affected pore diameters ...........................43

4-20 Mercury Porosimeter results for 30-day specimens and Glades core.............................44

4-21 Pore diameter histogram from ImageJ analysis for Ocala limestone .............................45

4-22 Pore diameter histogram from ImageJ analysis for Miami limestone.............................45

4-23 Pore diameter histogram from ImageJ analysis for Loxahatchee shell rock ...................46

4-24 Pore diameter histogram from ImageJ analysis for Glades core ...................................46

4-25 Ocala limestone pore diameter distribution from ImageJ analysis...............................47

4-26 Miami limestone pore diameter distribution from ImageJ analysis..............................47

4-27 Loxahatchee shell rock pore diameter distribution from ImageJ analysis.......................48

4-28 Image processing steps with ImageJ software............................................................. 49

4-29 Theoretical relative humidity values and corresponding total suction ...........................50

A-i Ocala limestone Modified Proctor and LBR data..........................................................54

A-2 Miami limestone Modified Proctor and LBR data .................................... ...............55

A-3 Loxahatchee shell rock Modified Proctor and LBR data............................................56

B-l Example 1 of frequency measured in Free-Free Resonant Column test..........................63

B-2 Example 2 of frequency measured in Free-Free Resonant Column test........................64
















Abstract of Thesis Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Master of Engineering

INVESTIGATION OF STIFFNESS GAIN
MECHANISM IN FLORIDA LIMESTONE
BASE COURSE MATERIAL


By

Luis Alfonso Campos

May 2008

Chair: Michael McVay
Major: Civil Engineering

The Florida Department of Transportation (FDOT) has observed stiffness increases

over time in limestone base course materials. It is a goal of the FDOT to understand the

mechanism involved so that it may implement design procedures to account for the

stiffness increase. Past studies have credited calcium carbonate cementation as providing

the stiffness increase. The objective of this study was to test the hypothesis that

cementation can occur if there are pressure gradients adjacent to grain contacts.

Laboratory investigation involved compacting three Florida limestones and curing in

chambers with high, medium and low relative humidities, which would induce various

degrees of such pressure gradients. Modulus values were obtained over time by

performing free-free resonant column tests on all materials. Compacted materials were

later looked at with a scanning electron microscope to search for crystal growth in the

materials.









It was found that no cementation had occurred during the 30-day test period and

that the observed stiffness gains were a result of capillary suction within the nano and

micro-pores. SEM imagery for an aged field core paired with porosity data suggests that

cementation occurs, but at a much slower rate than observed in the compacted laboratory

specimens. Image analysis of the field core showed the presence of calcite crystals and

much less fine void space than the compacted specimen of similar material. Porosity

measurements were compared between the three compacted materials and the field core

to help clarify what processes are involved with the stiffness increases.














CHAPTER 1
INTRODUCTION

1.1 Background

The state of Florida has over 90,000 miles of paved public roads that commuters

rely on a daily basis. These roadways are designed by highway engineers using the

highest quality of material available while at the same time maximizing the design for

economy. The engineer will try out different material and thickness configurations to deal

with anticipated traffic loads and pick the least expensive design. The highways are

typically designed to last for 25 years or more, but as pavements progress through their

design life, the need to repair or replace the pavement arises.

With routine maintenance, the asphalt surface is milled and made thicker upon

replacement. This asphalt surface layer is by far the most expensive material used for

roadway construction, so optimization is important. The State of Florida Department of

Transportation (FDOT) has studied limestones and has noted significant increases in the

stiffness of the limestone base course materials over time. With stronger base course

materials, less asphalt concrete can be used, saving taxpayer money. Likewise, if the

potential for an increase in stiffness is known before the initial design, the highway

engineers could use this information to further improve upon their designs.

Understanding the behavior and properties of these materials, both present and future, is

the key to better engineering.









1.2 Purpose and Scope

As mentioned, studies have been done that note an increase in stiffness over time in

limerock base course materials (Gartland, 1979; Graves, 1987; Zimpher, 1989). The

FDOT has made attempts to reevaluate design parameters associated with base course

materials to account for the stiffness increase. A problem is that there are many sources

from different geological deposits from which these base course materials are mined. The

need to characterize the engineering properties effectively for each of these sources is

required. Simple tests to characterize some of the properties (such as stiffness) have been

established and are performed on a routine basis by local testing consultants. While

stiffness increases in limestone base course materials have been observed, no test has

been successful in predicting what a generic stiffness increase will be because the

mechanism is not yet fully understood.

One proposed possibility of the stiffness increase is due to calcite crystal growth

and cementation in the micro-pore structure of the limestone. Limestone is mostly

CaCO3, calcium carbonate, which will dissociate and precipitate under various natural

environmental conditions. Calcite crystals will precipitate within what was previously a

void in the limestone. These crystals bond calcite particles together and also create more

contact points with which to resist deformation, resulting in a stiffness increase. The

purpose of this study was to try and create conditions which are favorable for the

precipitation of calcite crystals and observe different material properties which may

affect this phenomenon.

1.3 Methodology

Bricker (1971) noted that cementation in carbonate material occurs due to many

factors, one of which is local pressure gradients adjacent to grain contacts. It is proposed









that by controlling the relative humidity within a curing chamber such a pressure gradient

will be induced and accelerate the cementation process within compacted limestone base

course specimens. The limestone materials were compacted, cured under varying relative

humidities and tested over time for an increase in stiffness.

Three types of limestones representing different geologic formations were used in

this study. Physical and chemical properties were determined for each material. The main

tool used in determining the stiffness increase in the base course materials was the free-

free resonant column test to find modulus values. Scanning electron microscopy (SEM)

techniques and imaging software was used to find pore structure characteristics in the

three cured materials. Pore structure data for a field core sample was also measured for

comparison.














CHAPTER 2
LITERATURE REVIEW

2.1 Introduction

The purpose of this research project was to create conditions which are favorable

for the precipitation of calcite crystals and observe different material properties which

may affect this phenomenon. A review of the literature was conducted to find information

on base course materials, carbonate cementation and compaction issues for limestone

base course materials.

2.2 Base Course Materials

Highway pavements fall into three design categories: flexible, rigid or composite

pavements. The most commonly used pavement type in Florida is the flexible design.

This design consists of an asphalt surface course, a base course just below that, and the

subgrade which consists of the existing soil. The goal of a pavement system is to protect

the subgrade. Therefore, high quality materials are used for the surface and base courses.

Pavements layers are designed using the concept of structural numbers. In order to

prevent an anticipated amount of damage to the layer just below, a structural number

requirement should be met. The quality and stiffness of each layer of material is indicated

by a structural layer coefficient, a. The structural number for each layer can be calculated

by multiplying the structural layer coefficient by the layer thickness. A diagram of the

pavement system and design is shown in Fig. 2-1. Design procedures can be found in

many textbooks, including Huang (2004). In the state of Florida, limestone is the most

commonly used base course material. Before the pavements are designed by engineers,









the structural layer coefficient, a, is know for each material. Materials with higher a

values are desired since designers can use less of the stiffer material, which cuts costs.

Past studies on limestone base course materials have observed increase in stiffness

over time, and have credited these stiffness increases to calcite cementation. Gartland

(1979) used treatment methods which mimicked vadose and phreatic conditions, as well

as using different water sources to test their effect on stiffness increase. It was found that

the greatest stiffness increases occurred under phreatic conditions (no cycling) and when

using plain water. The time required for significant cementation to occur was not

generically identified. Graves (1987) continued on a similar study by testing mixtures

with varying ratios of calcite to quartz. Phreatic curing conditions were simulated in an

attempt to find the length of time required for a significant stiffness increase. It was found

that the highest stiffness increase in untreated materials occurred after 14 days. Materials

with higher carbonate to quartz ratios showed greater stiffness increases. Similar work

and field testing has caused the FDOT to reevaluate the structural coefficient for base

course materials (Smith and Lofroos, 1981). Structural layer coefficients were changed

from 0.15 to 0.18 as recommended to account for the future increases in stiffness, but the

authors felt that more testing should be completed.

2.2 Chemistry of Carbonate Cementation

The goal of this research was to create conditions which are favorable for carbonate

cementation, as past studies have shown that this is the mechanism responsible for

stiffness increases. Calcium carbonate is very common throughout the state of Florida.

Carbonate cements are responsible for a significant amount of the cements which hold

together sedimentary rocks. Calcium carbonate will also dissolve and reprecipitate as

under typical changes in environmental conditions.









Carbon dioxide, C02, plays a major role in the solubility of CaCO3. Various

sources of CO2 in water exist. Carbon dioxide from the atmosphere may dissolve in

falling rainwater or CO2 may be provided to groundwater by bacteria or other organisms

in soil. With increased CO2 levels in water, more CaCO3 can be dissolved. Miller (1952)

described the process that CO2 in the atmosphere combines with water to form carbonic

acid which in turn reacts with calcium carbonate to form the soluble bicarbonate:

H20 + CO2 H2CO3 H H + (HCO3)-

CaCO3 + H+ + (HCO3)- Ca2+ + 2(HCO3)

These reactions show that CO2 gas must be present in order for the calcium carbonate to

dissolve or precipitate. Bricker (1971) states that the emplacement of carbonate cements

require precipitation from solution. Also, one way that CaCO3 can be made

supersaturated (and thus more able to precipitate) is through pressure reduction, or by

having local pressure gradients adjacent to grain contacts.

Other work has been done on the pore filling material. Lindholm (1974) states that

aragonite, a polymorph of calcite, is instable at near-surface environmental conditions.

Aragonite is not expected to be present in the base course materials, therefore only

rhombohedral calcite crystals are expected to be found. Although calcite cements may

precipitate, Moore (1989) notes that much of the porosity in limestones is intraparticle,

which is unique to carbonates. The living chambers, or shells, of various organisms

provide this source of porosity. Although calcite cement may be present in such pores,

they would not contribute to any stiffness increase. Caution must be used when searching

for calcite crystals, as this may be the case.









2.3 Kelvin's Equation

The use of saturated salt solutions is a way to control the relative humidity in a

confined space. Saturated salt solutions are able to adsorb relatively large quantities of

water while maintaining a constant relative humidity (Lu and Likos, 2004). Also, the

resulting relative humidities from the use of saturated salt solutions will cause the

pressure gradients which will drive the calcium carbonate precipitation within the pore

spaces. Kelvin's equation governs the relationship between the pressure changes across a

curved air-liquid boundary to the vapor pressure above the boundary. One form of

Kelvin's equation can be written:

4Tsvw
ln(RH) =- (2.1)
dRT

where RH is the relative humidity, Ts is surface tension (N/m), vw is the partial molar

volume of water vapor (m3/mol), d is the pore diameter (m), R is the universal gas

constant (N-m/K-mol) and Tis temperature (K). The pore structure can be idealized as a

system of capillary tubes with diameter d. These capillaries will fill with liquid and form

a meniscus dependant on the above variables. In the presence of a given relative

humidity, the pores will either lose or gain water, causing the meniscus to change and the

resulting vapor pressure above the air-liquid boundary will cause a pressure gradient to

exist within the material pores. The effect of curvature on the vapor pressures explains

the ability of the vapors and solutions in the pores to supersaturate (Shaw, 1992). Figure

2-2 shows the relationship between relative humidity and the pore diameter which it will

effect.

The relative humidities exhibited by the saturated salt solutions effects the pore

water in specimens. The relative humidity of the saturated salt solutions will cause the









pore water to evaporate until equilibrium is reached between the vapor and liquid in the

pore spaces, which causes suction. Kelvin's equation can also be rewritten in terms of

total suction as:

RT
yVt ln(RH) (2.2)
VwOCOv

where Vt is the total soil suction (kPa), vwo is the specific volume of the liquid (m3/kg), coy

is the molecular mass of the liquid vapor (kg/kmol), and R and Tare defined as above.

Figure 2-3 shows the relationship between relative humidity and total suction.

2.4 Compaction Issues

It is proposed that the specimens be compacted at 1% wet of the optimum moisture

content even though for granular materials, this generally decreases initial stiffness

values. This was done for two reasons. First, the extra fluid will be able to contain more

calcium carbonate in solution. Second, laboratory compaction curves generally yield

somewhat lower optimum moisture contents than the actual field optimum (Lambe and

Whitman, 1969). It is hoped that this will mimic field results better and more calcite

cements will precipitate, resulting in higher stiffness increases.












al


SN1 = D, x a


BASE
D2 a2 SN2 = D2X a2



SUB-BASE
D3 a3 SN3 = D3X a3


Figure 2-1. Schematic of pavement layers showing concept of structural numbers.


1.E-09 1.E-08 1.E-07

Pore Diameter (meters)

General relationship between pore diameter and relative humidity.


AC


SN


1.0

0.8

0.6

0.4

0.2

0.0
1.E-10


Figure 2-2.


1.E-06


D,










1.E+07

1.E+06

a 1.E+05
a-

S1.E+04

1.E+03

o 1.E+02

1.E+01

1.E+00 -
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Relative Humidity


General relationship between total suction and relative humidity.


Figure 2-3.














CHAPTER 3
MATERIALS AND METHODS

3.1 Selection of Materials

For roadway construction projects, the State of Florida allows the contractor to

choose the base course material in accordance with standard specifications, although

many contractors favor local materials as transportation costs are the major deciding

factor. There are many acceptable aggregate sources from different geological formations

across the State of Florida. The stiffness of these limestone base course materials is based

on many factors. The gradation, mineralogy, particle shape, moisture content and

compactive effort will determine the initial stiffness of the base course material.

The objective of this research was to better understand the stiffness gain

mechanism in base course material. As stated earlier, the physical and mineralogical

properties of Florida limestones vary from one geologic formation to the other, as well as

within the formations themselves. Three commonly used limestones from across Florida

were chosen as representative aggregates. The base course materials chosen were Ocala

limestone, Miami limestone and Loxahatchee shell rock (mines 26002, 87090 and 93406,

respectively, Fig. 3-1). These aggregates come from the Ocala Group, Miami Oolite and

Anastasia Formation, respectively.

For comparison, a field core taken from Glades County, Florida will be examined.

The base course material in the Glades core appears to be Miami limestone based on

physical characteristics and specific gravity, although it is uncertain what mine the

material originated from as attempts at verification have been unsuccessful.









3.2 Material Preparation

Aggregate was obtained from each of the three quarries in Florida. The material

was then dried and sieved to obtain grain size distribution curves as shown in Fig. 3-2.

Sieve analysis shows that the Miami limestone is the coarsest material, followed by the

Loxahatchee shell rock then the Ocala limestone. The Ocala Limestone had the highest

percentage of material passing the #200 sieve, followed by the Miami limestone and then

the Loxahatchee shell rock. Materials were separated by the #4 sieve in order to separate

the coarse and fine aggregate. Prior to compaction, specimens were remixed according to

the overall proportions in an attempt to maximize uniformity for the multiple specimens.

Material greater than 34" was omitted because there is a maximum allowable aggregate

size for both the resonant column (ASTM D 4015) and Limerock Bearing Ratio (LBR)

testing (FM 5-515).

Modified Proctor (ASTM D 1557) and LBR testing was also completed on the

aggregates in order to verify that the materials meet the FDOT standards. Detailed

Modified Proctor and LBR data are presented in Appendix A. The LBR testing was

performed in accordance with FM 5-515 except for the fact that, as stated earlier, material

greater than 34" was discarded instead of crushed to 34" as required in the test. The FDOT

State Materials Office (SMO) completed Modified Proctor and LBR testing on the three

materials and descriptive data is given in Table 3-1. It should be noted that the material

from the Ocala quarry did not meet the minimum required LBR value of 100 as shown in

Table 3-1, but was used regardless since the increase in stiffness is of concern rather than

the initial stiffness values.









3.3 Compaction Procedures

Modified Proctor data gave the optimum moisture content required for compaction.

Materials were compacted at 1% wet of the optimum moisture content (See

LITERATURE REVIEW) into 4" diameter by 8" height plastic cylinders because

resonant column testing requires an aspect ratio of no less than 2:1. It should be noted

these dimensions are different from ASTM D 1557 which requires either a 4" or 6"

diameter by 4.584" height rigid metal mold. Plastic cylinders were chosen because

portions would later be sawed out for the destructive testing portion of this experiment.

Compaction procedures from ASTM D 1557 had to be modified to ensure that the

modified compactive effort of 56,000 ft-lbf/ft3 was still achieved. The specimens were

compacted in 9 layers with 25 blows per layer to achieve the Modified Proctor density.

The 10 pound hammer and 18" drop were still used. Materials were compacted using a

Rainhart automatic tamper at the FDOT SMO.

Two specimens were compacted for each testing variation and the resulting

modulus values and moisture content reductions were averaged. The testing variations

consisted of four different time periods and three different curing humidities. In total, 24

duplicate specimens were compacted for each of the three aggregate sources.

3.4 Curing Procedures

Curing periods of 2, 7, 15 and 30 days were used in this study to assess stiffness

increase over time. After compaction, the cylinders were placed in curing chambers for

the allotted time periods. Desiccator cabinets of approximately 0.75 ft3 were used as

curing chambers. The seals were previously tested to ensure no leakage. To maintain a

constant relative humidity in each of the chambers, different saturated salt solutions were









used. It was desired to use solutions which exhibited high, medium and low relative

humidities.

Saturated salt solutions were prepared by mixing a quantity of lithium chloride (RH

S11%), magnesium nitrate (RH z 53%) or potassium sulfate (RH Z 97%) with gently

heated, distilled water. Once the solution cools, excess solids will precipitate if the

solution is beyond saturation. This allows moisture from the compacted specimens to be

absorbed by the saturated salt solutions until excess solids are no longer present.

Approximately 250 mL of solution were used in each of the curing chambers and either

replaced or remixed as necessary to ensure that solids were present. Conditions inside

curing chambers were monitored with the use of temperature and humidity gages. The

temperature dependencies of the saturated salt solutions according to ASTM E 104 are

presented in Table 3-2. The temperature remained at a constant 250 C within the

chambers throughout the test period.

3.5 Resonant Column Testing

Testing for an increase in stiffness for each of the materials was the main concern

of this research. The testing program was designed to investigate the stiffness increase as

a function of relative humidity and time. It was important that the modulus test be non-

destructive as the later tests that would characterize different properties of the materials

are destructive.

The free-free resonant-column modulus test is a small strain (less than 10-4 in/in)

test which consists of applying a vibration excitation at one end of the specimen and

measuring the resulting vibration patterns from the applied compression wave at the other

end. Fifteen tests were conducted and averaged to obtain the resonant frequency of each

specimen. The resonant frequency was then used along with and geometric properties and









the compression wave speed to calculate Young's modulus values. Initial measurements

were taken immediately after compaction and final measurements were taken after the

allotted curing time for each specimen. After testing was completed, cylinders were

capped to ensure no further loss in moisture.

3.6 Scanning Electron Microscopy

3.6.1 Sample Preparation

In order to view specimens in the SEM, portions of the compacted specimens had

to be cut in order to be mounted and fit in the SEM. A major problem which must be

overcome is the brittleness of the compacted materials. Upon cutting the material from

the cylinders to the size required to fit in the SEM (approximately 1 in3), most of the

material will break apart from the vibration caused by the cutting saw which prevents the

examination of coherent pieces. In order to prepare samples for SEM analysis, large

slices measuring approximately 1.5" thick and 4" diameter were cut from the plastic

cylinders dried in an oven. The pieces were further broken by hand into the 1 in3 size

required to fit in the SEM mounting chamber. These samples were impregnated with a

low viscosity epoxy in order to fill as many voids as possible. Epoxied samples were then

cut and sanded until polished. When viewed in the SEM, the density of the epoxy makes

it appears black, allowing for easy identification of voids.

3.6.2 Scanning Electron Microscopy Analysis

SEM examinations of the three compacted materials and the field core were

conducted in order to search for the presence of calcite crystals. Specimens measured

approximately 3.0 cm by 2.5 cm and were flat. Fourteen random points were selected on

each specimen and images were taken. Any calcite crystals visible at this scale were

further investigated. As stated earlier, samples were polished so that the SEM settings









would not need to be reconfigured while investigating each sample and also in order to

run Energy Dispersive Spectrometer (EDS). The spectrometer identified and mapped the

chemicals present for selected images.

SEM examinations were conducted using a Hitachi S-3000 N Scanning Electron

Microscope with an EDS x-ray analyzer at the UF Department of Civil and Coastal

Engineering.

3.6.3 Imaging Software

ImageJ is an image processing program made available to the public. It was used to

characterize the number and size of voids in each of the SEM images. The SEM images

used for pore size analysis were taken at 90X magnification which limited the minimum

void size that the imaging software could discern as it only counts pixels. In the images, 1

mm is equal to 880 pixels and so the software will be able to recognize pore sizes greater

than 2 im. It was desired to count voids in this range as weight-volume relationships

were used to calculate bulk porosity and mercury porosimeter measurements were used to

describe pores smaller than 100 nm. If a higher magnification was used, it was felt that

the 14 images for each sample would not be a large enough sample population to describe

the pore structure.

A subroutine in ImageJ converted the SEM images from grayscale to binary. The

voids appeared black and were counted and sorted by total area. The software allows the

user to set the minimum pore size that the software will recognize.

3.7 Porosity Measurements

Porosity measurements were completed on 30-day samples cured under low

relative humidity. Specimens must be completely dry as any moisture will be turned into

compressible water vapor. This test is ran in two stages which cover a pore range









between approximately 150 [m and 1.8 nm. The specimen for this apparatus must fit

inside a glass sample cell as shown in Figure 3-3. Representative samples were difficult

to obtain since the compacted material is approximately 1650 cm3 and the mercury

porosimeter device accepts specimens of approximately 1.5 cm3. In an attempt to test

representative samples, aggregate pieces were taken with finer particles attached (no

"clean" aggregate).

All materials were tested in accordance with ASTM D 4404 using a Quantachrome

Autoscan 60 Mercury Porosimeter at the UF Particle Engineering Research Center

(PERC). Testing was completed by PERC personnel.

3.8 X-Ray Diffraction

X-Ray Diffraction (XRD) measurements were taken on the three virgin aggregate

sources. Approximately 5 grams of each aggregate was ground up with a mortar and

pestle and passed through the #200 sieve. From this, chemical and crystallographic

composition was obtained. The resulting plots are shown in Figs. 3-4, 3-5 and 3-6. These

plot show various intensities coupled with 2*0 angles. Each 2*0 angle pattern

corresponds to a unique crystalline structure, thereby making it possible not only to detect

quartz and calcite, but also to distinguish calcite from its polymorph aragonite. The

intensities at each angle, along with other data that may be obtained from the geometry of

these plots, represent the relative quantity of each mineral present. Minerals were

identified by matching the observed patterns to a mineralogical powder diffraction

database maintained by the Univ. of Arizona. From this database, quartz is known to

diffract with a major peak at 20 between 26.60 and 26.70, calcite with a major peak

(subsequent peaks exist and are present) at 20 between 29.40 and 29.50 and aragonite

with a major peak at 20 between 26.20 and 26.3.






18


As illustrated, calcite is the main component of each aggregate source. The Ocala

limestone is almost exclusively comprised of calcite while the Miami limestone and

Loxahatchee shell rock are comprised of calcite and quartz. It should also be noted that

aragonite was not present in any of the aggregate sources.

All materials were tested using a Philips APD 3720 powder diffractometer at the

UF Major Analytical Instrumentation Center (MAIC). Testing was completed by MAIC

personnel.




















26002


93406


87090


^p
+ P*~ -ra


Figure 3-1. Map of Florida showing approximate locations of aggregate source mines.














































/

cU II 0


0 0 0 0 0 0 0 0 0
m) co r- (D 10 'T co N N -


6U!SSed ZU03JOd


E



cn
N



CD
















Table 3-1. Descriptive data for three limestone base course materials.
Maximum Dry Optimum Water
Carbonate Density Content
Material Mine No. Content (pcf) (%) LBR
Ocala 26-002 99.2 111.8 13.4 92
Miami 87-090 77.5 129.6 7.8 175
Loxahatchee 93-406 53.8 127.2 7.9 131


Table 3-2. Equilibrium relative humidity values for saturated aqueous salt solutions.


Temperature
(C)
20
25
30


Lithium Chloride,
LiCl H20
11.3 + 0.3
11.3 + 0.3
11.3 + 0.2


Magnesium Nitrate,
Mg(NO3)2 6H20
54.4 + 0.2
52.9 + 0.2
51.4 + 0.2


Potassium Sulfate,
K2SO4
97.6 + 0.5
97.3 + 0.5
97.0 + 0.4


























SAMPLE CELL


1.0 cm
i_


SAMPLE


Figure 3-3. Mercury Porosimeter specimen set-up. Mercury is intruded from right
side. Approximate specimen size is 1 cm x 2 cm.


i









5000

4000

, 3000

" 2000

1000

0
25


30


n _
40
Angle (2*0)


Figure 3-4. X-Ray diffraction plot for untreated Ocala limestone.





5000

4000

S3000

r 2000

1000

0
25 30 35 40 45 50 55
Angle (2*0)


Figure 3-5. X-Ray diffraction plot for untreated Miami limestone.


h ~nn


'= ,-
























5000

4000

, 3000

" 2000

1000

0-
25


30 35 40 45 50 55
Angle (2*0)


Figure 3-6. X-Ray diffraction plot for untreated Loxahatchee limestone.














CHAPTER 4
RESULTS AND DISCUSSION

4.1 Resonant Column Results

The main test to determine the increase in modulus of the conditioned limestones

was the free-free resonant column test. Modulus and moisture content data for the

different materials and curing conditions are given in Tables 4-1 through 4-3. The

Young's modulus is compared relative to the 8 averaged initial modulus values for the

different relative humidities and the different compacted base course materials. Modulus

values are plotted as a percent increase over this initial reference modulus. Values

reported are averages of duplicate molds tested for each base course material and curing

condition. The data was plotted in Figs. 4-1 through 4-3 in order to better illustrate the

increases in stiffness. Each material showed increases in stiffness for all three relative

humidity levels with the greatest increase occurring when cured under low relative

humidity conditions. The stiffness of the Ocala limestone increased by approximately

2100%, the Miami limestone by 1600% and the Loxahatchee shell rock by 940% when

cured under low relative humidity conditions. Modulus values for materials cured under

high relative humidity conditions appear to be near their maximum as values are only

slightly increasing after 7 days. The Loxahatchee shell rock showed the lowest overall

modulus increases for each curing relative humidity and in general, modulus values only

slightly increase after 15 days. The modulus values of the Ocala and Miami limestones

increase at an almost constant rate for both the medium and low relative humidities and it

is evident from the plots that the modulus values show no sign of reaching a maximum









value. However, it is expected that the increase in modulus will diminish just as the

modulus values for the high relative humidity tests have. Resonant Column Testing data

is reported in Appendix B.

The initial weights for each test cylinder were record and compared with the

weights after curing. This weight loss is due to the saturated salt solutions absorbing

moisture from the specimens. The percentage of initial moisture lost was plotted against

the percent increase over the reference modulus as shown in Figs. 4-4 through 4-6. Each

material showed an approximately linear relationship between the percent moisture lost

and the percent increase in modulus, regardless of curing conditions. The Ocala limestone

gained more stiffness per moisture lost followed by the Miami limestone and finally the

Loxahatchee shell rock. These trends show that over this testing period the increase in

stiffness is related to moisture loss.

4.2 Scanning Electron Microscope Analysis

Scanning electron microscopy techniques were used in order to see whether the

moisture loss resulted in calcite cement growth, which could be responsible for the

observed stiffness increase in the resonant column testing portion of the research.

Specimens from materials cured for 30 days under low relative humidity were prepared

and examined because it was felt that they had the highest potential for showing calcite

cement bonding. Also, a section from a field core from Glades County was examined for

comparison with the laboratory compacted specimens.

After modulus testing, the selected specimens were cut out of the cylinder molds

and prepared for SEM analysis as stated in Chapter 3. Fourteen random locations on each

specimen were examined for the presence of calcite crystal and patterns which would

suggest growth. Selected images from the analysis showing typical characteristics are









presented. Figures 4-7 through 4-11 are typical examples of the Ocala, Miami and

Loxahatchee images. The light aggregates are calcium carbonate, grey aggregates are

quartz and the black areas are the intruded epoxy. SEM exploration of the laboratory

compacted specimens did not reveal zones with calcite cement growth. Figure 4-12

reveals a zone in the Loxahatchee shell rock containing textures related to calcite crystals.

Figure 4-13 is a close-up of the area of interest in Fig. 4-12, but reveals that the crystals

are only intraparticle and therefore would not contribute to any stiffness increase from

aggregate-to-aggregate cementation.

Scanning electron micrographs of the Glades core were also taken. Typically, the

Glades core shows less void area than the compacted specimens. Also, many of the

Glades core images contained easy to spot, relatively large calcite crystals which are

appear to be growing between aggregates. Typical features of the Glades core are shown

in Figs. 4-14 through 4-18. Rhombohedral calcite crystals are shown filling in the pore

spaces in Figures 4-16 and 4-18.

Additionally, element maps were taken for selected SEM images. Element maps for

the Ocala limestone consist of calcium, carbon and oxygen which indicates that only

calcite is present. Element maps for the Miami limestone and Loxahatchee shell rock

consist of calcium, carbon, oxygen and silicon which indicate the presence of calcite and

quartz. These measurements are in agreement with the XRD analysis.

4.3 Porosity Measurements

The initial moisture content values were taken for each material during the modulus

testing portion of this research. The theoretical porosity was calculated using classic

weight-volume relationships. Descriptive properties are presented in Table 4-4. These

values represent the bulk porosity for the materials and are useful for comparing the









different methods for finding porosity. The calculations for the bulk specimens show that

the porosity for these materials ranges between 0.238 and 0.318.

Mercury Porosimeter testing gave further insight into the void structure of the

compacted limestone. Mercury porosimetry is able to give distributions of pore sizes

while bulk porosity measurements do not. The mercury porosimetry test is capable of

giving measurements accurate to diameters ranging between 3.6 nm and 100 inm. This

range of pore diameters corresponds with Kelvin's equation as stated in eq (2.1) which

shows the pore diameters that are affected by the relative humidities. Figure 4-19 shows a

plot of this equation for typical values of water of Ts = 0.072 N/m, vw = 1.8x105 m3/mol.

The temperature used was T= 298.15 K and the universal gas constant R = 8.314472

N-m/K-mol. Results in Figure 4-20 show that the Ocala limestone has the greatest amount

of fine pores of all the materials followed by the Miami limestone and finally the

Loxahatchee shell rock. The slope of each line indicates the number of pores at each

diameter. The flat portions of the plot ranging between 10-6 and 10-5 meters are due to

testing inaccuracies. As stated earlier, the test is run in two stages and it is between these

ranges that the transition between testing stages occurs.

The ImageJ software was used to analyze all the images from the SEM exploration.

Each image was made binary and the software counted and gave the area for each void.

Imaging analysis was used to describe the pore diameter data between 2x10-6 and 1x10-3

meters which covers the range of the transition measurements in the mercury

porosimetry. Data was reduced and summary statistics are shown in Table 4-5.

Histograms of the pore data ranging between 2x10-6 and 2x105 meters are presented in

Figs. 4-21 through 4-24, as this data accounts for over 97% of the pores found with the









software. Figures 4-25 through 4-27 presents the pore diameter distribution from ImageJ

analysis in relation to porosity and shows what portion of the total porosity the analysis

represents. The Glades core data was omitted because the bulk porosity was not known.

An example of the image processing steps is shown in Fig. 4-28.

The three different porosity measurements were compared in Table 4-6. The

porosity results show that for both the Ocala and Miami limestones, the Mercury

Porosimeter test reports higher porosity values than the SEM image analysis, but for the

Loxahatchee shell rock, the opposite is true. These results can lead one to the conclusion

that overall, the pores in the Ocala and Miami limestone are generally smaller and those

found in the Loxahatchee shell rock are generally larger.

4.4 Discussion

The resonant column test indicated stiffness increases for all materials. The Ocala

limestone showed the greatest rate for stiffness increase while Loxahatchee shell rock

showed the slowest rate of stiffness increase. Although solubility calculations show that

in the time frame for the experiment, only a small amount of calcite cement was able to

precipitate, SEM exploration did not reveal the presence of cementing calcite crystals in

any of the laboratory compacted specimens. The maximum volume of calcite able to

precipitate was 9.0x10-4 cm3 in the Ocala limestone cured under low relative humidity for

30 days, which was the best-case scenario. The cylinder volume was approximately 1650

cm3, so this equates to 0.00005% of new material precipitation. Calculations appear in

Appendix C. This amount of calcite precipitation would be very difficult to locate.

However, images taken of the Glades core commonly show cementing calcite crystals

and filling most voids.









Even though calculations show that calcite cement was able to precipitate, it is

believed that it is not the source for the increase in stiffness. Instead, suction from the loss

of water in the pore spaces is reasonable. The potential for stiffness increase due to

suction is determined from the Kelvin's equation as stated in eq (2.2). Figure 4.29 shows

a plot of this equation for typical values for water of vo = 0.001 m3/kg, co, = 18.016

kg/kmol and T and R are previously defined. Table 4.7 shows this theoretical suction

pressure for each of the relative humidities used. The theoretical total suction values

differ by approximately an order of magnitude which provides an explanation for the

difference in stiffness increases for each curing condition. It is felt that the materials

cured under the medium and low relative humidities did not reach equilibrium with the

saturated salt solutions and therefore did not reach the potential moisture loss to show the

full effects of the stiffness increase due to the suction pressures. The materials cured

under high relative humidity reached near-constant moisture contents, so the effects of

the suction pressure are shown in the material stiffness.











Table 4-1. Summary of Ocala limestone under different curing conditions. Average
stiffness gain and reduction in moisture content versus time.
Average Time Average % Decrease Average % Increase
Curing Type (days) in Initial Moisture in Young's Modulus
Low RH 1.99 1.05% 142.0%
7.94 3.13% 573.5%
15.83 5.04% 959.7%
32.10 9.96% 2108.6%
Medium RH 1.99 0.76% 71.4%
7.95 2.52% 551.0%
15.83 3.35% 657.4%
32.04 8.03% 1513.3%
High RH 1.99 0.56% 58.2%
7.97 1.18% 466.1%
15.84 1.55% 475.1%
32.04 1.94% 536.8%











Table 4-2. Summary of Miami limestone under different curing conditions. Average
stiffness gain and reduction in moisture content versus time.
Average Time Average % Decrease Average % Increase
Curing Type (days) in Initial Moisture in Young's Modulus
Low RH 2.05 1.36% 42.0%
7.77 3.82% 457.9%
15.76 7.20% 971.8%
31.09 11.17% 1627.6%
Medium RH 2.05 1.03% 59.1%
7.79 3.39% 221.0%
15.77 4.86% 647.3%
31.07 9.35% 1118.8%
High RH 2.05 0.73% 22.6%
7.81 1.42% 28.0%
15.78 1.73% 73.0%
31.10 2.68% 149.4%


























Table 4-3. Summary of Loxahatchee shell rock under different curing conditions.
Average stiffness gain and reduction in moisture content versus time.
Average Time Average % Decrease Average % Increase
Curing Type (days) in Initial Moisture in Young's Modulus
Low RH 2.00 2.18% 170.4%
7.82 4.02% 354.6%
15.83 8.50% 798.8%
31.24 12.76% 940.0%
Medium RH 1.98 1.19% 121.0%
7.83 2.90% 265.9%
15.84 5.33% 596.9%
31.24 8.43% 637.9%
High RH 1.97 0.34% 52.4%
7.85 1.12% 187.2%
15.85 1.38% 277.1%
31.24 2.21% 307.7%










u 2400%
-5

0 2000%

S1600%
c
o 1200%
a-

a 800%

400%

0%


- Low
- Medium
-aHigh


0 5 10 15 20
Time (days)


25 30 35


Figure 4-1.






u 2400%

0 2000%

-1600%
c
o 1200%

a 800%
U,)

400%

0%


Ocala limestone stiffness gain versus time for different relative humidities.












Low
Medium
High


0 5 10 15 20 25 30 35
Time (days)


Figure 4-2. Miami limestone stiffness gain versus time for different relative
humidities.










2400%

2000%

1600%

1200%

800%

400%

0%


0 5 10 15 20
Time (days)


25 30 35


Figure 4-3. Loxahatchee shell rock stiffness gain versus time for different relative
humidities.




u, 2400%

0
| 2000% -

-S 1600%
-" -- Low
o 1200% Medium
.= +- High
S800%

o 400%

0%
0% 2% 4% 6% 8% 10% 12% 14%
% Decrease in Initial Moisture


Figure 4-4.


Ocala limestone stiffness gain versus decrease in initial moisture for
different relative humidities.


-- Low
- Medium
-aHigh










, 2400%

" 2000%

-, 1600%
00
o 1200%


800%

400%

0%
0% 2% 4% 6% 8% 10% 12% 14%
% Decrease in Initial Moisture


Figure 4-5.


-- Low
--Medium
-a-High


Miami limestone stiffness gain versus decrease in initial moisture for
different relative humidities.


u 2400%

" 2000%

-, 1600%
0 0
o 1200%


-- Low
- Medium
-- High


w 800%

- 400%

0% ,,-
0% 2% 4% 6% 8% 10% 12% 14%
% Decrease in Initial Moisture


Figure 4-6. Loxahatchee shell rock stiffness gain versus decrease in initial moisture
for different relative humidities.








































Ocala limestone typical image 1.


Ocala limestone typical image 2.


Figure 4-7.


Figure 4-8.


--.r r
.r
.i a rr~br
(I 'EL

a :II,'r: ~i~(t I

~?d~~:1

I: i
a9~ r. -



























Miami limestone typical image 1.


Figure 4-10. Miami limestone typical image 2.


Figure 4-9.


u

B






















Loxahatchee shell rock typical image 1.


Figure 4-12. Loxahatchee shell rock image 2 showing zone of possible calcite crystal
growth on left side.


Figure 4-11.


~4]4~88 ~~~j-
oa~C~"~:
'Q,"s!
~--cs~ L s1~slS 1











-4.
S VAR'


Figure 4-13. Loxahatchee shell rock close-up of highlighted region in Fig. 4-12.


Figure 4-14. Glades core typical image 1.































Figure 4-15.


Glades core typical image 2 showing zone of calcite crystal growth.


*' 1














.9
.4~ iia


Figure 4-16. Glades core close-up of highlighted region in Fig. 4-15.










L C

iJt


Figure 4-17.


Glades core typical image 3 showing zone of calcite crystal growth.


~4f L~et. .j


Figure 4-18. Glades core close-up of highlighted region in Fig. 4-17.












Table 4-4. Average bulk properties of base course materials.
Average Moisture
Specimen Specific Gravity Content (%) Porosity, n
Ocala Limestone 2.75 14.28 0.318
Miami Limestone 2.78 8.76 0.238
Loxahatchee Shell Rock 2.84 9.00 0.266


Glades Core


2.78


Table 4-5. Summary statistics for pore sizes from ImageJ analysis.


Specimen
Mean
Standard Error
Median
Mode
Standard Deviation
Sample Variance
Kurtosis
Skewness
Range
Minimum
Maximum
Sum
Count


Ocala
6.07E-06
8.59E-08
3.63E-06
2.57E-06
1.41E-05
1.99E-10
493.6809
18.9514
0.000522
2.57E-06
0.000524
0.163367
26917


Miami
5.55E-06
4.54E-08
3.63E-06
2.57E-06
9.28E-06
8.62E-11
701.3346
19.53987
0.000532
2.57E-06
0.000535
0.231454
41715


Loxahatchee
6.31E-06
1.37E-07
3.84E-06
2.56E-06
1.76E-05
3.1E-10
926.6147
24.77442
0.000932
2.56E-06
0.000934
0.104128
16497


Glades Core
5.39E-06
7.37E-08
3.63E-06
2.56E-06
1.09E-05
1.18E-10
1008.251
24.98864
0.000651
2.56E-06
0.000654
0.116765
21677


Table 4-6. Comparison of porosity values from different methods.
Bulk Mercury SEM Image
Specimen Measurements Porosimetry Analysis
Ocala Limestone 0.318 0.235 0.183
Miami Limestone 0.238 0.150 0.147
Loxahatchee Shell Rock 0.266 0.101 0.170


0.088


Glades Core


---


0.101
























1.0
0.973 ....................
0.9
0.8

0.7

0 0.6
0. 0.529 .. ... ......
0 0.5
I
S0.4D r
^ 0.3

0.2
0.113
0.1 ---------------------

0.0
1.E-10 1.E-09 1.E-08 1.E-07 1.E-06
Pore Diameter (meters)


Figure 4-19. Relative humidity values and corresponding affected pore diameters.
Horizontal lines represent targeted relative humidities.



























o

f =5
00





0




? o
E II
-E 0




oo
'-
0 -
E 0


o
0


0?

















10 0 10 0 0 o
S0 0

AI!soJod WlWOI|
i ^-^' // /:EE
J/^ ^ / : .




/^~~ ~ /// :Il
/ ~ ~~ / Q
/~~~~P / / T!r^r
















15300




5921


II2171


.0E-06


8.0E-06


1111 609 399

1.2E-05


280 185 134


1.6E-05


Pore Diameter (meters)


Figure 4-21. Pore diameter histogram from ImageJ analysis for Ocala limestone.
Values above bars are frequency.







100%
-0 100%


879 521 392 243 189


1.2E-05


1.6E-05


2.0E-05


Pore Diameter (meters)


Figure 4-22. Pore diameter histogram from ImageJ analysis for Miami limestone.
Values above bars are frequency.


100%


80%


60%


40%


20%


0%
4


2.0E-05
2.0E-05


80%

60%

40%

20%

0%


23664


9654


3505


1642


4.0E-06


8.0E-06
















8920



3900

1558

E-06 8. E-
OE-06 8.0E-06


351 230 158

1.2E-05 1.6E-05
1.2E-05 1.6E-05


121 65

2.OE-05
2.0E-05


Pore Diameter (meters)


Figure 4-23. Pore diameter histogram from ImageJ analysis for Loxahatchee shell rock.
Values above bars are frequency.




100%


80%


60%


40%


20%


13030


4678


1687


4.0E-06


8.0E-06


779 424 212 157 130 103


1.2E-05


1.6E-05


2.0E-05


Pore Diameter (meters)


Figure 4-24. Pore diameter histogram from ImageJ analysis for Glades core. Values
above bars are frequency.


100%


80%


60%


40%


20%


0%
4.











0.35
0
0.30
0.25
0.20
0.15
0.10
0.05
0.00
1.E-06


.318


1.E-05


1.E-04


1.E-03


Pore Diameter (meters)


Figure 4-25. Ocala limestone pore diameter distribution from ImageJ analysis in
relation to porosity. Horizontal line is the bulk porosity.


0.35
0.30
0.25 0.238
0.20
0.15
0.10
0.05
0.00
1.E-06


1.E-05


1.E-04


1.E-03


Pore Diameter (meters)


Figure 4-26. Miami limestone pore diameter distribution from ImageJ analysis in
relation to porosity. Horizontal line is the bulk porosity.



























0.35
0.30
^ 0.25
2 0.20
o
a-
- 0.15
0 0.10
0.05
0.00


0.266


1.E-06


1.E-05


1.E-04


1.E-03


Pore Diameter (meters)


Figure 4-27. Loxahatchee shell rock pore diameter distribution from ImageJ analysis in
relation to porosity. Horizontal line is the bulk porosity.







49



















-..^ ..






al l

**" ,*''-



',t f i ,t


A.4
**^*2wl.^ ^ -. 6 ,W. >Y-l' ;






















Figure 4-28. Image processing steps with ImageJ software. Example is from Ocala
specimen. A) Original SEM image taken in grayscale. B) Image converted
into binary. C) Binary image is converted into outlines and area data is
obtained.
"* .^ :.^ -^ -
Figre -2. Iageprcesingstps it Image sotwreExmlisfo ca
spcien A)Oiia E mg ae n rycl.B mg ovre
inobnr.C inr mg scnere nootiesadae aai
ob-taied











1.E+07

1.E+06

. 1.E+05
r-

g 1.E+04

" 1.E+03

5 1.E+02
I--


1.E+01

I C-i-nfl


I I


0.113 0.529 0.973


0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9


Relative Humidity


Figure 4-29.


Theoretical relative humidity values and corresponding total suction.
Vertical lines represent targeted relative humidities.


Table 4-7. Theoretical suction pressures for different relative humidities.
Suction Pressure Suction Pressure
Relative Humidity (kPa) (ksi)


Low
Medium
High


300,000
88,000
3800


43.6
12.8
0.55















CHAPTER 5
CONCLUSIONS AND RECOMMENDATIONS

5.1 Conclusions

1. Curing compacted specimens with different relative humidities resulted in

stiffness increases for each material type. Materials cured under low relative humidity

conditions showed the greatest increase in stiffness while materials cured under high

relative humidity conditions showed the lowest stiffness increase.

2. Materials cured under high relative humidity reached stable moisture contents

during the testing period. Materials cured under medium and low relative humidities did

not reach stable moisture contents in the allotted test period, but are likewise expected to

stabilize.

3. Stiffness increases in this experiment were due to increases in capillary suction

due to the removal of water from the system.

4. Materials with more fine pores in the sub-micron level and also more material

passing the #200 sieve resulted in greater stiffness increases. Ocala limestone showed the

greatest stiffness increase while Loxahatchee shell rock showed the lowest, which agrees

with this statement.

5. Materials showed a linear relationship between % increase in Young's modulus

and increased % reductions in moisture content. It is thought that the % increase in

Young's modulus will reach some maximum value, though the testing period was not

long enough to verify this.









6. Although all materials showed an increase in stiffness, calculations show the

potential crystal growth from calcite in solution was negligible. Expectantly, SEM

analysis did not reveal the presence of calcite crystals. It is concluded that the testing

period was not long enough to allow the materials to reach equilibrium with the saturated

salt solutions.

7. SEM imaging in the Glades core reveal the presence of relatively large calcite

crystals. The orientation of these crystals suggests that pores are being filled. Porosity

measurements in the Glades core also indicate that most of the pore volume has been

filled.

8. SEM analysis coupled with the ImageJ software provided excellent quantitative

analysis for describing voids.

5.2 Recommendations for Future Work

1. Roadway conditions of base course material should be studied. Sensors

recording the temperature, relative humidity, CO2 levels and moisture migration in pores

can be implemented during construction. Future test should be long term and mimic these

relevant field conditions rather than changing individual conditions that may be

irrelevant.

2. Doping the specimens with a know substance during compaction would be

beneficial when looking for new calcite growth. Due to the small quantities of calcite

crystals that precipitate and the heterogeneity of limestones, it is very difficult to

distinguish new crystal growth from crystals that may have formed hundreds or

thousands of years ago. Neoformed crystals would include the doped substance and

would be recognizable using EDS, XRD or cathodoluminescence techniques.






53


3. It may be coincidental that the materials with higher fines content resulted in

higher stiffness increases, but the effect of fines in regards to increases in stiffness should

be studied.

4. The effect of initial moisture content should be studied because contractors may

meet density requirements using moisture contents both wet and dry of the optimum. A

range of initial moisture contents and their effect on stiffness increase should be tested as

materials in this study were only compacted 1% wet of the optimum moisture content.















APPENDIX A
MODIFIED PROCTOR AND LBR RESULTS


e i
E s

0a

a a
ir

U,
Mrl


Ocala limestone Modified Proctor and LBR data


v9 tCO


MOISTURE (%)


_ ~


" -II I


Figure A-1.
























































S C


MOISTURE (%)

MOISTURE (%)


Miami limestone Modified Proctor and LBR data


C__


.. .1 .. A=


r u) (0 1-


CO 01


Figure A-2.























































0 I'- c C 0 C -


C3 S Co 0 -


MOISTURE(%)


Loxahatchee shell rock Modified Proctor and LBR data


_


yl II I


Figure A-3.
















APPENDIX B
RESONANT COLUMN TESTING DATA


Table B-1. Data for Ocala Limestone after Compaction
Quarry : Ocala Mold Wt: 0.242 Ibs
Pit Number : 26-002 Diameter: 4 in
Sample Number : 26-AII Height: 8 in
Testing Condition : Initial Volume: 100.531 in^3
_Volume: 0.0582 ft^3

Moisture Density,
Date, Time MIS Weight Freq. Vp E
Specimen Content p
(m/ddlyy hh:mm) (Ibs) () (Hz) (ftsec) (ksi)

26-L-02-1 9/1/07 23:40 8.05 14.44% 104 4.1714 139 0.56
26-L-02-2 9/4/07 23:40 8.07 14.14% 136 4.1821 181 0.95
26-L-07-1 8/18/07 20:55 7.99 14.31% 120 4.1393 160 0.74
26-L-07-2 8/18/07 21:05 7.97 14.49% 216 4.1286 288 2.38
26-L-14-1 7/15/07 19:50 8.03 14.00% 128 4.1607 171 0.84
26-L-14-2 8/7/07 19:55 7.99 14.37% 112 4.1393 149 0.64
26-L-30-1 7/15/07 19:30 8.03 14.36% 152 4.1607 203 1.19
26-L-30-2 7/15/07 19:35 8.04 14.35% 136 4.1660 181 0.95
26-M-02-1 9/1/07 23:45 8.03 14.55% 104 4.1607 139 0.56
26-M-02-2 9/4/07 23:45 8.06 14.32% 104 4.1767 139 0.56
26-M-07-1 8/18/07 20:45 8.00 14.35% 120 4.1447 160 0.74
26-M-07-2 8/18/07 20:50 8.06 14.18% 112 4.1767 149 0.65
26-M-14-1 7/15/07 19:50 8.00 14.19% 136 4.1447 181 0.95
26-M-14-2 8/7/07 19:45 8.00 14.19% 120 4.1447 160 0.74
26-M-30-1 7/15/07 19:20 8.09 14.02% 176 4.1927 235 1.60
26-M-30-2 7/15/07 19:25 8.08 14.14% 112 4.1874 149 0.65
26-H-02-1 9/1/07 23:50 8.05 14.35% 120 4.1714 160 0.74
26-H-02-2 9/4/07 23:50 8.01 14.33% 128 4.1500 171 0.84
26-H-07-1 8/18/07 20:30 7.96 14.45% 120 4.1233 160 0.73
26-H-07-2 8/18/07 20:40 8.01 14.43% 120 4.1500 160 0.74
26-H-14-1 7/15/07 19:40 8.02 14.07% 136 4.1553 181 0.95
26-H-14-2 8/7/07 19:40 7.97 14.30% 128 4.1286 171 0.84
26-H-30-1 7/15/07 19:10 8.04 14.04% 120 4.1660 160 0.74
26-H-30-2 7/15/07 19:15 8.03 14.24% 120 4.1607 160 0.74










Table B-2. Data for Ocala Limestone after Curing
Quarry : Ocala Mold Wt: 0.242 Ibs
Pit Number : 26-002 Diameter: 4 in
Sample Number : 26-All Height: 8 in
Testing Condition : Final Volume: 100.531 in^3
Volume: 0.0582 ft^3

M/S Moisture
Date, Time S Moistur eq. Density, p Vp E
Specimen Days Weight Content si)
(m/ddlyy hh:mm) (Hz) (Ibs/ft3) (ftsec) (ksi)
-__ (Ibs) (%) _
26-L-02-1 9/3/07 23:40 2.00 8.04 14.29% 152 4.1660 203 1.19
26-L-02-2 9/6/07 23:00 1.97 8.05 13.99% 224 4.1714 299 2.58
26-L-07-1 8/26/07 19:25 7.94 7.96 13.90% 376 4.1233 501 7.20
26-L-07-2 8/26/07 19:30 7.93 7.93 14.00% 416 4.1073 555 8.78
26-L-14-1 8/1/07 13:45 16.75 7.95 13.00% 416 4.1179 555 8.80
26-L-14-2 8/22/07 17:40 14.91 7.95 13.94% 368 4.1179 491 6.88
26-L-30-1 8/16/07 20:25 32.04 7.92 12.92% 696 4.1019 928 24.53
26-L-30-2 8/16/07 23:30 32.16 7.93 12.93% 664 4.1073 885 22.36
26-M-02-1 9/3/07 23:45 2.00 8.02 14.48% 144 4.1553 192 1.06
26-M-02-2 9/6/07 23:05 1.97 8.05 14.17% 128 4.1714 171 0.84
26-M-07-1 8/26/07 19:35 7.95 7.97 13.97% 336 4.1286 448 5.75
26-M-07-2 8/26/07 19:40 7.95 8.04 13.84% 256 4.1660 341 3.37
26-M-14-1 8/1/07 13:50 16.75 7.95 13.55% 360 4.1179 480 6.59
26-M-14-2 8/22/07 17:45 14.92 7.97 13.88% 344 4.1286 459 6.03
26-M-30-1 8/16/07 20:15 32.04 8.00 12.88% 568 4.1447 757 16.51
26-M-30-2 8/16/07 20:20 32.04 7.99 13.02% 528 4.1393 704 14.25
26-H-02-1 9/3/07 23:50 2.00 8.05 14.32% 152 4.1714 203 1.19
26-H-02-2 9/6/07 23:10 1.97 8.00 14.20% 160 4.1447 213 1.31
26-H-07-1 8/26/07 19:45 7.97 7.95 14.28% 306 4.1179 408 4.76
26-H-07-2 8/26/07 19:50 7.97 7.99 14.26% 264 4.1393 352 3.56
26-H-14-1 8/1/07 13:55 16.76 8.01 13.85% 360 4.1500 480 6.64
26-H-14-2 8/22/07 17:50 14.92 7.95 14.08% 272 4.1179 363 3.76
26-H-30-1 8/16/07 20:05 32.04 8.02 13.76% 344 4.1553 459 6.07
26-H-30-2 8/16/07 20:10 32.04 8.01 13.97% 256 4.1500 341 3.36





n~t~ for Mi;lmi T.ime8tnne ;Ifter C~nmn~ctinn


Table B-3


Quarry : Miami Mold Wt: 0.242 lbs
Pit Number : 87-090 Diameter: 4 in
Sample Number : 87-AII Height: 8 in
Testing Condition : Initial Volume: 100.531 in^3
Volume: 0.0582 ft^3

Moisture Density,
Date, Time MIS Weight Freq. Vp E
Specimen Content p
(m/ddlyy hh:mm) (Ibs) (Hz) (ft/sec) (ksi)
(%) (lbs/ft3
87-L-02-1 9/4/07 22:00 8.66 8.85% 184 4.4973 245 1.88
87-L-02-2 9/4/07 22:05 8.64 8.80% 144 4.4866 192 1.15
87-L-07-1 8/18/07 23:25 8.56 8.88% 224 4.4438 299 2.75
87-L-07-2 8/18/07 23:30 8.61 8.92% 136 4.4705 181 1.02
87-L-14-1 7/15/07 22:45 8.63 8.63% 152 4.4812 203 1.28
87-L-14-2 8/7/07 20:15 8.62 8.60% 208 4.4759 277 2.39
87-L-30-1 7/16/07 16:45 8.60 8.79% 152 4.4652 203 1.27
87-L-30-2 7/16/07 16:50 8.62 9.03% 160 4.4759 213 1.41
87-M-02-1 9/4/07 22:10 8.62 8.75% 144 4.4759 192 1.15
87-M-02-2 9/4/07 22:20 8.61 8.69% 160 4.4705 213 1.41
87-M-07-1 8/18/07 23:15 8.63 8.93% 184 4.4812 245 1.87
87-M-07-2 8/18/07 23:20 8.59 8.49% 136 4.4599 181 1.02
87-M-14-1 7/15/07 22:40 8.61 8.50% 144 4.4705 192 1.14
87-M-14-2 8/7/07 20:10 8.61 9.20% 216 4.4705 288 2.58
87-M-30-1 7/16/07 16:35 8.54 8.06% 152 4.4331 203 1.26
87-M-30-2 7/16/07 16:40 8.63 8.30% 136 4.4812 181 1.02
87-H-02-1 9/4/07 22:25 8.56 9.01% 112 4.4438 149 0.69
87-H-02-2 9/4/07 22:30 8.50 8.72% 112 4.4118 149 0.68
87-H-07-1 8/18/07 23:05 8.54 8.76% 152 4.4331 203 1.26
87-H-07-2 8/18/07 23:10 8.55 8.90% 152 4.4385 203 1.27
87-H-14-1 7/15/07 22:35 8.61 8.73% 192 4.4705 256 2.03
87-H-14-2 8/7/07 20:05 8.61 9.19% 160 4.4705 213 1.41
87-H-30-1 7/16/07 16:25 8.63 8.96% 152 4.4812 203 1.28
87-H-30-2 7/16/07 16:30 8.56 8.57% 184 4.4438 245 1.86





n~t~ for Mi;lmi T.ime8tnne ;Ifter C~llring


TableB-4


Quarry : Miami Mold Wt: 0.242 lbs
Pit Number 87-090 Diameter: 4 in
Sample Number : 87-All Height: 8 in
Testing Condition : Final Volume: 100.531 in^3
Volume: 0.0582 ft^3

SM/S Moisture
Date, Time Freq. Density, p Vp E
Specimen Days Weight Content si)
(m/ddlyy hh:mm) (Hz) (Ibs/ft3) (ft/sec) (ksi)
____ (Ibs) I(%) __
87-L-02-1 9/6/07 23:15 2.05 8.65 8.71% 224 4.4919 299 2.78
87-L-02-2 9/6/07 23:20 2.05 8.63 8.70% 168 4.4812 224 1.56
87-L-07-1 8/26/07 18:00 7.77 8.53 8.53% 304 4.4278 405 5.05
87-L-07-2 8/26/07 18:05 7.77 8.58 8.59% 416 4.4545 555 9.52
87-L-14-1 8/1/07 13:20 16.61 8.55 7.74% 584 4.4385 779 18.69
87-L-14-2 8/22/07 18:10 14.91 8.59 8.25% 544 4.4599 725 16.29
87-L-30-1 8/16/07 18:55 31.09 8.51 7.80% 688 4.4171 917 25.81
87-L-30-2 8/16/07 19:00 31.09 8.53 8.03% 608 4.4278 811 20.21
87-M-02-1 9/6/07 23:25 2.05 8.61 8.65% 176 4.4705 235 1.71
87-M-02-2 9/6/07 23:30 2.05 8.61 8.61% 208 4.4705 277 2.39
87-M-07-1 8/26/07 18:15 7.79 8.60 8.60% 240 4.4652 320 3.18
87-M-07-2 8/26/07 18:20 7.79 8.57 8.23% 296 4.4492 395 4.81
87-M-14-1 8/1/07 13:25 16.61 8.56 7.88% 496 4.4438 661 13.50
87-M-14-2 8/22/07 18:20 14.92 8.59 8.96% 384 4.4599 512 8.12
87-M-30-1 8/16/07 18:15 31.07 8.48 7.28% 432 4.4011 576 10.14
87-M-30-2 8/16/07 18:30 31.08 8.57 7.55% 552 4.4492 736 16.74
87-H-02-1 9/6/07 23:35 2.05 8.56 8.94% 128 4.4438 171 0.90
87-H-02-2 9/6/07 23:40 2.05 8.49 8.66% 120 4.4064 160 0.78
87-H-07-1 8/26/07 18:25 7.81 8.53 8.64% 176 4.4278 235 1.69
87-H-07-2 8/26/07 18:30 7.81 8.54 8.77% 168 4.4331 224 1.54
87-H-14-1 8/1/07 13:30 16.62 8.60 8.57% 224 4.4652 299 2.77
87-H-14-2 8/22/07 18:30 14.93 8.60 9.04% 232 4.4652 309 2.97
87-H-30-1 8/16/07 18:45 31.10 8.61 8.72% 176 4.4705 235 1.71
87-H-30-2 8/16/07 18:50 31.10 8.54 8.34% 352 4.4331 469 6.78





n~t~ for T.nx~h~tchee ~ihell Rnck;lfter C~nmn~ctinn


Table B-5


Quarry : Loxahatchee Mold Wt: 0.242 lbs
Pit Number : 93-406 Diameter: 4 in
Sample Number : 93-AII Height: 8 in
Testing Condition : Initial Volume: 100.531 in^3
Volume: 0.0582 ft^3

Moisture Density,
Date, Time MIS Weight Freq. Vp E
Specimen Content p
(m/ddlyy hh:mm) (Ibs) (Hz) (ft/sec) (ksi)
(%) (lbs/ft3
93-L-02-1 9/1/07 22:00 8.55 8.66% 240 4.4385 320 3.16
93-L-02-2 9/1/07 22:05 8.55 9.20% 264 4.4385 352 3.82
93-L-07-1 8/18/07 22:55 8.46 8.99% 288 4.3904 384 4.50
93-L-07-2 8/18/07 23:00 8.47 8.94% 232 4.3958 309 2.92
93-L-14-1 7/15/07 22:25 8.50 8.75% 216 4.4118 288 2.54
93-L-14-2 8/7/07 17:25 8.47 9.01% 168 4.3958 224 1.53
93-L-30-1 7/16/07 13:45 8.51 9.03% 208 4.4171 277 2.36
93-L-30-2 7/16/07 13:50 8.52 9.15% 216 4.4225 288 2.55
93-M-02-1 9/1/07 22:10 8.54 8.81% 256 4.4331 341 3.59
93-M-02-2 9/1/07 23:20 8.52 8.89% 272 4.4225 363 4.04
93-M-07-1 8/18/07 22:45 8.46 9.11% 192 4.3904 256 2.00
93-M-07-2 8/18/07 22:50 8.53 9.15% 248 4.4278 331 3.36
93-M-14-1 7/15/07 22:20 8.50 9.23% 192 4.4118 256 2.01
93-M-14-2 8/7/07 17:20 8.48 8.79% 192 4.4011 256 2.00
93-M-30-1 7/16/07 13:35 8.51 9.78% 280 4.4171 373 4.28
93-M-30-2 7/16/07 13:40 8.57 8.73% 208 4.4492 277 2.38
93-H-02-1 9/1/07 23:15 8.51 9.24% 272 4.4171 363 4.03
93-H-02-2 9/1/07 23:30 8.55 8.62% 300 4.4385 400 4.93
93-H-07-1 8/18/07 22:35 8.49 9.00% 160 4.4064 213 1.39
93-H-07-2 8/18/07 22:40 8.48 8.80% 184 4.4011 245 1.84
93-H-14-1 7/15/07 22:15 8.42 8.76% 208 4.3690 277 2.33
93-H-14-2 8/7/07 17:00 8.51 9.31% 216 4.4171 288 2.54
93-H-30-1 7/16/07 13:25 8.49 9.07% 144 4.4064 192 1.13
93-H-30-2 7/16/07 13:30 8.49 9.07% 192 4.4064 256 2.01





n~t~ for T.nx~h~tchee ~ihell Rnck;lfter C~llring


Table B-6


Quarry : Lox Mold Wt: 0.242 lbs
Pit Number : 93-406 Diameter: 4 in
Sample Number : 93-All Height: 8 in
Testing Condition : Final Volume: 100.531 in^3
Volume: 0.0582 ft^3

SM/S Moisture
Date, Time Freq. Density, p Vp E
Specimen Days Weight Content si)
(m/ddlyy hh:mm) (Hz) (Ibs/ft3) (ft/sec) (ksi)
____ (Ibs) I(%) __
93-L-02-1 9/3/07 22:00 2.00 8.54 8.51% 424 4.4331 565 9.84
93-L-02-2 9/3/07 22:05 2.00 8.53 8.96% 400 4.4278 533 8.75
93-L-07-1 8/26/07 18:35 7.82 8.43 8.63% 536 4.3744 715 15.52
93-L-07-2 8/26/07 18:40 7.82 8.44 8.58% 552 4.3797 736 16.48
93-L-14-1 8/1/07 13:00 16.61 8.42 7.73% 608 4.3690 811 19.94
93-L-14-2 8/22/07 18:40 15.05 8.43 8.52% 536 4.3744 715 15.52
93-L-30-1 8/16/07 19:35 31.24 8.42 7.84% 728 4.3690 971 28.59
93-L-30-2 8/16/07 19:40 31.24 8.43 8.02% 640 4.3744 853 22.12
93-M-02-1 9/3/07 22:10 2.00 8.54 8.73% 392 4.4331 523 8.41
93-M-02-2 9/3/07 22:20 1.96 8.51 8.76% 392 4.4171 523 8.38
93-M-07-1 8/26/07 18:45 7.83 8.44 8.82% 376 4.3797 501 7.64
93-M-07-2 8/26/07 18:50 7.83 8.51 8.91% 464 4.4171 619 11.74
93-M-14-1 8/1/07 13:05 16.61 8.45 8.60% 568 4.3851 757 17.47
93-M-14-2 8/22/07 18:45 15.06 8.46 8.46% 440 4.3904 587 10.49
93-M-30-1 8/16/07 19:25 31.24 8.45 8.95% 704 4.3851 939 26.83
93-M-30-2 8/16/07 19:30 31.24 8.51 8.00% 608 4.4171 811 20.16
93-H-02-1 9/3/07 22:30 1.97 8.50 9.20% 352 4.4118 469 6.75
93-H-02-2 9/3/07 22:40 1.97 8.54 8.60% 352 4.4331 469 6.78
93-H-07-1 8/26/07 18:55 7.85 8.49 8.90% 264 4.4064 352 3.79
93-H-07-2 8/26/07 19:00 7.85 8.47 8.70% 320 4.3958 427 5.56
93-H-14-1 8/1/07 13:15 16.63 8.41 8.63% 400 4.3637 533 8.62
93-H-14-2 8/22/07 18:50 15.08 8.50 9.19% 424 4.4118 565 9.79
93-H-30-1 8/16/07 19:15 31.24 8.47 8.81% 288 4.3958 384 4.50
93-H-30-2 8/16/07 19:20 31.24 8.48 8.93% 392 4.4011 523 8.35






























































III _____ I I I'-I
0 Ln Hz 3
X:188Hz Y:2.68517


Figure B-1. Example 1 of frequency measured in Free-Free Resonant Column test.
Initial value from specimen 93-L-14-2.

























































0 Un Hz 3
X:53-HI Y:2.52701


Figure B-2. Example 2 of frequency measured in Free-Free Resonant Column test.
Final value from specimen 93-L-14-2.















APPENDIX C
CALCULATIONS

From Faure (1998), the highest possible concentration of calcium ions in solution is:

[Ca2] = 4.86x 104 (mol/L)


Vcacite = 36.93 (cm3 mol)


Molar volume of calcite


36.93 (cm3/mol) x 4.86x 10-4 (mol/L) = 1.79x 10-2 cm3/L


1.79 x 102 cm3/L


Ocala volume of solution = 0.501 L

0.501 (L) x 79 x 10-2 (cm3/L) = 9. Ox 10-3 Cm3

Moisture loss = 10%


9.0x 0-l3x 0.10

9.0x 0-4 cm3


9.0x]0-4cm3


Amount of calcite able to precipitate

Initial volume of water in specimen

Volume of Calcite able to precipitate

Moisture loss observed for low RH
curing


Volume of calcite precipitated


Table C-1. Summary of values used for calculating precipitated calcite.
Volume of Maximum Maximum Vol. of
Amount of calcite able to Moisture Calcite able to
Solution precipitate Lost Precipitate for Test
Material (Liters) (cm3) (%) Conditions (cm3)
Ocala 0.501 9.0x10-3 10 9.0x10-4
Miami 0.330 5.9 x103 11 6.5 x10-4
Loxahatchee 0.336 6.0x 103 13 7.8x10-4














LIST OF REFERENCES


Allen, R.F. [et al.] (2000) Annual Book ofASTM Standards. Vol. 4.08. American Society
for Testing and Materials, Pennsylvania.

Bricker, O.P., ed. (1971) Carbonate Cements. The Johns Hopkins Press, Baltimore.

Faure, G. (1998) Principles and Applications of Geochemistry. 2nd Ed. Prentice Hall, Inc.,
New Jersey.

Florida Department of Transportation, (2007) "City County Mileage Report," FDOT
Homepage,
http://www2.dot.state.fl.us/planning/mileage/word/pdf/pdf reportfinalinet.asp
(Accessed May 2007)

Gartland, J.D. (1979) Experimental Dissolution-Reprecipitation Processes ihi1 Two
Florida Limestones. Master's Thesis, Univ. of Florida.

Goldstein, J.I. [et al.] (1992) Scanning Electron Microscopy and X-Ray Microanalysis.
2nd Ed. Plenum Press, New York.

Graves, R.E. (1987) S.t egili Developed from Carbonate Cementation in
.///Lh Carbonate Systems as Influenced by Cement-Particle Mineralogy. Master's
Thesis, Univ. of Florida.

Huang, Y.A. (2004) Pavement Analysis and Design. 2 d Ed. Pearson Prentice Hall, New
Jersey.

Lambe, T.W. and R.V. Whitman. (1969) SoilMechanics. John Wiley and Sons, Inc.,
New York.

Lindholm, R.C. (1974) Fabric and Chemistry of Pore Filling Calcite in Septarian Veins:
Models for Limestone Cementation. In D.S. Gorsline, Ed. Journal of Sedimentary
Petrology. Vol. 44. Society of Economic Paleontologists and Mineralogists,
Oklahoma.

Lu, N. and W.J. Likos. (2004) Unsaturated SoilMechanics. John Wiley and Sons, Inc.,
New Jersey.

Menq, F. (2003) Dynamic Properties of Sandy and Gravelly Soils. PhD Dissertation,
Univ. of Texas at Austin.









Miller, J.P. (1952) A Portion of the System Calcium Carbonate-Carbon Dioxide-Water,
with Geological Implications. In C.R. Longwell and J. Rodgers, Eds. American
Journal of Science. Vol. 250. Yale University, Connecticut.

Moore, C.H. (1989) Carbonate Diagenesis andPorosity. Elsevier Science Publishers
B.V., Amsterdam.

Rasband, W.S., ImageJ, U. S. National Institutes of Health, Bethesda, Maryland, USA,
http://rsb.info.nih.gov/ij/, (Accessed June 2007)

Shaw, D.J. (1992) Introduction to Colloid and Surface Chemistry. 4th Ed. Butterworth-
Heinemann Ltd, Oxford.

Smith, L.L. and W.N. Lofroos. (1981) Pavement Design Coefficients: A Re-Evaluation
ofFlorida Base Materials. Research Report. State of Florida Department of
Transportation.

University of Arizona, "The RRUFFTM Project." http://rruff.geo.arizona.edu/rruff/ (last
accessed October 2007)

Zimpfer, W.H. (1989) S. ength Gain and Cementation ofFlexible Pavement Bases. Final
Report for the Florida Department of Transportation. University of Florida,
Department of Civil Engineering.















BIOGRAPHICAL SKETCH

Luis Alfonso Campos was born in 1983 in Tampa, Florida. After

graduating from Sickles High School in 2001, he attended the University of

Florida where he received a Bachelor of Science degree in December 2005 with a

major in civil engineering.

During his undergraduate studies, he worked part time at a small

geotechnical engineering firm in Gainesville where he gained valuable experience

in geotechnical engineering. The experience that he gained led him to continue

with graduate studies at the University of Florida. He received a Master of

Engineering degree in May 2008 and plans to work at a geotechnical consulting

firm in North Carolina.





PAGE 1

INVESTIGATION OF STIFFNESS GAIN MECHANISM IN FLORIDA LIMESTONE BASE COURSE MATERIAL By LUIS ALFONSO CAMPOS A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF ENGINEERING UNIVERSITY OF FLORIDA 2008

PAGE 2

2008 Luis Alfonso Campos

PAGE 3

To my Parents and Sisters and to Carrie

PAGE 4

iv ACKNOWLEDGMENTS I would like to thank Dr. Bjorn Birgisson for giving m e the opportunity to work on this research project with wh ich most of the work was completed under. I would also like to thank Dr. Michael C. McVay for taking this research to completion and for his seemingly limitless knowledge and fascination in geotechnical engineering. I would also like to thank Dr. Philip S. Neuhoff of the De partment of Geology who helped shape this project and give it a new dir ection. I would also like to th ank Dr. Dennis R. Hiltunen and Dr. Reynaldo Roque for serving on my supervisory committee. I appreciate my former boss, the la te M. Fred Rwebyogo, and Dr. Frank C. Townsends guidance which steered me toward s my career in graduate school. I would also like to thank Dr. David Bloomquist for giving me the opportunity to work on a separate project which took me around the world to a place I would never have had a chance to see. I appreciate the patience and knowledge of Tanya Reidhammer with all of my chemistry and microscopy questions. I also appreciate the cooperation from the FDOT State Materials Office. Without their aid a nd experience th is research would not have been possible. Finally, I would like to thank my family for their support throughout the years. I also thank my friends for being such fantasti c distractions and entertainment in my life.

PAGE 5

v TABLE OF CONTENTS page ACKNOWLEDGMENTS............................................................................................................. iv LIST OF TABLES................................................................................................................. ....... vii LIST OF FIGURES..................................................................................................................... viii ABSTRACT.....................................................................................................................................x CHAP TER 1 INTRODUCTION....................................................................................................................1 1.1 Background ....................................................................................................................1 1.2 Purpose and Scope .........................................................................................................2 1.3 Methodology ..................................................................................................................2 2 LITERATURE REVIEW.........................................................................................................4 2.1 Introduction ................................................................................................................... .4 2.2 Base Course Materials ...................................................................................................4 2.2 Chemistry of Carbonate Cementation............................................................................ 5 2.3 Kelvins Equation ..........................................................................................................7 2.4 Compaction Issues......................................................................................................... 8 3 MATERIALS AND METHODS........................................................................................... 11 3.1 Selection of Materials ..................................................................................................11 3.2 Material Preparation.....................................................................................................12 3.3 Compaction Procedures............................................................................................... 13 3.4 Curing Procedures ........................................................................................................13 3.5 Resonant Colum n Testing............................................................................................ 14 3.6 Scanning Electron Microscopy ....................................................................................15 3.6.1 Sample Preparation............................................................................................15 3.6.2 Scanning Electron Microscopy Analysis ...........................................................15 3.6.3 Imaging Software............................................................................................... 16 3.7 Porosity Measurem ents................................................................................................ 16 3.8 X-Ray Diffr action........................................................................................................17 4 RESULTS AND DISCUSSION............................................................................................. 25 4.1 Resonant Colum n Results............................................................................................ 25 4.2 Scanning Electron Microscope Analysis .....................................................................26 4.3 Porosity Measurem ents................................................................................................ 27 4.4 Discussion ....................................................................................................................29

PAGE 6

vi 5 CONCLUSIONS AND RECOMME NDATIONS................................................................. 51 5.1 Conclusions ..................................................................................................................51 5.2 Recommendations for Future W ork.............................................................................52 APPENDIX A Modified Proctor and LBR Results........................................................................................ 54 B Resonant Column Testing Data.............................................................................................. 57 C Calculations............................................................................................................................65 LIST OF REFERENCES...............................................................................................................66 BIOGRAPHICAL SKETCH.........................................................................................................68

PAGE 7

vii LIST OF TABLES Table page 3-1 Descriptive data for three lim es tone base course materials............................................... 21 3-2 Equilib rium relative humidity values fo r saturated aqueous salt solutions....................... 21 4-1 Summ ary of Ocala limestone unde r different curing conditions....................................... 31 4-2 Summ ary of Miami limestone unde r different curing conditions...................................... 31 4-3 Summ ary of Loxahatchee shell rock under different curing conditions............................ 32 4-4 Average bulk properties of base course m aterials............................................................. 42 4-5 Summ ary statistics for pore sizes from ImageJ analysis................................................... 42 4-6 Comparison of porosity values from different methods.................................................... 42 4-7 Theoretical suction p ressures for different relative humidities.......................................... 50 B-1 Data for Ocala lim estone after compaction....................................................................... 57 B-2 Data for Ocala limestone after curing................................................................................ 58 B-3 Data for Miam i limest one after compaction...................................................................... 59 B-4 Data for Miam i limestone after curing............................................................................... 60 B-5 Data for Loxahatchee shell rock after com paction............................................................ 61 B-6 Data for Loxahatchee shell rock after curing ..................................................................... 62 C-1 Summary of values used fo r calculating precipitated calcite............................................. 65

PAGE 8

viii LIST OF FIGURES Figure page 2-1 Schem atic of pavement layers showing concept of structural numbers.............................. 9 2-2 General relationship between pore diam eter and relative humidity.................................... 9 2-3 General relationship between tota l suction and relative hum idity..................................... 10 3-1 Map of Florida showing approxim ate lo cations of aggregate source mines..................... 19 3-2 Grain size distribution curves for lim estone materials...................................................... 20 3-3 Mercury Porosim eter specimen set-up............................................................................... 22 3-4 X-Ray diffr action plot for untreated Ocala limestone.......................................................23 3-5 X-Ray diffr action plot for untreated Miami limestone...................................................... 23 3-6 X-Ray diffr action plot for untre ated Loxahatchee limestone............................................ 24 4-1 Ocala lim estone stiffness gain versus time........................................................................ 33 4-2 Miam i limestone stiffness gain versus time....................................................................... 33 4-3 Loxahatchee shell rock stiffness gain versus tim e............................................................. 34 4-4 Ocala lim estone stiffness gain vers us decrease in initial moisture.................................... 34 4-5 Miam i limestone stiffness gain versus decrease in initial moisture................................... 35 4-6 Loxahatchee shell rock stiffness gain versus decrease in initial m oisture......................... 35 4-7 Ocala lim estone typical image 1........................................................................................ 36 4-8 Ocala lim estone typical image 2........................................................................................ 36 4-9 Miam i limestone typical image 1....................................................................................... 37 4-10 Miam i limestone typical image 2....................................................................................... 37 4-11 Loxahatchee shell rock typical im age 1............................................................................. 38 4-12 Loxahatchee shell rock image 2 showing zone of possible calcite crystal growth ............ 38 4-13 Loxahatchee shell rock close-up of highlighted region in Fig. 4-12 ................................. 39 4-14 Glades core typical im age 1............................................................................................... 39

PAGE 9

ix 4-15 Glades core typical im age 2 showi ng zone of calcite crystal growth................................ 40 4-16 Glades core close-up of highlighted region in Fig. 4-15 ................................................... 40 4-17 Glades core typical im age 3 showi ng zone of calcite crystal growth................................ 41 4-18 Glades core close-up of highlighted region in Fig. 4-17 ................................................... 41 4-19 Relative hum idity values and corr esponding affected pore diameters.............................. 43 4-20 Mercury Porosim eter results for 30-day specimens and Glades core................................ 44 4-21 Pore diam eter histogram from Imag eJ analysis for Ocala limestone................................ 45 4-22 Pore diam eter histogram from ImageJ analysis for Miami limestone............................... 45 4-23 Pore diam eter histogram from ImageJ analysis for Loxahatchee shell rock..................... 46 4-24 Pore diam eter histogram from ImageJ analysis for Glades core....................................... 46 4-25 Ocala lim estone pore diameter dist ribution from ImageJ analysis.................................... 47 4-26 Miam i limestone pore diameter dist ribution from ImageJ analysis................................... 47 4-27 Loxahatchee shell rock pore diam eter distribution from ImageJ analysis......................... 48 4-28 Image processing steps w ith ImageJ software................................................................... 49 4-29 Theoretical relative hum idity values and corresponding total suction.............................. 50 A-1 Ocala lim estone Modified Proctor and LBR data.............................................................. 54 A-2 Miam i limestone Modified Proctor and LBR data............................................................ 55 A-3 Loxahatchee shell rock Modi fied Proctor and L BR data................................................... 56 B-1 Exam ple 1 of frequency measured in Free-Free Resonant Column test............................ 63 B-2 Exam ple 2 of frequency measured in Free-Free Resonant Column test............................ 64

PAGE 10

x Abstract of Thesis Presen ted to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Engineering INVESTIGATION OF STIFFNESS GAIN MECHANISM IN FLORIDA LIMESTONE BASE COURSE MATERIAL By Luis Alfonso Campos May 2008 Chair: Michael McVay Major: Civil Engineering The Florida Department of Transportation (FDOT) has observed stiffness increases over time in limestone base course materials. It is a goal of the FDOT to understand the mechanism involved so that it may implem ent design procedures to account for the stiffness increase. Past studi es have credited calcium car bonate cementation as providing the stiffness increase. The objective of th is study was to test the hypothesis that cementation can occur if there are pressure gradients adjacent to grain contacts. Laboratory investigation involved compacting three Florida limestones and curing in chambers with high, medium and low relative humidities, which would induce various degrees of such pressure gradients. M odulus values were obtained over time by performing free-free resonant column tests on all materials. Compacted materials were later looked at with a scanning electron microscope to search for crystal growth in the materials.

PAGE 11

xi It was found that no cementation had occu rred during the 30-day test period and that the observed stiffness gains were a resu lt of capillary sucti on within the nano and micro-pores. SEM imagery for an aged field co re paired with porosity data suggests that cementation occurs, but at a much slower rate than observed in the compacted laboratory specimens. Image analysis of the field core showed the presence of calcite crystals and much less fine void space than the compacted specimen of similar material. Porosity measurements were compared between the th ree compacted materials and the field core to help clarify what processes are in volved with the stiffness increases.

PAGE 12

1 CHAPTER 1 INTRODUCTION 1.1 Background The state of Florida has over 90,000 m iles of paved public roads that commuters rely on a daily basis. These roadways ar e designed by highway engineers using the highest quality of material available while at the same time maximizing the design for economy. The engineer will try out different mate rial and thickness conf igurations to deal with anticipated traffic loads and pick the least expensive design. The highways are typically designed to last for 25 years or more, but as pavements progress through their design life, the need to repair or replace the pavement arises. With routine maintenance, the asphal t surface is milled and made thicker upon replacement. This asphalt surface layer is by far the most expensive material used for roadway construction, so optimization is impor tant. The State of Florida Department of Transportation (FDOT) has studied limestones and has noted significant increases in the stiffness of the limestone base course materi als over time. With st ronger base course materials, less asphalt concrete can be us ed, saving taxpayer money. Likewise, if the potential for an increase in stiffness is known before the initia l design, the highway engineers could use this information to further improve upon their designs. Understanding the behavior and properties of these materials, both present and future, is the key to better engineering.

PAGE 13

2 1.2 Purpose and Scope As m entioned, studies have been done that no te an increase in stiffness over time in limerock base course materials (Gartla nd, 1979; Graves, 1987; Zimpher, 1989). The FDOT has made attempts to reevaluate desi gn parameters associated with base course materials to account for the stiffness increase. A problem is that there are many sources from different geological deposits from which these base course materials are mined. The need to characterize the engineering propertie s effectively for each of these sources is required. Simple tests to characte rize some of the properties (s uch as stiffness) have been established and are performed on a routine basis by local testing consultants. While stiffness increases in limestone base course materials have been observed, no test has been successful in predicting what a gene ric stiffness increase will be because the mechanism is not yet fully understood. One proposed possibility of the stiffness in crease is due to calc ite crystal growth and cementation in the micro-pore structur e of the limestone. Limestone is mostly CaCO3, calcium carbonate, which will dissociate and precipitate unde r various natural environmental conditions. Calcite crystals will precipitate within what was previously a void in the limestone. These crys tals bond calcite particles toge ther and also create more contact points with which to resist deforma tion, resulting in a stiffness increase. The purpose of this study was to try and create conditions which are favorable for the precipitation of calcite crystals and observ e different material properties which may affect this phenomenon. 1.3 Methodology Bricker (1971) noted that cem entation in carbonate mate rial occurs due to many factors, one of which is local pressure gradie nts adjacent to grain contacts. It is proposed

PAGE 14

3 that by controlling the relative humidity within a curing chamber such a pressure gradient will be induced and accelerate the cementation process within compacted limestone base course specimens. The limestone materials were compacted, cured under varying relative humidities and tested over time for an increase in stiffness. Three types of limestones representing diffe rent geologic formations were used in this study. Physical and chemical properties were determined for each material. The main tool used in determining the stiffness increase in the base course materials was the freefree resonant column test to find modulus values. Scanning electron microscopy (SEM) techniques and imaging software was used to find pore structure characteristics in the three cured materials. Pore structure data fo r a field core sample was also measured for comparison.

PAGE 15

4 CHAPTER 2 LITERATURE REVIEW 2.1 Introduction The purpose of this research project was to create conditions which are favorable for the precipitation of calcite crystals and observe different m ateri al properties which may affect this phenomenon. A review of the literature was conducted to find information on base course materials, carbonate cementation and compaction issues for limestone base course materials. 2.2 Base Course Materials Highway pavem ents fall into three design ca tegories: flexible, rigid or composite pavements. The most commonly used pavement type in Florida is the flexible design. This design consists of an asphalt surface cour se, a base course just below that, and the subgrade which consists of the existing soil. The goal of a pave ment system is to protect the subgrade. Therefore, high quality material s are used for the surface and base courses. Pavements layers are designed using the con cept of structural nu mbers. In order to prevent an anticipated amount of damage to the layer just below, a structural number requirement should be met. The quality and stiffn ess of each layer of material is indicated by a structural layer coefficient, a. The structural number for each layer can be calculated by multiplying the structural la yer coefficient by the layer thickness. A diagram of the pavement system and design is shown in Fi g. 2-1. Design procedur es can be found in many textbooks, including Huang (2004). In the st ate of Florida, limestone is the most commonly used base course material. Before the pavements are designed by engineers,

PAGE 16

5 the structural layer coefficient, a, is know for each materi al. Materials with higher a values are desired since designers can use less of the stiffer material, which cuts costs. Past studies on limestone base course mate rials have observed increase in stiffness over time, and have credited these stiffne ss increases to calcite cementation. Gartland (1979) used treatment methods which mimick ed vadose and phreatic conditions, as well as using different water sources to test their effect on stiffn ess increase. It was found that the greatest stiffness increases occurred under phreatic conditions ( no cycling) and when using plain water. The time required for significant cementation to occur was not generically identified. Graves (1987) conti nued on a similar study by testing mixtures with varying ratios of calcite to quartz. Phr eatic curing conditions were simulated in an attempt to find the length of time required fo r a significant stiffness increase. It was found that the highest stiffness increase in untreated materials occurred after 14 days. Materials with higher carbonate to quartz ratios showed greater st iffness increases. Similar work and field testing has caused the FDOT to reevaluate the structural coefficient for base course materials (Smith and Lofroos, 1981). St ructural layer coeffi cients were changed from 0.15 to 0.18 as recommended to account for th e future increases in stiffness, but the authors felt that more testing should be completed. 2.2 Chemistry of Carbonate Cementation The goal of this research was to create conditions which are fa vorable for carbonate cem entation, as past studies have shown th at this is the mechanism responsible for stiffness increases. Calcium carbonate is ve ry common throughout the state of Florida. Carbonate cements are responsible for a sign ificant amount of the cements which hold together sedimentary rocks. Calcium carbonate will also dissolve and reprecipitate as under typical changes in environmental conditions.

PAGE 17

6 Carbon dioxide, CO2, plays a major role in the solubility of CaCO3. Various sources of CO2 in water exist. Carbon dioxide from the atmosphere may dissolve in falling rainwater or CO2 may be provided to groundwater by bacteria or other organisms in soil. With increased CO2 levels in water, more CaCO3 can be dissolved Miller (1952) described the process that CO2 in the atmosphere combines with water to form carbonic acid which in turn reacts with calcium car bonate to form the soluble bicarbonate: H2O + CO2 H2CO3 H+ + (HCO3)CaCO3 + H+ + (HCO3)Ca2+ + 2(HCO3)These reactions show that CO2 gas must be present in orde r for the calcium carbonate to dissolve or precipitate. Bricker (1971) states that the emplacement of carbonate cements require precipitation from solu tion. Also, one way that CaCO3 can be made supersaturated (and thus more able to precipitate) is thr ough pressure reduction, or by having local pressure gradients adjacent to grain contacts. Other work has been done on the pore fill ing material. Lindholm (1974) states that aragonite, a polymorph of calcite, is instable at near-surface environmental conditions. Aragonite is not expected to be present in the base course materials, therefore only rhombohedral calcite crystals are expected to be found. Although calcite cements may precipitate, Moore (1989) notes that much of the porosity in limestones is intraparticle, which is unique to carbonates. The living ch ambers, or shells, of various organisms provide this source of porosit y. Although calcite cement may be present in such pores, they would not contribute to any stiffness increase. Caution must be used when searching for calcite crystals, as this may be the case.

PAGE 18

7 2.3 Kelvins Equation The use of saturated salt solutions is a wa y to control the relative humidity in a confined space. Saturated salt solutions are able to adsorb relatively large quantities of water while maintaining a constant relative humidity (Lu and Likos, 2004). Also, the resulting relative humidities from the use of saturated salt solutions will cause the pressure gradients which will drive the calci um carbonate precipitation within the pore spaces. Kelvins equation governs the relationship between the pressure changes across a curved air-liquid boundary to the vapor pr essure above the boundary. One form of Kelvins equation can be written: dRT vTws4 ln(RH) (2.1) where RH is the relative humidity, Ts is surface tension (N/m), vw is the partial molar volume of water vapor (m3/mol), d is the pore diameter (m), R is the universal gas constant (Nm/Kmol) and T is temperature (K). The pore st ructure can be idealized as a system of capillary tubes with diameter d. These capillaries will fill with liquid and form a meniscus dependant on the above variable s. In the presence of a given relative humidity, the pores will either lose or gain water, causing the meniscus to change and the resulting vapor pressure above the air-liquid boundary will ca use a pressure gradient to exist within the material pores. The effect of curvature on the vapor pressures explains the ability of the vapors and solutions in the pores to s upersaturate (Shaw, 1992). Figure 2-2 shows the relationship between relative hum idity and the pore diameter which it will effect. The relative humidities exhibited by the sa turated salt solutions effects the pore water in specimens. The relative humidity of the saturated salt solutions will cause the

PAGE 19

8 pore water to evaporate until equilibrium is reached between the vapor and liquid in the pore spaces, which causes suction. Kelvins eq uation can also be rewritten in terms of total suction as: ln(RH) 0 vw tv RT (2.2) where t is the total soil suction (kPa), vw 0 is the specific volume of the liquid (m3/kg), v is the molecular mass of the liquid vapor (kg/kmol), and R and T are defined as above. Figure 2-3 shows the relationship between relative humidity and total suction. 2.4 Compaction Issues It is proposed that the specimens be comp acted at 1% wet of the optimum moisture content even though for granular materials, this generally decreases initial stiffness values. This was done for two reasons. First, the extra fluid will be able to contain more calcium carbonate in solution. Second, labor atory compaction curves generally yield somewhat lower optimum moisture contents than the actual field optimum (Lambe and Whitman, 1969). It is hoped that this will mimic field results better and more calcite cements will precipitate, resulti ng in higher stiffness increases.

PAGE 20

9 BASE AC SUB-BASE D D D1 2 3a a a1 2 3SN = D x a111SN = D x a222SN = D x a333SN Figure 2-1. Schematic of pavement layers showing concept of structural numbers. 0.0 0.2 0.4 0.6 0.8 1.0 1.E-10 1.E-09 1.E-08 1.E-07 1.E-06 Pore Diameter (meters)Relative Humidity, RH Figure 2-2. General relationship between pore diameter and relative humidity.

PAGE 21

10 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 0.00.10.20.30.40.50.60.70.80.91.0 Relative HumidityTotal Suction (kPa) Figure 2-3. General relationship between total suction and relative humidity.

PAGE 22

11 CHAPTER 3 MATERIALS AND METHODS 3.1 Selection of Materials For roadway construction projects, the Stat e of Florida allows the contractor to choose the base course material in accord ance with standard specifications, although many contractors favor local materials as transportation costs are the major deciding factor. There are many acceptable aggregate sour ces from different geological formations across the State of Florida. The stiffness of th ese limestone base course materials is based on many factors. The gradation, mineralogy, particle shape, moisture content and compactive effort will determine the initial stiffness of the base course material. The objective of this research was to better understand th e stiffness gain mechanism in base course material. As stat ed earlier, the physical and mineralogical properties of Florida limestones vary from one geologic formation to the other, as well as within the formations themselves. Three co mmonly used limestone s from across Florida were chosen as representative aggregates. Th e base course materials chosen were Ocala limestone, Miami limestone and Loxahatc hee shell rock (mines 26002, 87090 and 93406, respectively, Fig. 3-1). These aggregates come from the Ocala Group, Miami Oolite and Anastasia Formation, respectively. For comparison, a field core taken from Glades County, Florida will be examined. The base course material in the Glades co re appears to be Miami limestone based on physical characteristics and specific gravity, although it is uncertain what mine the material originated from as attempts at verification have been unsuccessful.

PAGE 23

12 3.2 Material Preparation Aggregate was obtained from each of the th ree quarries in Florida. The material was then dried and sieved to obtain grain size distribution curves as shown in Fig. 3-2. Sieve analysis shows that the Miami limestone is the coarsest material, followed by the Loxahatchee shell rock then the Ocala limestone. The Ocala Limestone had the highest percentage of material passing the #200 sieve, followed by the Miami limestone and then the Loxahatchee shell rock. Materials were se parated by the #4 sieve in order to separate the coarse and fine aggregate. Prior to co mpaction, specimens were remixed according to the overall proportions in an attempt to maximize uniformity for the multiple specimens. Material greater than was omitted because there is a maximum allowable aggregate size for both the resonant column (ASTM D 4015) and Limerock Bearing Ratio (LBR) testing (FM 5-515). Modified Proctor (ASTM D 1557) and LBR testing was also completed on the aggregates in order to verify that the ma terials meet the FDOT standards. Detailed Modified Proctor and LBR data are presen ted in Appendix A. The LBR testing was performed in accordance with FM 5-515 except for the fact that, as stated earlier, material greater than was discarded in stead of crushed to as required in the test. The FDOT State Materials Office (SMO) completed Modi fied Proctor and LBR testing on the three materials and descriptive data is given in Table 3-1. It should be noted that the material from the Ocala quarry did not meet the minimum required LBR value of 100 as shown in Table 3-1, but was used regardless since the incr ease in stiffness is of concern rather than the initial stiffness values.

PAGE 24

13 3.3 Compaction Procedures Modified Proctor data gave the optimum moisture content required for compaction. Materials were compacted at 1% wet of the optimum moisture content (See LITERATURE REVIEW) into 4 diameter by 8 height plastic cylinders because resonant column testing require s an aspect ratio of no less than 2:1. It should be noted these dimensions are different from ASTM D 1557 which requires either a 4 or 6 diameter by 4.584 height rigid metal mold. Plastic cylinders were chosen because portions would later be sawed out for the dest ructive testing portion of this experiment. Compaction procedures from ASTM D 1557 had to be modified to ensure that the modified compactive effort of 56,000 ft-lbf/ft3 was still achieved. The specimens were compacted in 9 layers with 25 blows per laye r to achieve the Modified Proctor density. The 10 pound hammer and 18 drop were still us ed. Materials were compacted using a Rainhart automatic tamper at the FDOT SMO. Two specimens were compacted for each testing variation and the resulting modulus values and moisture content reducti ons were averaged. The testing variations consisted of four different time periods and three different curing humidities. In total, 24 duplicate specimens were compacted for each of the three aggregate sources. 3.4 Curing Procedures Curing periods of 2, 7, 15 and 30 days were used in this study to assess stiffness increase over time. After compaction, the cyli nders were placed in curing chambers for the allotted time periods. Desiccato r cabinets of approximately 0.75 ft3 were used as curing chambers. The seals were previously tested to ensure no leak age. To maintain a constant relative humidity in each of the chambers, different saturated salt solutions were

PAGE 25

14 used. It was desired to use solutions whic h exhibited high, medium and low relative humidities. Saturated salt solutions were prepared by mixing a quantity of lithium chloride (RH 11%), magnesium nitrate (RH 53%) or potassium sulfate (RH 97%) with gently heated, distilled water. Once the solution c ools, excess solids will precipitate if the solution is beyond saturation. This allows moisture from the compacted specimens to be absorbed by the saturated salt solutions until excess solids are no longer present. Approximately 250 mL of solution were used in each of the curing chambers and either replaced or remixed as necessary to ensure that solids were present. Conditions inside curing chambers were monitored with the us e of temperature and humidity gages. The temperature dependencies of the saturated sa lt solutions according to ASTM E 104 are presented in Table 3-2. The temperature re mained at a constant 25 C within the chambers throughout the test period. 3.5 Resonant Column Testing Testing for an increase in stiffness for each of the materials was the main concern of this research. The testing program was desi gned to investigate the stiffness increase as a function of relative humidity and time. It was important that the modulus test be nondestructive as the later tests that would char acterize different properties of the materials are destructive. The free-free resonant-column modulus test is a small strain (less than 10-4 in/in) test which consists of applying a vibrati on excitation at one end of the specimen and measuring the resulting vibrati on patterns from the applied compression wave at the other end. Fifteen tests were conducted and averag ed to obtain the resonant frequency of each specimen. The resonant frequency was then used along with and geometric properties and

PAGE 26

15 the compression wave speed to calculate Young s modulus values. Initial measurements were taken immediately after compaction and final measurements were taken after the allotted curing time for each sp ecimen. After testing was completed, cylinders were capped to ensure no further loss in moisture. 3.6 Scanning Electron Microscopy 3.6.1 Sample Preparation In order to view specimens in the SEM, portions of the compacted specimens had to be cut in order to be mounted and fit in the SEM. A major problem which must be overcome is the brittleness of the compacted materials. Upon cutting the material from the cylinders to the size required to fit in the SEM (approximately 1 in3), most of the material will break apart from the vibrati on caused by the cutting saw which prevents the examination of coherent pieces. In order to prepare samples for SEM analysis, large slices measuring approximately 1.5 thick a nd 4 diameter were cut from the plastic cylinders dried in an oven. The pieces we re further broken by hand into the 1 in3 size required to fit in the SEM mounting chamber. These samples were impregnated with a low viscosity epoxy in order to fill as many voi ds as possible. Epoxied samples were then cut and sanded until polished. When viewed in the SEM, the dens ity of the epoxy makes it appears black, allowing for easy identification of voids. 3.6.2 Scanning Electron Microscopy Analysis SEM examinations of the three compacted materials and the field core were conducted in order to search for the presence of calcite crystals. Specimens measured approximately 3.0 cm by 2.5 cm and were fl at. Fourteen random point s were selected on each specimen and images were taken. Any cal cite crystals visible at this scale were further investigated. As stated earlier, samp les were polished so that the SEM settings

PAGE 27

16 would not need to be reconfi gured while investigating each sample and also in order to run Energy Dispersive Spectrometer (EDS). The spectrometer identified and mapped the chemicals present for selected images. SEM examinations were conducted usi ng a Hitachi S-3000 N Scanning Electron Microscope with an EDS x-ray analyzer at the UF Department of Civil and Coastal Engineering. 3.6.3 Imaging Software ImageJ is an image processing program made available to the public. It was used to characterize the number and size of voids in each of the SEM images. The SEM images used for pore size analysis were taken at 90X magnification which limited the minimum void size that the imaging software could disc ern as it only counts pixels. In the images, 1 mm is equal to 880 pixels and so the software will be able to recognize pore sizes greater than 2 m. It was desired to count voids in this range as weight -volume relationships were used to calculate bulk porosity and mercury porosimeter measurements were used to describe pores smaller than 100 m. If a hi gher magnification was used, it was felt that the 14 images for each sample would not be a large enough sample population to describe the pore structure. A subroutine in ImageJ converted the SEM images from grayscale to binary. The voids appeared black and were counted and so rted by total area. The software allows the user to set the minimum pore size that the software will recognize. 3.7 Porosity Measurements Porosity measurements were completed on 30-day samples cured under low relative humidity. Specimens must be completely dry as any moisture will be turned into compressible water vapor. This test is ran in two stages whic h cover a pore range

PAGE 28

17 between approximately 150 m and 1.8 nm. The specimen for this apparatus must fit inside a glass sample cell as shown in Figur e 3-3. Representative samples were difficult to obtain since the compacted material is approximately 1650 cm3 and the mercury porosimeter device accepts spec imens of approximately 1.5 cm3. In an attempt to test representative samples, aggregate pieces were taken with finer pa rticles attached (no clean aggregate). All materials were tested in accordance with ASTM D 4404 using a Quantachrome Autoscan 60 Mercury Porosimeter at the UF Particle Engineering Research Center (PERC). Testing was completed by PERC personnel. 3.8 X-Ray Diffraction X-Ray Diffraction (XRD) measurements were taken on the three virgin aggregate sources. Approximately 5 grams of each a ggregate was ground up with a mortar and pestle and passed through the #200 sieve. Fr om this, chemical and crystallographic composition was obtained. The resulting plots ar e shown in Figs. 3-4, 3-5 and 3-6. These plot show various inte nsities coupled with 2* angles. Each 2* angle pattern corresponds to a unique crystall ine structure, thereby making it possible not only to detect quartz and calcite, but also to distinguis h calcite from its polymorph aragonite. The intensities at each angle, along with other data that may be obtained from the geometry of these plots, represent the relative quantity of each mineral present. Minerals were identified by matching the observed patte rns to a mineralogical powder diffraction database maintained by the Univ. of Arizona. From this database, quartz is known to diffract with a major peak at 2 between 26.6 and 26.7, calcite with a major peak (subsequent peaks exist and are present) at 2 between 29.4 and 29.5 and aragonite with a major peak at 2 between 26.2 and 26.3.

PAGE 29

18 As illustrated, calcite is the main component of each aggregate source. The Ocala limestone is almost exclusively comprised of calcite while the Miami limestone and Loxahatchee shell rock are comprised of calcite and quartz. It shoul d also be noted that aragonite was not present in any of the aggregate sources. All materials were tested using a Ph ilips APD 3720 powder diffractometer at the UF Major Analytical Instrumentation Center (MAIC). Testing was completed by MAIC personnel.

PAGE 30

19 Figure 3-1. Map of Florida showing approxima te locations of aggregate source mines. 26002 93406 87090

PAGE 31

20 0 10 20 30 40 50 60 70 80 90 100 0.01 0.1 1 10 100 Grain Size (mm)Percent Passing a c b Figure 3-2. Grain size distribution curves for limestone materials. (a = Ocala limestone; b = Miami limes tone; c = Loxahatchee shell rock)

PAGE 32

21 Table 3-1. Descriptive data for th ree limestone base course materials. Material Mine No. Carbonate Content Maximum Dry Density (pcf) Optimum Water Content (%) LBR Ocala 26-002 99.2 111.8 13.4 92 Miami 87-090 77.5 129.6 7.8 175 Loxahatchee 93-406 53.8 127.2 7.9 131 Table 3-2. Equilibrium relative humidity va lues for saturated aqueous salt solutions. Temperature (C) Lithium Chloride, LiCl H2O Magnesium Nitrate, Mg(NO3)2 6H2O Potassium Sulfate, K2SO4 20 11.3 0.3 54.4 0.2 97.6 0.5 25 11.3 0.3 52.9 0.2 97.3 0.5 30 11.3 0.2 51.4 0.2 97.0 0.4

PAGE 33

22 1.0 cm SAMPLE SAMPLE CELL Figure 3-3. Mercury Porosimeter specimen set-up. Mercury is intruded from right side. Approximate specimen size is 1 cm x 2 cm.

PAGE 34

23 0 1000 2000 3000 4000 5000 25303540455055 Angle (2* )Intensity Figure 3-4. X-Ray diffraction plot for untreated Ocala limestone. 0 1000 2000 3000 4000 5000 25303540455055 Angle (2* )Intensity Figure 3-5. X-Ray di ffraction plot for untreated Miami limestone.

PAGE 35

24 0 1000 2000 3000 4000 5000 25303540455055 Angle (2* )Intensity Figure 3-6. X-Ray diffr action plot for untreated Loxahatchee limestone.

PAGE 36

25 CHAPTER 4 RESULTS AND DISCUSSION 4.1 Resonant Column Results The main test to determine the increase in modulus of the conditioned limestones was the free-free resonant column test. M odulus and moisture content data for the different materials and curi ng conditions are given in Tables 4-1 through 4-3. The Youngs modulus is compared relative to the 8 averaged initial m odulus values for the different relative humidities and the different compacted base course materials. Modulus values are plotted as a per cent increase over this initial reference modulus. Values reported are averages of duplicate molds tested for each base course material and curing condition. The data was plotted in Figs. 4-1 through 4-3 in order to better illustrate the increases in stiffness. Each material showed increases in stiffness for all three relative humidity levels with the greatest increas e occurring when cured under low relative humidity conditions. The stiffness of the Ocala limestone increased by approximately 2100%, the Miami limestone by 1600% and the Loxahatchee shell rock by 940% when cured under low relative humidity conditions. Modulus values for materials cured under high relative humidity conditions appear to be near their maximum as values are only slightly increasing afte r 7 days. The Loxahatchee shell ro ck showed the lowest overall modulus increases for each curing relative humid ity and in general, modulus values only slightly increase afte r 15 days. The modulus values of the Ocala and Miami limestones increase at an almost constant rate for both the medium and low relative humidities and it is evident from the plots that the modulus values show no sign of reaching a maximum

PAGE 37

26 value. However, it is expected that the in crease in modulus will diminish just as the modulus values for the high relative humidity tests have. Resonant Column Testing data is reported in Appendix B. The initial weights for each test cylinder were record and compared with the weights after curing. This weight loss is due to the saturated salt solutions absorbing moisture from the specimens. The percentage of initial moisture lost was plotted against the percent increase over the reference modulus as shown in Figs. 4-4 through 4-6. Each material showed an approximately linear relationship between the percent moisture lost and the percent increase in modulus, regardless of curing conditions. The Ocala limestone gained more stiffness per moisture lost followed by the Miami limestone and finally the Loxahatchee shell rock. These trends show th at over this testing period the increase in stiffness is related to moisture loss. 4.2 Scanning Electron Microscope Analysis Scanning electron microscopy techniques were used in order to see whether the moisture loss resulted in calcite cement growth, which could be responsible for the observed stiffness increase in the resonant column testing portion of the research. Specimens from materials cured for 30 days under low relative humidity were prepared and examined because it was felt that they had the highest potential for showing calcite cement bonding. Also, a section from a field core from Glades County was examined for comparison with the laboratory compacted specimens. After modulus testing, the selected specimens were cu t out of the cylinder molds and prepared for SEM analysis as stated in Chapter 3. Fourteen random locations on each specimen were examined for the presence of calcite crystal and patterns which would suggest growth. Selected images from the an alysis showing typical characteristics are

PAGE 38

27 presented. Figures 4-7 through 4-11 are typi cal examples of the Ocala, Miami and Loxahatchee images. The light aggregates are calcium carbonate, grey aggregates are quartz and the black areas are the intruded epoxy. SEM exploration of the laboratory compacted specimens did not reveal zone s with calcite cement growth. Figure 4-12 reveals a zone in the Loxahatchee shell rock co ntaining textures related to calcite crystals. Figure 4-13 is a close-up of the area of interest in Fig. 4-12, but reveals that the crystals are only intraparticle and theref ore would not contribute to any stiffness increase from aggregate-to-aggregate cementation. Scanning electron micrographs of the Glades core were also taken. Typically, the Glades core shows less void area than the compacted specimens. Also, many of the Glades core images contained easy to spot relatively large calcite crystals which are appear to be growing between aggregates. Typi cal features of the Glades core are shown in Figs. 4-14 through 4-18. Rhombohedral calci te crystals are show n filling in the pore spaces in Figures 4-16 and 4-18. Additionally, element maps were taken for selected SEM images. Element maps for the Ocala limestone consist of calcium, carbon and oxygen wh ich indicates that only calcite is present. Element maps for the Miami limestone and Loxahatchee shell rock consist of calcium, carbon, oxygen and silicon which indicate the pres ence of calcite and quartz. These measurements are in agreement with the XRD analysis. 4.3 Porosity Measurements The initial moisture content values were taken for each material during the modulus testing portion of this research. The theoretical porosity was calculated using classic weight-volume relationships. Descriptive prope rties are presented in Table 4-4. These values represent the bulk porosity for the ma terials and are useful for comparing the

PAGE 39

28 different methods for finding porosity. The calcu lations for the bulk specimens show that the porosity for these material s ranges between 0.238 and 0.318. Mercury Porosimeter testing gave further insight into the void structure of the compacted limestone. Mercury porosimetry is able to give distributions of pore sizes while bulk porosity measurements do not. The mercury porosimetry test is capable of giving measurements accurate to diameters ranging between 3.6 nm and 100 m. This range of pore diameters corres ponds with Kelvins equation as stated in eq (2.1) which shows the pore diameters that are affected by the relative humidities. Figure 4-19 shows a plot of this equation for t ypical values of water of Ts = 0.072 N/m, vw = 1.8x10-5 m3/mol. The temperature used was T = 298.15 K and the universal gas constant R = 8.314472 Nm/Kmol. Results in Figure 4-20 show that the Ocala limestone has the greatest amount of fine pores of all the materials followed by the Miami limestone and finally the Loxahatchee shell rock. The slope of each li ne indicates the number of pores at each diameter. The flat portions of the plot ranging between 10-6 and 10-5 meters are due to testing inaccuracies. As stated earlier, the test is run in two stages and it is between these ranges that the transition between testing stages occurs. The ImageJ software was used to analyze all the images from the SEM exploration. Each image was made binary and the software counted and gave the area for each void. Imaging analysis was used to describe the pore diameter data between 2x10-6 and 1x10-3 meters which covers the range of the transition measurements in the mercury porosimetry. Data was reduced and summar y statistics are shown in Table 4-5. Histograms of the pore data ranging between 2x10-6 and 2x10-5 meters are presented in Figs. 4-21 through 4-24, as this data account s for over 97% of the pores found with the

PAGE 40

29 software. Figures 4-25 through 427 presents the pore diameter distribution from ImageJ analysis in relation to poros ity and shows what portion of th e total porosity the analysis represents. The Glades core data was omitte d because the bulk porosity was not known. An example of the image processing steps is shown in Fig. 4-28. The three different porosity measurements were compared in Table 4-6. The porosity results show that for both the Ocala and Miami limestones, the Mercury Porosimeter test reports higher porosity values than the SEM image analysis, but for the Loxahatchee shell rock, the opposite is true. These results can lead one to the conclusion that overall, the pores in th e Ocala and Miami limestone ar e generally smaller and those found in the Loxahatchee shell rock are generally larger. 4.4 Discussion The resonant column test indicated stiffness increases for all materials. The Ocala limestone showed the greatest rate for sti ffness increase while Loxahatchee shell rock showed the slowest rate of s tiffness increase. Although solubili ty calculations show that in the time frame for the experiment, only a sm all amount of calcite cement was able to precipitate, SEM exploration did not reveal the presence of cementing calcite crystals in any of the laboratory compacted specimens. The maximum volume of calcite able to precipitate was 9.0x10-4 cm3 in the Ocala limestone cured under low relative humidity for 30 days, which was the best-case scenario The cylinder volume was approximately 1650 cm3, so this equates to 0.00005% of new material precipitation. Calc ulations appear in Appendix C. This amount of calcite precip itation would be very difficult to locate. However, images taken of the Glades core commonly show cementing calcite crystals and filling most voids.

PAGE 41

30 Even though calculations show that calcit e cement was able to precipitate, it is believed that it is not the source for the increas e in stiffness. Instead, suction from the loss of water in the pore spaces is reasonable. The potential for stiffness increase due to suction is determined from the Kelvins equati on as stated in eq (2.2). Figure 4.29 shows a plot of this equation for typical values for water of vw 0 = 0.001 m3/kg, v = 18.016 kg/kmol and T and R are previously defined. Table 4. 7 shows this theoretical suction pressure for each of the relative humidities used. The theoretical total suction values differ by approximately an order of magnit ude which provides an explanation for the difference in stiffness increases for each curi ng condition. It is felt that the materials cured under the medium and low relative humid ities did not reach equilibrium with the saturated salt solutions and therefore did not reach the potential moisture loss to show the full effects of the stiffness increase due to the suction pressures. The materials cured under high relative humidity reached near-consta nt moisture contents, so the effects of the suction pressure are shown in the material stiffness.

PAGE 42

31 Table 4-1. Summary of Ocala limestone under different curing conditions. Average stiffness gain and reduction in moisture content versus time. Curing Type Average Time (days) Average % Decrease in Initial Moisture Average % Increase in Youngs Modulus Low RH 1.99 1.05% 142.0% 7.94 3.13% 573.5% 15.83 5.04% 959.7% 32.10 9.96% 2108.6% Medium RH 1.99 0.76% 71.4% 7.95 2.52% 551.0% 15.83 3.35% 657.4% 32.04 8.03% 1513.3% High RH 1.99 0.56% 58.2% 7.97 1.18% 466.1% 15.84 1.55% 475.1% 32.04 1.94% 536.8% Table 4-2. Summary of Miami limestone under different curing conditions. Average stiffness gain and reduction in moisture content versus time. Curing Type Average Time (days) Average % Decrease in Initial Moisture Average % Increase in Youngs Modulus Low RH 2.05 1.36% 42.0% 7.77 3.82% 457.9% 15.76 7.20% 971.8% 31.09 11.17% 1627.6% Medium RH 2.05 1.03% 59.1% 7.79 3.39% 221.0% 15.77 4.86% 647.3% 31.07 9.35% 1118.8% High RH 2.05 0.73% 22.6% 7.81 1.42% 28.0% 15.78 1.73% 73.0% 31.10 2.68% 149.4%

PAGE 43

32 Table 4-3. Summary of Loxahatchee shel l rock under different curing conditions. Average stiffness gain and reduction in moisture content versus time. Curing Type Average Time (days) Average % Decrease in Initial Moisture Average % Increase in Youngs Modulus Low RH 2.00 2.18% 170.4% 7.82 4.02% 354.6% 15.83 8.50% 798.8% 31.24 12.76% 940.0% Medium RH 1.98 1.19% 121.0% 7.83 2.90% 265.9% 15.84 5.33% 596.9% 31.24 8.43% 637.9% High RH 1.97 0.34% 52.4% 7.85 1.12% 187.2% 15.85 1.38% 277.1% 31.24 2.21% 307.7%

PAGE 44

33 0% 400% 800% 1200% 1600% 2000% 2400% 05101520253035 Time (days)% Increase in Young's Modulus Low Medium High Figure 4-1. Ocala limestone stiffness gain versus time for different relative humidities. 0% 400% 800% 1200% 1600% 2000% 2400% 05101520253035 Time (days)% Increase in Young's Modulus Low Medium High Figure 4-2. Miami limestone stiffness ga in versus time for different relative humidities.

PAGE 45

34 0% 400% 800% 1200% 1600% 2000% 2400% 05101520253035 Time (days)% Increase in Young's Modulus Low Medium High Figure 4-3. Loxahatchee shell rock stiffness gain versus time for different relative humidities. 0% 400% 800% 1200% 1600% 2000% 2400% 0%2%4%6%8%10%12%14% % Decrease in Initial Moisture% Increase in Young's Modulus Low Medium High Figure 4-4. Ocala limestone stiffness gain versus decrease in initial moisture for different relative humidities.

PAGE 46

35 0% 400% 800% 1200% 1600% 2000% 2400% 0%2%4%6%8%10%12%14% % Decrease in Initial Moisture% Increase in Young's Modulus Low Medium High Figure 4-5. Miami limestone stiffness gain versus decrease in initial moisture for different relative humidities. 0% 400% 800% 1200% 1600% 2000% 2400% 0%2%4%6%8%10%12%14% % Decrease in Initial Moisture% Increase in Young's Modulus Low Medium High Figure 4-6. Loxahatchee shell rock stiffness gain versus decrease in initial moisture for different relative humidities.

PAGE 47

36 Figure 4-7. Ocala limestone typical image 1. Figure 4-8. Ocala limestone typical image 2.

PAGE 48

37 Figure 4-9. Miami limestone typical image 1. Figure 4-10. Miami limestone typical image 2.

PAGE 49

38 Figure 4-11. Loxahatchee she ll rock typical image 1. Figure 4-12. Loxahatchee shell rock image 2 showing zone of possible calcite crystal growth on left side.

PAGE 50

39 Figure 4-13. Loxahatchee shell rock closeup of highlighted region in Fig. 4-12. Figure 4-14. Glades core typical image 1.

PAGE 51

40 Figure 4-15. Glades core typical image 2 showing zone of calci te crystal growth. Figure 4-16. Glades core close-up of highlighted region in Fig. 4-15.

PAGE 52

41 Figure 4-17. Glades core typical image 3 showing zone of calci te crystal growth. Figure 4-18. Glades core close-up of highlighted region in Fig. 4-17.

PAGE 53

42 Table 4-4. Average bulk propertie s of base course materials. Specimen Specific Gravity Average Moisture Content (%) Porosity, n Ocala Limestone 2.75 14.28 0.318 Miami Limestone 2.78 8.76 0.238 Loxahatchee Shell Rock 2.84 9.00 0.266 Glades Core 2.78 ----Table 4-5. Summary statistics for pore sizes from ImageJ analysis. Specimen Ocala Miami Loxahatchee Glades Core Mean 6.07E-065.55E-066.31E-06 5.39E-06 Standard Error 8.59E-084.54E-081.37E-07 7.37E-08 Median 3.63E-063.63E-063.84E-06 3.63E-06 Mode 2.57E-062.57E-062.56E-06 2.56E-06 Standard Deviation 1.41E-059.28E-061.76E-05 1.09E-05 Sample Variance 1.99E-108.62E-113.1E-10 1.18E-10 Kurtosis 493.6809701.3346926.6147 1008.251 Skewness 18.951419.5398724.77442 24.98864 Range 0.0005220.0005320.000932 0.000651 Minimum 2.57E-062.57E-062.56E-06 2.56E-06 Maximum 0.0005240.0005350.000934 0.000654 Sum 0.1633670.2314540.104128 0.116765 Count 269174171516497 21677 Table 4-6. Comparison of porosity values from different methods. Specimen Bulk Measurements Mercury Porosimetry SEM Image Analysis Ocala Limestone 0.318 0.235 0.183 Miami Limestone 0.238 0.150 0.147 Loxahatchee Shell Rock 0.266 0.101 0.170 Glades Core --0.088 0.101

PAGE 54

43 0.113 0.973 0.5290.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.E-10 1.E-09 1.E-08 1.E-07 1.E-06 Pore Diameter (meters)Relative Humidity, RH Figure 4-19. Relative humidity values and corresponding affected pore diameters. Horizontal lines represent targeted relative humidities.

PAGE 55

44 0.00 0.05 0.10 0.15 0.20 0.25 Pore Diameter (meters)Total Porosity b c a d Figure 4-20. Mercury Porosimeter results for 30-day specimens and Glades core. (a = Ocala limestone; b = Miami limestone; c = Loxahatchee shell rock; d = Glades core) 109 108 107 106 105 104 103

PAGE 56

45 15300 5921 1111 2171 609 399 280 185 1340% 20% 40% 60% 80% 100% 4.0E-068.0E-061.2E-051.6E-052.0E-05 Pore Diameter (meters)Percent of Counted Voids Figure 4-21. Pore diameter histogram from ImageJ analysis for Ocala limestone. Values above bars are frequency. 189 243 392 521 879 1642 3505 9654 236640% 20% 40% 60% 80% 100% 4.0E-068.0E-061.2E-051.6E-052.0E-05 Pore Diameter (meters)Percent of Counted Voids Figure 4-22. Pore diameter histogram from ImageJ analysis for Miami limestone. Values above bars are frequency.

PAGE 57

46 65 121 158 230 351 738 1558 8920 39000% 20% 40% 60% 80% 100% 4.0E-068.0E-061.2E-051.6E-052.0E-05 Pore Diameter (meters)Percent of Counted Voids Figure 4-23. Pore diameter histogram from ImageJ analysis for Loxahatchee shell rock. Values above bars are frequency. 103 130 157 212 424 779 1687 13030 46780% 20% 40% 60% 80% 100% 4.0E-068.0E-061.2E-051.6E-052.0E-05 Pore Diameter (meters)Percent of Counted Voids Figure 4-24. Pore diameter histogram from ImageJ analysis for Glades core. Values above bars are frequency.

PAGE 58

47 0.3180.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 1.E-06 1.E-05 1.E-04 1.E-03 Pore Diameter (meters)Total Porosity Figure 4-25. Ocala limestone pore diameter distribution from ImageJ analysis in relation to porosity. Horizontal line is the bulk porosity. 0.2380.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 1.E-06 1.E-05 1.E-04 1.E-03 Pore Diameter (meters)Total Porosity Figure 4-26. Miami limestone pore diameter distribution from ImageJ analysis in relation to porosity. Horizontal line is the bulk porosity.

PAGE 59

48 0.2660.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 1.E-061.E-051.E-041.E-03 Pore Diameter (meters)Total Porosity Figure 4-27. Loxahatchee shell rock pore diameter distribution from ImageJ analysis in relation to porosity. Horizontal line is the bulk porosity.

PAGE 60

49 A B C Figure 4-28. Image processing steps with ImageJ software. Example is from Ocala specimen. A) Original SEM image taken in grayscale. B) Image converted into binary. C) Binary image is converted into outlines and area data is obtained.

PAGE 61

50 0.529 0.113 0.9731.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 0.00.10.20.30.40.50.60.70.80.91.0 Relative HumidityTotal Suction (kPa) Figure 4-29. Theoretical relative humidity va lues and corresponding total suction. Vertical lines represent targeted relative humidities. Table 4-7. Theoretical suction pressures for different relative humidities. Relative Humidity Suction Pressure (kPa) Suction Pressure (ksi) Low 300,000 43.6 Medium 88,000 12.8 High 3800 0.55

PAGE 62

51 CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS 5.1 Conclusions 1. Curing compacted specimens with diffe rent relative humidities resulted in stiffness increases for each material type. Materials cured under low relative humidity conditions showed the greatest increase in stiffness while materials cured under high relative humidity conditions showed the lowest stiffness increase. 2. Materials cured under high relative hum idity reached stable moisture contents during the testing period. Materials cured under medium and low relative humidities did not reach stable moisture contents in the allo tted test period, but are likewise expected to stabilize. 3. Stiffness increases in this experiment were due to increases in capillary suction due to the removal of water from the system. 4. Materials with more fine pores in th e sub-micron level and also more material passing the #200 sieve resulted in greater sti ffness increases. Ocala limestone showed the greatest stiffness increase while Loxahatchee sh ell rock showed the lowest, which agrees with this statement. 5. Materials showed a linear relations hip between % increase in Youngs modulus and increased % reductions in moisture conten t. It is thought th at the % increase in Youngs modulus will reach some maximum value, though the testing period was not long enough to verify this.

PAGE 63

52 6. Although all materials showed an increa se in stiffness, calculations show the potential crystal growth from calcite in solution was negligible. Expectantly, SEM analysis did not reveal the presence of calcite crystals. It is concluded that the testing period was not long enough to allow the material s to reach equilibrium with the saturated salt solutions. 7. SEM imaging in the Glades core reveal the presence of relatively large calcite crystals. The orientation of these crystals suggests that pores are being filled. Porosity measurements in the Glades core also indicate that most of the pore volume has been filled. 8. SEM analysis coupled with the ImageJ software provided ex cellent quantitative analysis for describing voids. 5.2 Recommendations for Future Work 1. Roadway conditions of base course material should be studied. Sensors recording the temperature, relative humidity, CO2 levels and moisture migration in pores can be implemented during construction. Future test should be long term and mimic these relevant field conditions rather than ch anging individual conditions that may be irrelevant. 2. Doping the specimens with a know substance during compaction would be beneficial when looking for ne w calcite growth. Due to the small quantities of calcite crystals that precipitate and the heterogeneity of limestones, it is very difficult to distinguish new crystal grow th from crystals that may have formed hundreds or thousands of years ago. Neoformed crysta ls would include the doped substance and would be recognizable using EDS, XRD or cathodoluminescence techniques.

PAGE 64

53 3. It may be coincidental that the mate rials with higher fines content resulted in higher stiffness increases, but the effect of fines in regards to increases in stiffness should be studied. 4. The effect of initial moisture conten t should be studied because contractors may meet density requirements using moisture co ntents both wet and dry of the optimum. A range of initial moisture contents and their e ffect on stiffness increase should be tested as materials in this study were only compacted 1% wet of the optimum moisture content.

PAGE 65

54 APPENDIX A MODIFIED PROCTOR AND LBR RESULTS Figure A-1. Ocala limestone Modified Proctor and LBR data

PAGE 66

55 Figure A-2. Miami limestone Modi fied Proctor and LBR data

PAGE 67

56 Figure A-3. Loxahatchee shell rock Modified Proctor and LBR data

PAGE 68

57 APPENDIX B RESONANT COLUMN TESTING DATA Table B-1. Data for Ocala Limestone after Compaction Ocala Mold Wt: 0.242lbs 26-002 Diameter: 4in 26-All Height: 8in Initial V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 26-L-02-19/1/07 23:408.0514.44%1044.17141390.56 26-L-02-29/4/07 23:408.0714.14%1364.18211810.95 26-L-07-18/18/07 20:557.9914.31%1204.13931600.74 26-L-07-28/18/07 21:057.9714.49%2164.12862882.38 26-L-14-17/15/07 19:508.0314.00%1284.16071710.84 26-L-14-28/7/07 19:557.9914.37%1124.13931490.64 26-L-30-17/15/07 19:308.0314.36%1524.16072031.19 26-L-30-27/15/07 19:358.0414.35%1364.16601810.95 26-M-02-19/1/07 23:458.0314.55%1044.16071390.56 26-M-02-29/4/07 23:458.0614.32%1044.17671390.56 26-M-07-18/18/07 20:458.0014.35%1204.14471600.74 26-M-07-28/18/07 20:508.0614.18%1124.17671490.65 26-M-14-17/15/07 19:508.0014.19%1364.14471810.95 26-M-14-28/7/07 19:458.0014.19%1204.14471600.74 26-M-30-17/15/07 19:208.0914.02%1764.19272351.60 26-M-30-27/15/07 19:258.0814.14%1124.18741490.65 26-H-02-19/1/07 23:508.0514.35%1204.17141600.74 26-H-02-29/4/07 23:508.0114.33%1284.15001710.84 26-H-07-18/18/07 20:307.9614.45%1204.12331600.73 26-H-07-28/18/07 20:408.0114.43%1204.15001600.74 26-H-14-17/15/07 19:408.0214.07%1364.15531810.95 26-H-14-28/7/07 19:407.9714.30%1284.12861710.84 26-H-30-17/15/07 19:108.0414.04%1204.16601600.74 26-H-30-27/15/07 19:158.0314.24%1204.16071600.74 Sample Number : Testing Condition : Quarry : Pit Number :

PAGE 69

58 Table B-2. Data for Ocala Limestone after Curing Ocala Mold Wt: 0.242lbs 26-002 Diameter: 4in 26-All Height: 8in Final V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) Days M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 26-L-02-19/3/07 23:402.008.0414.29%1524.16602031.19 26-L-02-29/6/07 23:001.978.0513.99%2244.17142992.58 26-L-07-18/26/07 19:257.947.9613.90%3764.12335017.20 26-L-07-28/26/07 19:307.937.9314.00%4164.10735558.78 26-L-14-18/1/07 13:4516.757.9513.00%4164.11795558.80 26-L-14-28/22/07 17:4014.917.9513.94%3684.11794916.88 26-L-30-18/16/07 20:2532.047.9212.92%6964.101992824.53 26-L-30-28/16/07 23:3032.167.9312.93%6644.107388522.36 26-M-02-19/3/07 23:452.008.0214.48%1444.15531921.06 26-M-02-29/6/07 23:051.978.0514.17%1284.17141710.84 26-M-07-18/26/07 19:357.957.9713.97%3364.12864485.75 26-M-07-28/26/07 19:407.958.0413.84%2564.16603413.37 26-M-14-18/1/07 13:5016.757.9513.55%3604.11794806.59 26-M-14-28/22/07 17:4514.927.9713.88%3444.12864596.03 26-M-30-18/16/07 20:1532.048.0012.88%5684.144775716.51 26-M-30-28/16/07 20:2032.047.9913.02%5284.139370414.25 26-H-02-19/3/07 23:502.008.0514.32%1524.17142031.19 26-H-02-29/6/07 23:101.978.0014.20%1604.14472131.31 26-H-07-18/26/07 19:457.977.9514.28%3064.11794084.76 26-H-07-28/26/07 19:507.977.9914.26%2644.13933523.56 26-H-14-18/1/07 13:5516.768.0113.85%3604.15004806.64 26-H-14-28/22/07 17:5014.927.9514.08%2724.11793633.76 26-H-30-18/16/07 20:0532.048.0213.76%3444.15534596.07 26-H-30-28/16/07 20:1032.048.0113.97%2564.15003413.36 Testing Condition : Quarry : Pit Number : Sample Number :

PAGE 70

59 Table B-3. Data for Miami Limestone after Compaction Miami Mold Wt: 0.242lbs 87-090 Diameter: 4in 87-All Height: 8in Initial V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 87-L-02-19/4/07 22:008.668.85%1844.49732451.88 87-L-02-29/4/07 22:058.648.80%1444.48661921.15 87-L-07-18/18/07 23:258.568.88%2244.44382992.75 87-L-07-28/18/07 23:308.618.92%1364.47051811.02 87-L-14-17/15/07 22:458.638.63%1524.48122031.28 87-L-14-28/7/07 20:158.628.60%2084.47592772.39 87-L-30-17/16/07 16:458.608.79%1524.46522031.27 87-L-30-27/16/07 16:508.629.03%1604.47592131.41 87-M-02-19/4/07 22:108.628.75%1444.47591921.15 87-M-02-29/4/07 22:208.618.69%1604.47052131.41 87-M-07-18/18/07 23:158.638.93%1844.48122451.87 87-M-07-28/18/07 23:208.598.49%1364.45991811.02 87-M-14-17/15/07 22:408.618.50%1444.47051921.14 87-M-14-28/7/07 20:108.619.20%2164.47052882.58 87-M-30-17/16/07 16:358.548.06%1524.43312031.26 87-M-30-27/16/07 16:408.638.30%1364.48121811.02 87-H-02-19/4/07 22:258.569.01%1124.44381490.69 87-H-02-29/4/07 22:308.508.72%1124.41181490.68 87-H-07-18/18/07 23:058.548.76%1524.43312031.26 87-H-07-28/18/07 23:108.558.90%1524.43852031.27 87-H-14-17/15/07 22:358.618.73%1924.47052562.03 87-H-14-28/7/07 20:058.619.19%1604.47052131.41 87-H-30-17/16/07 16:258.638.96%1524.48122031.28 87-H-30-27/16/07 16:308.568.57%1844.44382451.86 Testing Condition : Quarry : Pit Number : Sample Number :

PAGE 71

60 Table B-4. Data for Miami Limestone after Curing Miami Mold Wt: 0.242lbs 87-090 Diameter: 4in 87-All Height: 8in Final V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) Days M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 87-L-02-19/6/07 23:152.058.658.71%2244.49192992.78 87-L-02-29/6/07 23:202.058.638.70%1684.48122241.56 87-L-07-18/26/07 18:007.778.538.53%3044.42784055.05 87-L-07-28/26/07 18:057.778.588.59%4164.45455559.52 87-L-14-18/1/07 13:2016.618.557.74%5844.438577918.69 87-L-14-28/22/07 18:1014.918.598.25%5444.459972516.29 87-L-30-18/16/07 18:5531.098.517.80%6884.417191725.81 87-L-30-28/16/07 19:0031.098.538.03%6084.427881120.21 87-M-02-19/6/07 23:252.058.618.65%1764.47052351.71 87-M-02-29/6/07 23:302.058.618.61%2084.47052772.39 87-M-07-18/26/07 18:157.798.608.60%2404.46523203.18 87-M-07-28/26/07 18:207.798.578.23%2964.44923954.81 87-M-14-18/1/07 13:2516.618.567.88%4964.443866113.50 87-M-14-28/22/07 18:2014.928.598.96%3844.45995128.12 87-M-30-18/16/07 18:1531.078.487.28%4324.401157610.14 87-M-30-28/16/07 18:3031.088.577.55%5524.449273616.74 87-H-02-19/6/07 23:352.058.568.94%1284.44381710.90 87-H-02-29/6/07 23:402.058.498.66%1204.40641600.78 87-H-07-18/26/07 18:257.818.538.64%1764.42782351.69 87-H-07-28/26/07 18:307.818.548.77%1684.43312241.54 87-H-14-18/1/07 13:3016.628.608.57%2244.46522992.77 87-H-14-28/22/07 18:3014.938.609.04%2324.46523092.97 87-H-30-18/16/07 18:4531.108.618.72%1764.47052351.71 87-H-30-28/16/07 18:5031.108.548.34%3524.43314696.78 Testing Condition : Quarry : Pit Number : Sample Number :

PAGE 72

61 Table B-5. Data for Loxahatchee Shell Rock after Compaction Loxahatchee Mold Wt: 0.242lbs 93-406 Diameter: 4in 93-All Height: 8in Initial V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 93-L-02-19/1/07 22:008.558.66%2404.43853203.16 93-L-02-29/1/07 22:058.559.20%2644.43853523.82 93-L-07-18/18/07 22:558.468.99%2884.39043844.50 93-L-07-28/18/07 23:008.478.94%2324.39583092.92 93-L-14-17/15/07 22:258.508.75%2164.41182882.54 93-L-14-28/7/07 17:258.479.01%1684.39582241.53 93-L-30-17/16/07 13:458.519.03%2084.41712772.36 93-L-30-27/16/07 13:508.529.15%2164.42252882.55 93-M-02-19/1/07 22:108.548.81%2564.43313413.59 93-M-02-29/1/07 23:208.528.89%2724.42253634.04 93-M-07-18/18/07 22:458.469.11%1924.39042562.00 93-M-07-28/18/07 22:508.539.15%2484.42783313.36 93-M-14-17/15/07 22:208.509.23%1924.41182562.01 93-M-14-28/7/07 17:208.488.79%1924.40112562.00 93-M-30-17/16/07 13:358.519.78%2804.41713734.28 93-M-30-27/16/07 13:408.578.73%2084.44922772.38 93-H-02-19/1/07 23:158.519.24%2724.41713634.03 93-H-02-29/1/07 23:308.558.62%3004.43854004.93 93-H-07-18/18/07 22:358.499.00%1604.40642131.39 93-H-07-28/18/07 22:408.488.80%1844.40112451.84 93-H-14-17/15/07 22:158.428.76%2084.36902772.33 93-H-14-28/7/07 17:008.519.31%2164.41712882.54 93-H-30-17/16/07 13:258.499.07%1444.40641921.13 93-H-30-27/16/07 13:308.499.07%1924.40642562.01 Testing Condition : Quarry : Pit Number : Sample Number :

PAGE 73

62 Table B-6. Data for Loxahatchee Shell Rock after Curing Lox Mold Wt: 0.242lbs 93-406 Diameter: 4in 93-All Height: 8in Final V olume: 100.531in^3 V olume: 0.0582ft^3 Specimen Date, Time (m/dd/yy hh:mm) Days M/S Weight (lbs) Moisture Content (%) Freq. (Hz) Density, (lbs/ft3) Vp (ft/sec) E (ksi) 93-L-02-19/3/07 22:002.008.548.51%4244.43315659.84 93-L-02-29/3/07 22:052.008.538.96%4004.42785338.75 93-L-07-18/26/07 18:357.828.438.63%5364.374471515.52 93-L-07-28/26/07 18:407.828.448.58%5524.379773616.48 93-L-14-18/1/07 13:0016.618.427.73%6084.369081119.94 93-L-14-28/22/07 18:4015.058.438.52%5364.374471515.52 93-L-30-18/16/07 19:3531.248.427.84%7284.369097128.59 93-L-30-28/16/07 19:4031.248.438.02%6404.374485322.12 93-M-02-19/3/07 22:102.008.548.73%3924.43315238.41 93-M-02-29/3/07 22:201.968.518.76%3924.41715238.38 93-M-07-18/26/07 18:457.838.448.82%3764.37975017.64 93-M-07-28/26/07 18:507.838.518.91%4644.417161911.74 93-M-14-18/1/07 13:0516.618.458.60%5684.385175717.47 93-M-14-28/22/07 18:4515.068.468.46%4404.390458710.49 93-M-30-18/16/07 19:2531.248.458.95%7044.385193926.83 93-M-30-28/16/07 19:3031.248.518.00%6084.417181120.16 93-H-02-19/3/07 22:301.978.509.20%3524.41184696.75 93-H-02-29/3/07 22:401.978.548.60%3524.43314696.78 93-H-07-18/26/07 18:557.858.498.90%2644.40643523.79 93-H-07-28/26/07 19:007.858.478.70%3204.39584275.56 93-H-14-18/1/07 13:1516.638.418.63%4004.36375338.62 93-H-14-28/22/07 18:5015.088.509.19%4244.41185659.79 93-H-30-18/16/07 19:1531.248.478.81%2884.39583844.50 93-H-30-28/16/07 19:2031.248.488.93%3924.40115238.35 Testing Condition : Quarry : Pit Number : Sample Number :

PAGE 74

63 Figure B-1. Example 1 of frequency measur ed in Free-Free Resonant Column test. Initial value from specimen 93-L-14-2.

PAGE 75

64 Figure B-2. Example 2 of frequency measur ed in Free-Free Resonant Column test. Final value from specimen 93-L-14-2.

PAGE 76

65 APPENDIX C CALC ULATIONS From Faure (1998), the highest possible concentration of cal cium ions in solution is: [Ca2+] = 4.86-4 (mol/L) Vcalcite = 36.93 (cm3/mol) Molar volume of calcite 36.93 (cm3/mol) 4.86-4 (mol/L) = 1.79-2 cm3/L 1.79-2 cm3/L Amount of calcit e able to precipitate Ocala volume of solution = 0.501 L Initial volume of water in specimen 0.501 (L) 1.79-2 (cm3/L) = 9.0-3 cm3 Volume of Calcite able to precipitate Moisture loss = 10% Moisture loss observed for low RH curing 9.0-3 0.10 = 9.0-4 cm3 9.0-4 cm3 Volume of calcite precipitated Table C-1. Summary of values used for calculating precipitated calcite. Material Amount of Solution (Liters) Volume of calcite able to precipitate (cm3) Maximum Moisture Lost (%) Maximum Vol. of Calcite able to Precipitate for Test Conditions (cm3) Ocala 0.501 9.0-3 10 9.0-4 Miami 0.330 5.9-3 11 6.5-4 Loxahatchee 0.336 6.0-3 13 7.8-4

PAGE 77

66 LIST OF REFERENCES Allen, R.F. [et al.] (2000) Annual Book of ASTM Standards Vol. 4.08. American Society for Testing and Materials, Pennsylvania. Bricker, O.P., ed. (1971) Carbonate Cements. The Johns Hopkins Press, Baltimore. Faure, G. (1998) Principles and Applicat ions of Geochemistry 2nd Ed. Prentice Hall, Inc., New Jersey. Florida Department of Transportation, (2007) City County Mileage Report, FDOT Homepage, http://www2.dot.state.fl.us /planning/m ileage/word/pdf /pdf_report_final_inet.asp (Accessed May 2007) Gartland, J.D. (1979) Experimental Dissolution-Repreci pitation Processes with Two Florida Limestones. Masters Thesis, Univ. of Florida. Goldstein, J.I. [et al.] (1992) Scanning Electron Microsc opy and X-Ray Microanalysis 2nd Ed. Plenum Press, New York. Graves, R.E. (1987) Strength Developed from Carbonate Cementation in Silica/Carbonate Systems as Influenc ed by Cement-Particle Mineralogy Masters Thesis, Univ. of Florida. Huang, Y.A. (2004) Pavement Analysis and Design 2nd Ed. Pearson Prentice Hall, New Jersey. Lambe, T.W. and R.V. Whitman. (1969) Soil Mechanics John Wiley and Sons, Inc., New York. Lindholm, R.C. (1974) Fabric and Chemistry of Pore Filling Calcite in Septarian Veins: Models for Limestone Cementation. In D.S. Gorsline, Ed. Journal of Sedimentary Petrology Vol. 44. Society of Economic Paleonto logists and Mineralogists, Oklahoma. Lu, N. and W.J. Likos. (2004) Unsaturated Soil Mechanics John Wiley and Sons, Inc., New Jersey. Menq, F. (2003) Dynamic Properties of Sandy and Gravelly Soils PhD Dissertation, Univ. of Texas at Austin.

PAGE 78

67 Miller, J.P. (1952) A Portion of the Syst em Calcium Carbonate-Carbon Dioxide-Water, with Geological Implications. In C.R. Longwell and J. Rodgers, Eds. American Journal of Science Vol. 250. Yale University, Connecticut. Moore, C.H. (1989) Carbonate Diagenesis and Porosity Elsevier Science Publishers B.V., Amsterdam. Rasband, W.S., ImageJ, U. S. National Instit utes of Health, Bethesda, Maryland, USA, http://rsb.info.nih.gov/ij/ (Accessed June 2007) Shaw, D.J. (1992) Introduction to Colloid and Surface Chemistry 4th Ed. ButterworthHeinemann Ltd, Oxford. Smith, L.L. and W.N. Lofroos. (1981) Pavement Design Coefficients: A Re-Evaluation of Florida Base Materials Research Report. State of Florida Department of Transportation. University of Arizona, The RRUFF Project. http://rruff.geo.arizona.edu/rruff/ (las t accessed October 2007) Zimpfer, W.H. (1989) Strength Gain and Cementation of Flexible Pavement Bases Final Report for the Florida Department of Tr ansportation. University of Florida, Department of Civil Engineering.

PAGE 79

68 BIOGRAPHICAL SKETCH Luis Alfonso Ca mpos was born in 1983 in Tampa, Florida. After graduating from Sickles High School in 2001, he attended the University of Florida where he received a Bachelor of Science degree in December 2005 with a major in civil engineering. During his undergraduate studies, he worked part time at a small geotechnical engineering firm in Gainesville where he gained valuable experience in geotechnical engineering. The experience that he gained led him to continue with graduate studies at the University of Florida. He received a Master of Engineering degree in May 2008 and plans to work at a geotechnical consulting firm in North Carolina.


xml version 1.0 encoding UTF-8
REPORT xmlns http:www.fcla.edudlsmddaitss xmlns:xsi http:www.w3.org2001XMLSchema-instance xsi:schemaLocation http:www.fcla.edudlsmddaitssdaitssReport.xsd
INGEST IEID E20101117_AAAACQ INGEST_TIME 2010-11-17T22:32:21Z PACKAGE UFE0021855_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES
FILE SIZE 73089 DFID F20101117_AABQLC ORIGIN DEPOSITOR PATH campos_l_Page_27.jpg GLOBAL false PRESERVATION BIT MESSAGE_DIGEST ALGORITHM MD5
2b5b75a5e6c524d7ac80f1258002817b
SHA-1
0924b3937e9f52bca4b590c50a09c0df95c0e1cd
2887 F20101117_AABQXU campos_l_Page_69.txt
885733616ccb293eee67f3927a0eb944
14b9cb22ea46e146cad0789f96f2a92a71eb6b7b
47889 F20101117_AABQSX campos_l_Page_07.pro
7b97f72fb29e905a8a773a3bf4bf597e
4a60e068afd36afa8aed98013d697fb3aea6195b
2836 F20101117_AABQXV campos_l_Page_70.txt
25dc4887b1ec1428da38213d89132cba
25e88819915d3be38302d21fb75bf404b6274ebc
25271604 F20101117_AABQQA campos_l_Page_05.tif
08ca8f7e818ee137764439b9059ced3e
d8a22104dce47f78e4534befff0d0d2161b7766a
71552 F20101117_AABQSY campos_l_Page_08.pro
e6b33ed83ab3689672c860db0e2eac86
9243124f28785ffd82093544febdf0fc1eae4274
77269 F20101117_AABQLD campos_l_Page_28.jpg
1e440c82ead2e864779572a28784e38e
ffdfb39dfa4aa0f378ddda507d4bdd304188757a
2846 F20101117_AABQXW campos_l_Page_71.txt
e6e20c65044bb329d4dc99f18c682a77
cdd725ce5b4397eacb43b63e00cf2a9470342d96
F20101117_AABQQB campos_l_Page_06.tif
e025231dd6ec5ccaa08dd7fed0e64e7a
59b254039ed41614bb3c6c13ba62dd418b85f99e
54556 F20101117_AABQSZ campos_l_Page_09.pro
fd6e4987b3e2d7863e58cd08e9ff2b94
f4e77f1062f4d9a0d60c85b8341aad7cfa46032c
27416 F20101117_AABQLE campos_l_Page_29.jpg
b5f62cce3a1c51156cc533fcec8a91ca
53624a8b3946a4fd7c98878797b6a75ef1b0f239
2842 F20101117_AABQXX campos_l_Page_72.txt
d56eab06353de2d9bf89ca48150ae659
545d4f58c9925d05b47ffa8d0991d5ea84353a57
F20101117_AABQQC campos_l_Page_07.tif
74b7f0091e924f5431d3322cfd2ec662
e53f96cb015aae42fdf21abcb2cf7bb6ba1aa3ee
25770 F20101117_AABQLF campos_l_Page_30.jpg
a14d08bb6d54effe2018433a2726e9d7
04ae4230bd0757bf78c07aa8fa7823bc7715b19b
62446 F20101117_AABQVA campos_l_Page_71.pro
b7f095a55813096921fa4f143c3874f9
712fa2111fb39d728305bdadcf10eee29e7c56e4
2854 F20101117_AABQXY campos_l_Page_73.txt
2302f8f537ad4ac61c1cd538ef4daced
f7439bf9834c437c30c35bda88e3387576a61bc8
F20101117_AABQQD campos_l_Page_08.tif
1765065957ecb0817c8a0ea2c905e29a
336f7258bf3d51efbc7dba0effcad411cbe30a4e
415 F20101117_AABQXZ campos_l_Page_74.txt
0dd8c62fa360d9149c8695f61f278b90
998245287df1af3dcacf922108729e59d859d603
59772 F20101117_AABQVB campos_l_Page_72.pro
8aa1356c502ba51ed9a30fbc028ff763
f4fceab3eab4b2820aa68ac28dfedd4ce92c3137
F20101117_AABQQE campos_l_Page_09.tif
717dd7c39681cdb69b77ff712cad1cd4
f37078e0e7a04f38f6c0468fe1def82f89e11180
36546 F20101117_AABQLG campos_l_Page_31.jpg
352fc7b622ba57c9d474ee1211fb9297
1dd6c145b30bc05ffc5d36dbff3a04fb6b5a9f46
62755 F20101117_AABQVC campos_l_Page_73.pro
327faa995af096c31c3db87fae6a5039
738f1695b03db819737744041b78e0eb6293f574
F20101117_AABQQF campos_l_Page_10.tif
9596db357a82cd7695f1bbb09e97c9f7
0d23d0011f315cedd2b05ae49aeb1e985ec3179b
33640 F20101117_AABQLH campos_l_Page_32.jpg
2867183c87019d2f1a07b5b4d0ed2a04
eaed002375196062d0681461a5765277c4a64529
17667 F20101117_AABRCA campos_l_Page_53.QC.jpg
a82a95e56776b8fc75a02786507b88cf
db54ab8979118eb552e1468648511bb42ec8424e
6118 F20101117_AABQVD campos_l_Page_74.pro
6231b280775d58993db5c37859555dbd
98df70248755b3326924cdde1495f9832a9291bc
F20101117_AABQQG campos_l_Page_11.tif
11fc14ff6392d2da08db0b3237f35a18
325dce0a24767f9978ee1f601fbd15349e92e1d5
18677 F20101117_AABQLI campos_l_Page_33.jpg
0a972fe3ef5342e4f13e0c7836f704ac
73afdd372a233d7b1bb2711cb4443ecda9c3fbf1
5031 F20101117_AABRCB campos_l_Page_53thm.jpg
5df988e19aa04182c9e81841220e6995
e03af777d7a2c58e98d1377fe440a2e3e17d62bc
5232 F20101117_AABQVE campos_l_Page_75.pro
77f9938a6ad24861b6ffc124b7c8f0ac
d19f9b0be85ff3af9dace265e553d9cbbed5b291
F20101117_AABQQH campos_l_Page_12.tif
68da17d14d4ce37ca54cb102b94e7f1e
a7760fc279b4da9697ccf37036af6516612ee6fc
29044 F20101117_AABQLJ campos_l_Page_34.jpg
a6129bbf54d61b8dddab36c19f2240d3
1f057597978a70eed3f0978bd389c4be1890a2d4
9529 F20101117_AABRCC campos_l_Page_54.QC.jpg
27d6d77549dcdb5cc80ad1708d9e5cb0
8679be8c1a8442a101a9435d3dcb3afab20bb846
28436 F20101117_AABQVF campos_l_Page_76.pro
337765fb043a62af6c5d839e6742b494
0f5c87b111c7f7114488921a79e23d21c02e0953
F20101117_AABQQI campos_l_Page_13.tif
83174a497b0664fa3454896e389e06b8
9b632df642d9f31b390894e216ba4389c1638619
19301 F20101117_AABQLK campos_l_Page_35.jpg
14b67b5956955b7d755e0b06345bd865
5749678ba70da01a05df4e6007a382654abc3040
9781 F20101117_AABRCD campos_l_Page_55.QC.jpg
acebeee6c6a8739f0e703dee77f8f99b
8497ae053f864b3779830fb5e06885a89d68d446
42301 F20101117_AABQVG campos_l_Page_77.pro
3a13131bb4e832777c1c999f05c5c9b1
dde52aba183d961afabfe8a4dcb5b968be9cf285
F20101117_AABQQJ campos_l_Page_14.tif
bab662b750d6ada21b2193399c886922
ecf78d66664f33d67ae84257207ae34007b9f388
72919 F20101117_AABQLL campos_l_Page_36.jpg
7a66c1b1371a71aa74e72a6f82ea1f0f
665a7d89c679707d010b09c52e3c6264b3a7c0aa
11996 F20101117_AABRCE campos_l_Page_56.QC.jpg
7689ce3fd8f487e222b14c343009a794
48447fce1b593d3814aca5934af5a207d4bc5208
27537 F20101117_AABQVH campos_l_Page_78.pro
f6569102617160a543defc5230dbb62a
58c286c7c2418f7f155fa5309bd15f334165ca8b
F20101117_AABQQK campos_l_Page_15.tif
b0698e72b2ce8f4149ce85e2512c8485
07f4bc781bc83925251a0b128447e6a84664dd49
80447 F20101117_AABQLM campos_l_Page_37.jpg
fe5ac4a8bd14cdbb6fc903fa8c8b86fe
4e6b39689fd530dfd91d6ea4a697b5f2bfd6414c
3840 F20101117_AABRCF campos_l_Page_56thm.jpg
e0ec495e50c58970177248d6982d31e3
88cf375d742987ecaaa6c1cea882774c2685c049
17753 F20101117_AABQVI campos_l_Page_79.pro
714b970c318c679abad6377114359cb3
949d25338981da58bb9fba0eebf0cdd0a1103ce8
79138 F20101117_AABQLN campos_l_Page_38.jpg
7c475fea35c59f389aa1d4ea98fe75d2
c6ff4c7fe920714c636ef317c3a8bca70b113198
12190 F20101117_AABRCG campos_l_Page_57.QC.jpg
82c74782a90e7afdfde5a56c5ddaba14
e5054e0f9cb84052ae8c71ee9a9363e618ad447a
428 F20101117_AABQVJ campos_l_Page_01.txt
dc08ac02d39d66b48128abb067e6d975
9cb2daa1ea476461aca37c9e32cf8c2076cbf1ca
F20101117_AABQQL campos_l_Page_16.tif
a193562fc7cbdebec43573358f762a6f
1f5d8086b1518bc1aa1086502fe9f79b17a3f7d3
80511 F20101117_AABQLO campos_l_Page_39.jpg
56db5a092fd60ff2f824bda9bcdeb08a
1b80099eed111cd2644508d3230c837029abe30d
3946 F20101117_AABRCH campos_l_Page_57thm.jpg
5172afc27b6ced1a93b7bd637c7fdc22
62f716495b23b53892d0a81bbde0dc71b3909c13
93 F20101117_AABQVK campos_l_Page_02.txt
c9126ace07f2bb5825e530d30d862b2a
82e5877bec6ca8b7b7d152496dad11afbd2ab3b3
F20101117_AABQQM campos_l_Page_17.tif
2a0b74b76310fc07c73d778f9744927e
cca625f648ecebff7b61a158a72e2cdab5e5cd3d
76552 F20101117_AABQLP campos_l_Page_40.jpg
c6a5544080986042c621eac99db0225e
312918c0fd064c483b3747a6f0b040fe0d08586b
11102 F20101117_AABRCI campos_l_Page_58.QC.jpg
32d98955bc632fbdf9165265f0bf4707
c6c1259c7612f529260cc636f6f3418af6243db8
106 F20101117_AABQVL campos_l_Page_03.txt
ff68fb6a80cb717df2a42b5c59f1bdf4
6b3c3ac51f9f058370eaa82ba3811056b79a7b3e
F20101117_AABQQN campos_l_Page_18.tif
6a6e7aa525bae4c3e7a37bbfb3e79395
7a60d361a8e1fe9c350ba5ac3ba44917ffd587a7
52224 F20101117_AABQLQ campos_l_Page_41.jpg
74279aea2482a471c921fb80f0eab422
dc3c4aa07d921b7d5f53e5ce2b9d6966d8305510
3761 F20101117_AABRCJ campos_l_Page_58thm.jpg
7b96acc14c9408c988123455492d07b5
3fb0e02f2219126ebd8e39e9c2707d19747e8abd
F20101117_AABQQO campos_l_Page_19.tif
586ecc599a277bec6b29fa06b97c8087
99f0eac33aa5a315a62a596d17f751dbd74b05e3
31403 F20101117_AABQLR campos_l_Page_43.jpg
e510a4b1f1e7368f0c94b732631cbf72
ab6ed3520249e6b7afc29fec9d72ff3fa0f79489
3900 F20101117_AABQVM campos_l_Page_05.txt
26afed53b7323a9e11494c89d97be213
25764c087eaeaf8563ad955a9e220a6dec30e082
7462 F20101117_AABRCK campos_l_Page_59.QC.jpg
77cfb1a05135748688462455514bed69
eec40b628d7e235dc80d67e77b0e947ef6a10d26
F20101117_AABQQP campos_l_Page_20.tif
1a09abe5eff9eb26f846ab39afebf8ad
18f88acda691ea7b45717c3c38e0daf30161501a
38507 F20101117_AABQLS campos_l_Page_44.jpg
9f1a67225a1a16421ddd4b6b1d476663
f56b79a6c191647af6cacdeb9e65cf7579d8e19a
1149 F20101117_AABQVN campos_l_Page_06.txt
c297f809cfc7951f0ddd833650e2e606
706d20546b6ed60d5dbcb165bdcb3d3fb10f4f37
2677 F20101117_AABRCL campos_l_Page_59thm.jpg
1eafba23f43439aed31ba2bed65e0bca
bb7967462159bc63b5fb0fbfb1e89851ace69672
F20101117_AABQQQ campos_l_Page_21.tif
ba80058974b4c1ec913f1d2997ef91f5
a554e88ce3990eab473cd21444db90ffffe68fd9
38019 F20101117_AABQLT campos_l_Page_45.jpg
c4590973dddb20ce963ff146f9aad5df
14b730a5de4b3c70374a9321a8a432d474ccbe22
1945 F20101117_AABQVO campos_l_Page_07.txt
12c477098bcd117ba8d4e3c48d7019fd
1584e12741f89d653e2823009d9e13be248ac945
17776 F20101117_AABRCM campos_l_Page_60.QC.jpg
6c2c9b0fbcc5a5a27a9a5fc2f2f96203
0095aa2e8a65374ae5188ff4fba0d16c7ef89bc1
F20101117_AABQQR campos_l_Page_22.tif
daa5fc71acdb9b6ce3283ab9cc183fde
7856b5a68b0f7a0959107f63ca959c82330b695c
39684 F20101117_AABQLU campos_l_Page_46.jpg
5d8ee28ad7e4ea9f1a6d1413f6631d30
2a2231002d64e8160615435d7e5a2e6fadf71446
2862 F20101117_AABQVP campos_l_Page_08.txt
24d9b53ec364e4639c8c443dfa2dea25
3d7be7b1c59b6e1bb561b96f20134b8fc8e438e0
5127 F20101117_AABRCN campos_l_Page_60thm.jpg
3e72450efbe57a54eb27c20f29c9afe3
ea37cbec1ded5df2fd1bd17e1a4985bbbda8556c
F20101117_AABQQS campos_l_Page_23.tif
8b3dc83939fb6ab816cd8c9eda0da354
0c2d9542ee3c41682a42206f72f591b1e3417c0d
76308 F20101117_AABQLV campos_l_Page_47.jpg
587b14272b5c4559152410fb120d8835
495f04cecf4cc4d649c39cb4418d4eb43445ff34
10877 F20101117_AABRCO campos_l_Page_61.QC.jpg
c8354c819d7b86c6fd8817004b24b9a8
e6329bb2774b4b2f1fdebde6c9000206bd96e283
F20101117_AABQQT campos_l_Page_24.tif
07409032a29ee55aebd2409d5263e768
c6281f74b38076a1a0805daad2078ebe9ab2bedb
74714 F20101117_AABQLW campos_l_Page_48.jpg
5b55a03ec4b6650bc73c8d8764b8bc26
c5d13f971069e835950a4430b62014ef475c157e
2171 F20101117_AABQVQ campos_l_Page_09.txt
33b9d549736031a3cd86f0bbdadbfb7d
d3393a6ba1155b204e4ebd52113e8d8cfcde2722
3600 F20101117_AABRCP campos_l_Page_61thm.jpg
4e62c56f684bce7f3011f7a63d211d2c
30d04622e3f238d362778e8102e66ff54946f1dc
F20101117_AABQQU campos_l_Page_25.tif
0cc91fbc13012158d55ff8d0796cebeb
969d792bddbc81aaf6a1ba6d1865a29772bc3724
59269 F20101117_AABQLX campos_l_Page_49.jpg
1efa48bc1d77921d6aa9dde2b40b9520
ef83ac706a774c8114f67e07effd5cf2197efb5b
1575 F20101117_AABQVR campos_l_Page_10.txt
41c5cf9e65b1dd0c5181e3c5c10d6d30
f05e0e7d3a379ce2dc04f9f06116f7320a637e02
5303 F20101117_AABRCQ campos_l_Page_62thm.jpg
6b7911ef916677de860851d22e2fc2e5
3c41e8ff209bd07e913acc5555d7c51d67292678
F20101117_AABQQV campos_l_Page_26.tif
fefdffc4bc67a98c3be41492587f9c17
a8ad1283e758ecad0acd54964d952909a03db3a7
F20101117_AABQJA campos_l_Page_77.tif
a1a95bd1e414197832f060e5b06d33ea
edf093c0974808a6c08b4d3eba7443e842782c74
77392 F20101117_AABQLY campos_l_Page_50.jpg
12e1ea7f77cd64b2f60bcd4ec184e257
a17be8897e93dc820b19ce050c519927b60a09f0
718 F20101117_AABQVS campos_l_Page_11.txt
aeb9b3ebe1ff7572adb418dcbcfaab9c
4aac0e615558b765fba0c3d3bc851a75042602bd
22331 F20101117_AABRCR campos_l_Page_63.QC.jpg
a60f097aa451bd9af69ea9dc998821de
277624a261ddf3703f6c2df2dbd9d24007d83039
F20101117_AABQQW campos_l_Page_27.tif
ca3a3aa5cb762e7cba97e48d5a3c81f4
4ce5ab003bfeef68666ddbe8f5f3f50e413debee
F20101117_AABQJB campos_l_Page_73.tif
179d8e01aeba74657499654f1995a63e
83d3c4d8d21e58c6760a37041597590be149d6a5
70853 F20101117_AABQLZ campos_l_Page_51.jpg
e1ade51db4123967c3e8212a6dab3c38
fe703cca548b9fb04844303ce455ae7405bda286
1608 F20101117_AABQVT campos_l_Page_12.txt
aed9e04f97cf88da94637f9c83fe8304
4a7f3326f23f6e290bd7f262ca02b86224d88b52
6476 F20101117_AABRCS campos_l_Page_63thm.jpg
9f636b2f1dae62bdf2991896b1853d25
98941b659a84feec35efea701b53ba36ccae47bf
F20101117_AABQQX campos_l_Page_28.tif
4aae3dce2938e3a17df052e0b5342e8e
cacc8a52fec354720281d12ca35ffeb9714ec118
15970 F20101117_AABQJC campos_l_Page_61.pro
1324c50aa1745dbd6d8e326e76170297
d4cc5589bad13c03948196a0bca524fedd215263
1998 F20101117_AABQVU campos_l_Page_13.txt
e0cde01224bc8189acbb78797ac9a5f7
fa1c5cead0c9a1414b810051c51285f6e1f4ec33
9270 F20101117_AABRCT campos_l_Page_64.QC.jpg
532a60d7a7137084d820b90ca341d20f
27371362545c33c0a869aaeaf6a63210657bf400
F20101117_AABQQY campos_l_Page_30.tif
cce995def6a408521fe18a4af1678d5f
7384d2fbb3d20c94cd8b0a36ac9093b5681ad22d
31760 F20101117_AABQJD campos_l_Page_41.pro
6f6b9962be5b69ecd8572d2345b8176f
5e834e7123f61434c28aa19e59a8ed156aaea8a9
914 F20101117_AABQVV campos_l_Page_14.txt
541e7d3fc0c49ca967bebfdca124ca73
0e1473165a510154fe11edce0167cfd46cc75130
1036953 F20101117_AABQOA campos_l_Page_27.jp2
598df5937491d143a47188f014f4282a
70e7909d823a625147556c0993b0064445d4642f
2996 F20101117_AABRCU campos_l_Page_64thm.jpg
9565ca314c5005fcf305ac2c60dad432
98760be97de7e272aaf32c139e7838e203c2fabc
F20101117_AABQQZ campos_l_Page_31.tif
0b46cf233b06e6ce3155dbf09edd81f9
146cf4cec1ce8c57852743df176bd64c8af34dff
1800 F20101117_AABQVW campos_l_Page_15.txt
8bc512ce20ea76336eeda54f0a7bdfe8
81cf181153637167c3111fcb9d2097a191bffc7f
1051984 F20101117_AABQOB campos_l_Page_28.jp2
d103368f983404afa187acc10ad191c9
2f563053b65f2c63396579c64f66a976a8f23c5d
12028 F20101117_AABRCV campos_l_Page_65.QC.jpg
f4902ca7770fd0e04a9f3ff229a86747
ffa248984595fdb40f013c5222d7392ebeb3d6a0
386500 F20101117_AABQJE campos_l_Page_61.jp2
7e784ac41e2038d68908c4b25473d7fc
c23e6bcf458276c7a9a0b4ab43287dfc45280b41
2110 F20101117_AABQVX campos_l_Page_16.txt
c16439b9dac2ef9fae4e417e3ceb3871
4152306417dced8865b77a805344eb8caf1b1c18
303561 F20101117_AABQOC campos_l_Page_29.jp2
fbeb04d8a15a7a8098f526236194a7cc
5124a153c7cfd8d8d48a810c82aca89e73e80689
4030 F20101117_AABRCW campos_l_Page_65thm.jpg
db3a97429574bd3f1b98330163d0bb6c
ae4345485bf7c22f091b241daa222bdb4f05740a
551002 F20101117_AABQJF campos_l_Page_46.jp2
ebe0c0042146359132c5e2f978c85aba
c26f2441451069f1eed9ae064cf9d54322186ace
33956 F20101117_AABQTA campos_l_Page_10.pro
26cc79f0638031cfa97a296973f75c34
ac5cca4dbe8ced10ade25c244d47f49ab27b5d64
1857 F20101117_AABQVY campos_l_Page_17.txt
0f517ba994c8735e8727c6b0701dafb2
72b9a8c89b0296dd3ec08032daf0f9460e881cda
265205 F20101117_AABQOD campos_l_Page_30.jp2
645c43f5b8dd51a8bbe0c0025d99f8b5
ae752e6c356dfafd61d3372122a38c8743610945
14050 F20101117_AABRCX campos_l_Page_66.QC.jpg
3c0fac7692922145d6c0dbe7d763095e
81ea356115606dd8fb6b35ab885df6a6866ffe25
63098 F20101117_AABQJG campos_l_Page_12.jpg
54c4d8de76935484682dce4033fcd251
f4131c522b31addd27ba787daa076afac74ef45f
17915 F20101117_AABQTB campos_l_Page_11.pro
3029b72b914bb926ea8bab3afe7cf4de
04d93fc1d0c2022ceafac1a0c58f67cc60e2b0ab
2025 F20101117_AABQVZ campos_l_Page_18.txt
84f3eaf0411b9cfbf9b285c54d9ec26a
50f786ab853e6cdaeb30e3861313cfd1c4d38233
492937 F20101117_AABQOE campos_l_Page_31.jp2
398c5f2f5b955260ee97380cea05c17c
3f87dda148ee03085c77662ac9694a1546c50352
4614 F20101117_AABRCY campos_l_Page_66thm.jpg
168e9c5405d92bc7ce31ec0ee51efd08
57161611ee46bc3be6021b96329f92a3924a3746
3229 F20101117_AABQJH campos_l_Page_11thm.jpg
1d620aa81fc2a93b7e370f92cbb25b8e
0537dba480e9198ea6f40c45f9fb52ca07e14663
37533 F20101117_AABQTC campos_l_Page_12.pro
58694990d7ca6545a02e222e7290edca
a5eb5053328e7c3cfcfc5e3142a145e3222cb03d
368262 F20101117_AABQOF campos_l_Page_32.jp2
a1426e876289a6815a82bae489d1772e
758a3a9894680c1783acd555e04d9e28008fa9b0
14233 F20101117_AABRCZ campos_l_Page_67.QC.jpg
f859e7c929c07bf0d45a9fa3325e2247
285ee363ff1cd0afb0f69798a47f0dff9980e544
24667 F20101117_AABRAA campos_l_Page_26.QC.jpg
013b53b3bf1c39156133b42eb4f6987f
72eb43dde85c9b3613139db89ea828cae8c40d3b
358 F20101117_AABQYA campos_l_Page_75.txt
442c3c0e2ab77211699306caddac7dbd
b1860a56835fade3988349bf955df7bb1553c379
1051970 F20101117_AABQJI campos_l_Page_70.jp2
20156b189c65d0ddfbb148a1b783930b
f4167fac3752ed445c91a77501e8d169cfce62c1
48755 F20101117_AABQTD campos_l_Page_13.pro
f7afe4d5a7a974a28e929d298e0ae56c
d89786e4073f23a4104225d484b554faad28e426
140161 F20101117_AABQOG campos_l_Page_33.jp2
19c4776957995bf30b7294ceb6bfba07
79cfd523195d1f6c522ae0270821492e522e141e
6893 F20101117_AABRAB campos_l_Page_26thm.jpg
a004245a4d71349b36554d1f340cca53
3d895f1cade5c8a409dec59fd1a7467531989e5a
1359 F20101117_AABQYB campos_l_Page_76.txt
3d55813bb56a8dac4ae9a411ebe5f370
9eea01fc5e173495aa14d4a6430341e9b5d134f6
1847 F20101117_AABQJJ campos_l_Page_27.txt
f2eeff959436b70431e98babb9411af4
ed5de364e8cff37bd0acfc1e9b67a9a6fb9527af
22823 F20101117_AABQTE campos_l_Page_14.pro
9b34118d581ee13b09b04915267b3d2f
a1bb71e2054c823d798e7017d5ecd90207688e1f
432772 F20101117_AABQOH campos_l_Page_34.jp2
501146c6afa504f68bb0384a6b542a03
b7ac3eab2af1b07c152471c8df2aa576ddd765d6
23958 F20101117_AABRAC campos_l_Page_27.QC.jpg
304ba4b0fcf48865e2a3bba7dc4a57e6
a1eddcd7ec02c3e033ae052e34ae93196c3e191d
1134 F20101117_AABQYC campos_l_Page_78.txt
1ab8d791492bf9984649228b6d4ca54a
0d0c06599184bb86a1bff0601de2518450022fd5
6001 F20101117_AABQJK campos_l_Page_15thm.jpg
de3017bb927e6d088b42433513e0f263
f9eb636155148f2b0ea33f0cb08bb698937b3467
42171 F20101117_AABQTF campos_l_Page_15.pro
f6978eb5862ef8e7612b1db79dd00965
9dbede0b44735359f69e1b785a1d4dabc2e846e2
220246 F20101117_AABQOI campos_l_Page_35.jp2
202a86def6c3f9eae8b591b2a0e45631
26f500287d83623f34091c533fc3d53aa9e4630e
6813 F20101117_AABRAD campos_l_Page_27thm.jpg
bf312a986c3ca2eb221378103eacaa59
f0df3e827a03c55d02ed0df8e2921b6058eae225
759 F20101117_AABQYD campos_l_Page_79.txt
b91a3f307d2cceb497ec4769ac83c2a8
50c79ce82821ad3c9a9e0051036883055c8d4594
937752 F20101117_AABQJL campos_l_Page_15.jp2
27878f776a59e767848312248c1ebe8a
ab8ef0450d32e2a8aa0205cc7273e333b2c93d5d
53147 F20101117_AABQTG campos_l_Page_16.pro
8e25db187a814af6e1a69f0a7a88edde
9e2e9680e2b962462b9988f5ae5445fbf87b0ecc
23904 F20101117_AABRAE campos_l_Page_28.QC.jpg
d3fde96a10ca271d7b32447707b73605
f952f22f04355017bee3e4f40295c71e9b3b3719
5212826 F20101117_AABQYE campos_l.pdf
91f28ce687feb5d175b2d0a91300f797
6a486a86f6d323335647ee135b872e157831986f
29176 F20101117_AABQJM campos_l_Page_19.pro
ad34df3af03e83add90c39318f565eab
85bf8a96687a09b76d0a95a0050e7182075178bf
45538 F20101117_AABQTH campos_l_Page_17.pro
ef993d110fae62c7b647ee4e2ea4c3d6
1c7b6e8c0ff16fadeb9792b07e9f782796831fe2
1009903 F20101117_AABQOJ campos_l_Page_36.jp2
129c40b411ba54c11db15845eeb84fbd
ccbd3b2534b3ba50a792c5973a4beda29dd22254
6906 F20101117_AABRAF campos_l_Page_28thm.jpg
f3fd04be126a054770c906f62d70bed9
8e45e984e3f4050f8857afcd6cebb43b17a578e0
2401 F20101117_AABQYF campos_l_Page_01thm.jpg
c4ba21267b2baf421dfd64fa73a5003a
506265676266da5e7e9b333eae6eb8ef91a73040
75791 F20101117_AABQJN campos_l_Page_25.jpg
bad1cf48b0bdf51d910aa53b4aef61f3
ba85e74759e643b7e8fb17397ba9364fe78b2e2f
47124 F20101117_AABQTI campos_l_Page_18.pro
e883368d98e58411e5e3410a39be19a1
6d2d392b52aa6f0cd8e3946a37de947a21c36156
1051976 F20101117_AABQOK campos_l_Page_37.jp2
50fc4f7a5a5dbc8df963113c8a99ce39
cd9ad7d1d1d022163bfc36822ed43722d4cdbc63
8932 F20101117_AABRAG campos_l_Page_29.QC.jpg
dbe7356caf621545026da6ac956330ef
c48fb58e1f9388edd706fba684817e3b4ad18a58
7081 F20101117_AABQYG campos_l_Page_01.QC.jpg
c8f8a3d334f475f8aab2be9765818581
ea85e19b4df5d59b921cc4d03ad7f0ef3bde87fd
19509 F20101117_AABQJO campos_l_Page_62.QC.jpg
8c42d385fba9a32405b979e2a811b41d
f4744930ce2d5dff7b1513993f3ac7785a7211d6
10285 F20101117_AABQTJ campos_l_Page_20.pro
bbe19253df8b5dd470879a008aa41c07
e16c9090c7f49572ecae41c162e1f17ebe29d0a4
1051959 F20101117_AABQOL campos_l_Page_38.jp2
0a8c4659bb3ac2898b8180b2311b832c
6ed2a098735f7399c69986ba14ebc93fe2e76c4a
2787 F20101117_AABRAH campos_l_Page_29thm.jpg
ecaa9329db2920212dedc61657a60f92
c9c13e458bc1c39ea9e9e5279ee96aafcf3542b7
3094 F20101117_AABQYH campos_l_Page_02.QC.jpg
a28a8b083a67ca8630c6125b7d350834
3638905e3e034a3128edba5b0f3daffeb9c30656
4666 F20101117_AABQJP campos_l_Page_42thm.jpg
e1cb266fded11dd68cad52828184f9c2
835e8ef86463d793dbec5a2ee3aa4c3d830c31c7
43227 F20101117_AABQTK campos_l_Page_22.pro
77cfcf238ddfa6b1c3689f83c9e755d0
5b7368c526feaecfeed5e3f8975147ff5a301171
1051915 F20101117_AABQOM campos_l_Page_39.jp2
f0470a11d03f625f2c9dcb8d1b7ca282
eca41a7638ead4f2e10edd21cc2c94d678a6cf8c
9330 F20101117_AABRAI campos_l_Page_30.QC.jpg
f35ab46ec17dd991e07e74c5bc168e31
562f9704f119b7ab1c26c47988a1f008436c04d0
1344 F20101117_AABQYI campos_l_Page_02thm.jpg
19a1d8a8039a3e0db1d47b77f5e9daa6
47269ce7a25dfdf715dd4e1c9e74d76c7a82acc9
42683 F20101117_AABQJQ campos_l_Page_63.pro
50426e670275209d8d6ac97452539df6
d1acecb31c2e059932f66198caca9392a4a8ad9d
45460 F20101117_AABQTL campos_l_Page_23.pro
dabf75dee2c9d32eeffff493583284d4
4c16a80993fbbb3546fbb7995bd9c77036d60697
694450 F20101117_AABQON campos_l_Page_41.jp2
11899178d4b0015750c82d2123f071c7
e87c86749dbcd56c86fea4c35ac4756ca9b543df
3387 F20101117_AABRAJ campos_l_Page_30thm.jpg
c604a1b4f2f15402ddc1f1a5f48903cd
780e294a860d6129035be0d3a5e6fda52d8ba84a
3199 F20101117_AABQYJ campos_l_Page_03.QC.jpg
a7762e69b5e919b6a6b221e1a162125c
6825e6677ae667d09e5860d76babe3a277748cba
54611 F20101117_AABQJR campos_l_Page_42.jpg
65f38e8ecdb256f46b6e1dc2866eb419
5eda208baf843af75cee5bea2763aa10ea65720e
46950 F20101117_AABQTM campos_l_Page_24.pro
6cdbd572f3db66921d83a9c5e8ca2b1c
dd518037670984ca00ded7836b2f20fc50a7364b
348088 F20101117_AABQOO campos_l_Page_43.jp2
686f7c2853fc1d083de2d0c727b603fb
a5eccce0d8bcba666faeb14e0a238ada1c08540a
12069 F20101117_AABRAK campos_l_Page_31.QC.jpg
bb395f19539bc4ba4f1827c9ad9daf5b
07fe103dd993725364be717e84fa6afe024f64f7
1470 F20101117_AABQYK campos_l_Page_03thm.jpg
1d42fd28dac3228b5c94ab7ba626ad37
0665881d7ad6d8726fbed82b2dce9e7d0e81c06e
1051949 F20101117_AABQJS campos_l_Page_40.jp2
242436e606e8078ff193dfb97518610c
339790dd9037eeb62a0a4a2bad52c7a4c5278e0d
48652 F20101117_AABQTN campos_l_Page_25.pro
0f30e978d365dcf0e5241c4219f1ef5a
bd7ed66a8ba0d6ef7085b7520a0740694abc40e4
545951 F20101117_AABQOP campos_l_Page_44.jp2
7d3bb209b2699263cb082d3d58be14dd
1fb07d50bd6874079a37efc528a3b5b2b322b42c
3752 F20101117_AABRAL campos_l_Page_31thm.jpg
e61305007c4def71a7a2b043255cad1c
51697df363ee4186deb6b6034a97a6fde2de6e92
19629 F20101117_AABQYL campos_l_Page_04.QC.jpg
b82aaa01e53e188604c91b921dc7e663
62e8d4c778d4550a8915426e829abaa8a2eb5968
45933 F20101117_AABQJT campos_l_Page_76.jpg
5e5bbcf30271831ba4356e3da6d31303
cefeba9775d0bcc0a347c2f52923a0b0e8c20822
533382 F20101117_AABQOQ campos_l_Page_45.jp2
712d0cd6144e1bec260a2b49217dcfc0
ae4c69410528e464fa01bcaaf3c3a01423dcadc1
9689 F20101117_AABRAM campos_l_Page_32.QC.jpg
e62925a4f6fd33719d5d75407b6ebce3
eedd69e86fbe9feb97cba64165cf35c669ccdeac
5722 F20101117_AABQYM campos_l_Page_04thm.jpg
4d81b4d1188e2fe1ec095988f7fec6e5
d53d1cc8626d02d0ec8235561e8fca225bb4d3c3
5032 F20101117_AABQJU campos_l_Page_51.pro
68ea405b4f31ad4d1f89b204ae5c60d3
2d16d123753ed0b92a9522fcb53fb35245b0f689
48772 F20101117_AABQTO campos_l_Page_26.pro
058ce9813945fc320f75de79edc69b4a
e6c740c48783bd5e3a3c45c71c9e6a4ebe2eada9
1051828 F20101117_AABQOR campos_l_Page_47.jp2
a455da33efb6c4a4d8b67fd2a3aaa03d
334f1f85996cb0a79c39de45e900c50f91e9bd69
5918 F20101117_AABRAN campos_l_Page_33.QC.jpg
d0e0f51878d39e6e2c44dc0570355321
0671a39eab48de24d00bed8a252c429d4f9593c6
20901 F20101117_AABQYN campos_l_Page_05.QC.jpg
d0e41fb0deead1ab6453c0b0a5391ad6
452f485d82424bb689dcfd3cc5308b6e07fce6e9
648 F20101117_AABQJV campos_l_Page_58.txt
7ceb4d27870bdb27477cb7ddd616018b
1bb98d4f98760fb70fa0aef57e953583c47f2c3e
45744 F20101117_AABQTP campos_l_Page_27.pro
47550f5e5e309cf0875ebb9eefe090af
0fb89ffbbaed4affd4962ef94f121fabc16d7f56
1051894 F20101117_AABQOS campos_l_Page_48.jp2
c04fdbd7195b4162d13ade85def80a40
ed12f29d061a01d50069efefdfcd536674dbaaf6
2309 F20101117_AABRAO campos_l_Page_33thm.jpg
47ef1f4e2753a64da12c6326695183ef
d6d6611650cc2a7a37bbf9fd84380723227f016a
5350 F20101117_AABQYO campos_l_Page_05thm.jpg
5d4081aa6f647efd63223d77decd340c
3f3c36331eebbd41ca7c54e7fa569a669036bd9d
5324 F20101117_AABQJW campos_l_Page_55.pro
da0fa8444c92b81d0f8f2ffa2964711d
868b3fea0aafad1d85339a09c84d680ff22d2ca9
48661 F20101117_AABQTQ campos_l_Page_28.pro
28c17d7bcbede67d1ad25380cd976a0f
f053aedb32f345c72bef10e1f6c9a721fffe97e4
1051708 F20101117_AABQOT campos_l_Page_49.jp2
daa394f389bd8b7264fcc56de45c2918
587eb33b12ce0afc9e411fd03ab42d7099ce6c2e
9552 F20101117_AABRAP campos_l_Page_34.QC.jpg
0bb15c1fdd7ac562a8a1dc61087c218d
c6d067851d0210d8e44b3314866124838716726e
8278 F20101117_AABQYP campos_l_Page_06.QC.jpg
28474866bd5d4f2b06e81f6368bf3f58
ef6986b7329b7cb99c5b6ac3388179f3863c29e6
1497 F20101117_AABQJX campos_l_Page_04.txt
8dc3be2d511b06604fc15f99b18b3610
023df692c9bf450bd3933396447f7cbab62a9034
13046 F20101117_AABQTR campos_l_Page_29.pro
c1dd5f6051e28548419e9c3dcb4618d2
5fdd62f455ddbf1e7a8b81918346c2fc2f8e9b08
1051866 F20101117_AABQOU campos_l_Page_50.jp2
29c3ec197ab4fb9218c27a34e6cc20a7
45d537bd01d8b512d524b147bd906394b7a78c8f
3282 F20101117_AABRAQ campos_l_Page_34thm.jpg
7280b06e8ccaac6d800c8858ddbf6aa4
591c9cfc0a38c72eb5d082b0ce10520bc87027f6
2474 F20101117_AABQYQ campos_l_Page_06thm.jpg
006c68e6cf7fe2c4fe91d4ac33b02bdc
6d63b538777afb6bd3e35fd112258d25683c289c
2009 F20101117_AABQJY campos_l_Page_38.txt
e0d4c14a234ebde54906b95fcad47acd
7b51960e1b1fbd6c6c234e96b49cab74b5ab6171
3782 F20101117_AABQTS campos_l_Page_30.pro
4aca9eec52d7831170cb18130ac27a5e
e3f7ae451d65cea41dac3098503f9eaf5e2ece02
1051938 F20101117_AABQOV campos_l_Page_51.jp2
71ecd18e827ce5da0d39c2bb2f730440
ef0723248376e5acdd41acbcd460372cb618f95d
6516 F20101117_AABRAR campos_l_Page_35.QC.jpg
40f2636af4ca4dcbcf2b456fc0c1babd
1d9e7f0b5bc91fda9a2e4c4e0739466ae4f21009
17610 F20101117_AABQYR campos_l_Page_07.QC.jpg
5dbf04f319b19c8abbfe81046cbc1b45
b739a709c4eeec57996bf0de687f3284308113b9
F20101117_AABQJZ campos_l_Page_70.tif
876796af435577ee5126bd8727dd8907
0cf5534d959f70d08d7637c407cfe9e0fce84e91
3012 F20101117_AABQTT campos_l_Page_31.pro
c93641dbde9ef431405bd9619bfc7063
898e3d5f843f66fd8df1d89f75f555f72dd9b969
1051722 F20101117_AABQOW campos_l_Page_52.jp2
8a18812c8a835487dc4482ffdb4152f0
8f5c503c55a6534334d278c68db098e974d587b9
2327 F20101117_AABRAS campos_l_Page_35thm.jpg
e84828bd9fac0aa6ac5a35844c38b555
8c89a5716a56f19385a0b794eca03d50109a5642
4442 F20101117_AABQYS campos_l_Page_07thm.jpg
67db377d58880c8ced001f426384abff
6e9dec83142c9478d7520f551ec5a8428a5a9d90
17584 F20101117_AABQTU campos_l_Page_32.pro
28159ed06e3803d4ba7cb26ad37ebe45
2c9e992a1954a72f0620aa8ec2e09f115b431cd0
801175 F20101117_AABQOX campos_l_Page_53.jp2
ec40069bf396a4de06b95f9b310204f0
7dcf298c6bfc7e3d6cdf60be9136cce5d41fc18c
22961 F20101117_AABRAT campos_l_Page_36.QC.jpg
9cccf15bd4e5d14770979e354f520bfc
bcbcd04126bf7c82f270744a0c146cd8d3c46e76
4785 F20101117_AABQTV campos_l_Page_33.pro
e61a88cfc35a0a9642818d75da2c4d1e
8b2edef8d323118b5a41f9e2ed9396dc8bc2313b
80742 F20101117_AABQMA campos_l_Page_52.jpg
f3ba6ed1ca99aa1e031140f2709b786c
bbc1ae7c81c9d3114ec1fc697269be9708348329
272699 F20101117_AABQOY campos_l_Page_54.jp2
c34c1e6edfb50e246ea1868dea2c5eed
6f5008b66ff3832a934ea61e86b2f54a980b45b9
6290 F20101117_AABRAU campos_l_Page_36thm.jpg
8862c29462293d0f52214705732dc491
4d83d5fa2be68c3463aaabe7541f79dfe8ccc619
23524 F20101117_AABQYT campos_l_Page_08.QC.jpg
9201dd1100a739e6e457e5a7f24a8ce7
62319fe24ebc09093533e8c82bc3c1e32c9d8ad5
8769 F20101117_AABQTW campos_l_Page_34.pro
42a42b19b1824bf3b921ba4b1ee8d9c2
79f29573220f55be689ddf13c973fba03fe15465
62170 F20101117_AABQMB campos_l_Page_53.jpg
31ba7d61169e881b6973ede651cc27d0
b5d32105b45b0cb12130f6632f5caaf73b6fac18
450212 F20101117_AABQOZ campos_l_Page_55.jp2
690ca57b623b84e89bed4142b0070dcf
17f43f06f10f62003d28877fdbf48e6ec3395883
25587 F20101117_AABRAV campos_l_Page_37.QC.jpg
b67b2eeb2f432dab6bcd55d8037ea376
b8890a5444756ccbd11ff1a5e9b3d78e5041c4dc
5901 F20101117_AABQYU campos_l_Page_08thm.jpg
19de7d0e794fce7b75869a53ad936fd9
d2ed77012fb7b2b6dab12182f828393d877076b9
4527 F20101117_AABQTX campos_l_Page_35.pro
dbddf9c154357561d1a976432a006570
74e28bbf3c500fd51992934d3c3457ef7722df56
28796 F20101117_AABQMC campos_l_Page_54.jpg
b3e6e26b54d5616426f835b5f9d5292f
c9184fa4e8a06e0f8f886d115690fbc5594425a9
6976 F20101117_AABRAW campos_l_Page_37thm.jpg
6f3c5931456c1bebdfbc92430602e9c9
1ba5f52155ca32ddfaf2f2fc3f42f6fdd907a30b
22220 F20101117_AABQYV campos_l_Page_09.QC.jpg
5f43e023d3c585481d0798aa8fb02997
e8ce68bbacb4637dc56a5d1110614e387859daa8
45431 F20101117_AABQTY campos_l_Page_36.pro
3fffa89c3059c708dcc4e93aff5382ad
928f18b65ee2d8b6ada675485bbdfc187a7c1e6b
30643 F20101117_AABQMD campos_l_Page_55.jpg
c86873e009ddcb6fb28d9a3e1404d858
7c19f94565a5fb7c4ca9c02221ddc26d75bab6a5
F20101117_AABQRA campos_l_Page_32.tif
3178a57087fe02a26570c8a04f3536d4
696c20e3d7fdc2e0127b316fee0f6ceec5c2ce37
25032 F20101117_AABRAX campos_l_Page_38.QC.jpg
01e70845c9b3a1cc18507f82eb4d172f
04e60b615b413bfd4bed5160a7e357e3c0e43a25
6130 F20101117_AABQYW campos_l_Page_09thm.jpg
55dd3fab8c9eb90fc4b1e79206a2878e
4735cce808f1022dcb60df9343d4243e6a0e1908
50107 F20101117_AABQTZ campos_l_Page_37.pro
d0ea8549f8fe21ffdc4a02bb82f33e3e
e22bb5aaa17a9b5ede610a15c42c0936eda36a9d
36445 F20101117_AABQME campos_l_Page_56.jpg
c5aeb51e97e03fdfa76e3f3fd2f3178c
1cbfdb6dd395176f4eab22f6c7ef8c2be694df02
F20101117_AABQRB campos_l_Page_33.tif
0e358451ddfd9d1035d3acd64b3f8a32
28071b495f2fb88ddf5e85f4db6dc50686ce8796
6791 F20101117_AABRAY campos_l_Page_38thm.jpg
436ac0349bec84ef37186c97f596464d
0d56d4aa6181eaf8dfe22273f7c2eaeb85e1711d
17504 F20101117_AABQYX campos_l_Page_10.QC.jpg
cfcfa167a5f19237c091ef8b5b7a2a68
67dcc70ed3cfed27a75de8b486b49e9a7eac3f6e
37685 F20101117_AABQMF campos_l_Page_57.jpg
3528600e0427f9ee747b21a025fff4f6
7c73417e85afd4b3701b4dc75e07fe1615f4fc52
F20101117_AABQRC campos_l_Page_34.tif
7d59f570bc9a13f75c82b287fa57c16d
0a67655bfcb71a1c080969a16b07984e6e8589b3
25312 F20101117_AABRAZ campos_l_Page_39.QC.jpg
538d7210086dc811e6e1ff99b7139b94
b1a5b0b655a49106608321b61abfe97051cbffef
5069 F20101117_AABQYY campos_l_Page_10thm.jpg
6639d105e25c7381735c78df44ac47cf
67c58b037a90b9762d8732f38bb3e5f4ba4270e2
35771 F20101117_AABQMG campos_l_Page_58.jpg
ab185b532f38603205045d7bbd4dd542
2cd3fda6d74014bf2b606c976c2ac33cb9aedac3
1315 F20101117_AABQWA campos_l_Page_19.txt
33fb4790da885d2a6432b560d3fb0652
85f73b30e41bebff907239c903c322a3d3ceb9de
F20101117_AABQRD campos_l_Page_35.tif
53af3b09d3151a251bcbff94263c16c5
b31cbb46580b2e1cb677764eed4b98e006653ff9
10733 F20101117_AABQYZ campos_l_Page_11.QC.jpg
cdb12298ae5c69e2ed230ab02f795751
cb1320195d988a2f87c78ef283ff1cc082af6517
496 F20101117_AABQWB campos_l_Page_20.txt
61cd7791d4619554448582fd48e39f12
9d4dbb2dba312995146948d9e4ff77ef2982f726
F20101117_AABQRE campos_l_Page_36.tif
24d7b416b70ebc163ec9a7656256bdf4
3d612d0959ca79ede05151bb526ce92222bb1eb2
22838 F20101117_AABQMH campos_l_Page_59.jpg
415c7a972318f5e0cbf4c5d9b55074b4
65eee48e46743e497595a9cc14b2bd5bc99938e5
1809 F20101117_AABQWC campos_l_Page_22.txt
74fe47bb059d470678c11d6a43566d95
b0d0563b3d822f10296d845b0f6b1af32525cfae
F20101117_AABQRF campos_l_Page_37.tif
2fd6fe4539bca1058212d2dbf0fadb23
3294ce72a9ba492930f10858fcb36ab0e3302d6c
22587 F20101117_AABRDA campos_l_Page_68.QC.jpg
6815c55dcd2ec726950ba12ed24301fc
5cb180b8bd9572e840d1681d5ab904a63a70a3b8
66705 F20101117_AABQMI campos_l_Page_60.jpg
d148af2ab03124300cc850722f7ce247
12b433aa03f8d23ccbefdac74c565bde2d28d689
1832 F20101117_AABQWD campos_l_Page_23.txt
b1d0449a1f4f398303fae3f0616ad0c2
b911e0bdadaee2a273362cbfe5db10a68d2fc204
F20101117_AABQRG campos_l_Page_38.tif
91c6b974af56c3d536d6b4502d238f80
6439572344591c8feefaec9bc5be8cc490df9809
6211 F20101117_AABRDB campos_l_Page_68thm.jpg
92aa95d47b2a41febe2dbcf59e01397e
29751bdf8aedf1526ad873f015fbee22d072a224
34350 F20101117_AABQMJ campos_l_Page_61.jpg
875aeed1189f65e750ce806ff5ad2487
6d8477f6cc03c3650fc4a6563562437c0797a2ca
1916 F20101117_AABQWE campos_l_Page_24.txt
d67f7e59fa54253479c82aec19ca2d06
cc833228ec3c4cd3319e7e3f2b0c5eef01ea4588
F20101117_AABQRH campos_l_Page_39.tif
c6576d3fa91ac07f529f1fc4c88805ca
e55b77f3dd101d7ac3dc201bad112d5010fa3a92
22952 F20101117_AABRDC campos_l_Page_69.QC.jpg
ccd939d65931a67eea8696ceb1d6f61b
44aefc738deccc86a77d902746bad5d19956177e
59583 F20101117_AABQMK campos_l_Page_62.jpg
bf34895e1311bb8e679cc3c9ae510dd6
fd240c9aac3a30202d9e8d95aefd527402bc553a
1946 F20101117_AABQWF campos_l_Page_25.txt
6dc8ba4a2d01a428a004c7290d658546
0e877fb1be7e0999ca77a633e69bc9c18ebb4e5d
F20101117_AABQRI campos_l_Page_40.tif
93eea5b9962caaaf42e490508087d571
2c6778656f4dee15aac095c0fc0294013a1c38e5
5915 F20101117_AABRDD campos_l_Page_69thm.jpg
3833f40e06f3c9ae709313a659f12b3f
f3aab2ceec5381fe0549fad1d924ac198268abb4
68812 F20101117_AABQML campos_l_Page_63.jpg
09864b0fa7a2d6fb584d21ab82728518
6e2be605f1cd3538fe0ab2e07e6ead6cd0572573
F20101117_AABQWG campos_l_Page_26.txt
03096ccfa743abc2b57263eccfabf13e
709e73d842fba5390e57a7669052ad91accaead9
F20101117_AABQRJ campos_l_Page_41.tif
87136a19fc1e4479e20a9756bce3425e
e2e387239110b70d066246b7a9fe630347b3cd66
21979 F20101117_AABRDE campos_l_Page_70.QC.jpg
27b43a3f83e282767ac6b8a7505645f4
b9fad7e7478c967607390799e723e47940b4bb1e
28195 F20101117_AABQMM campos_l_Page_64.jpg
caf8eadef6f32b1c7dcfae036a9683d2
d0d99aa1522415b0913d8b72e56f2b005d03423e
1950 F20101117_AABQWH campos_l_Page_28.txt
30ad918f21a76d537a37bd4f560c42cf
c7916dfa811b93079d7177ef29a83a07f989696c
F20101117_AABQRK campos_l_Page_42.tif
567ff5070733f8eda38f18c0ae196e72
e8a8caa5251e31341e74671d6e939ceadd5fa0b2
5969 F20101117_AABRDF campos_l_Page_70thm.jpg
35861bd61baffb04001a545581b349f2
fc35cd3c254857285a98200415688af3abf5e666
40734 F20101117_AABQMN campos_l_Page_65.jpg
6bd5529d63e9a7d60ecc0e401494549c
b3e5a81d26bc71760af5ce76681b13c4b76b5454
570 F20101117_AABQWI campos_l_Page_29.txt
224bbf70edb455525ffe21510ffeb5c4
e250b25bf81a16aa2c823dde3a631fd63a586daa
F20101117_AABQRL campos_l_Page_44.tif
4735cd174ccd3010c854906ec8a8e4cb
2894d28bbbdc4582c7d7dba814bd9cda1529da29
23059 F20101117_AABRDG campos_l_Page_71.QC.jpg
ba0070e23507e7c313f7cc28af9bbaab
c51007531dbacda3fc53e252538c95ec7d149de8
46147 F20101117_AABQMO campos_l_Page_66.jpg
988979fe2d8431aacda00252b81cfd94
bf562dc48e0c30bae27fb820cbd920c02618b2d7
188 F20101117_AABQWJ campos_l_Page_30.txt
c4e3cf5f78485f58c001a9d321a20a3e
545429a3590f83c782d31e20f48a3a478b935246
6096 F20101117_AABRDH campos_l_Page_71thm.jpg
82881f27cb1cdc50994e13055271b9f3
1ea097af325978da8d7c47b13ad71a288f87ac13
46680 F20101117_AABQMP campos_l_Page_67.jpg
359c442cd4b699e624766fcb14ce8414
595aa9016453bc1181e7eb07bccd4e7c774012c2
217 F20101117_AABQWK campos_l_Page_31.txt
912000dba82ce498ed30966ad93019f0
f87410d4f93fc7d1e2d0051c9d4e87641f6553aa
F20101117_AABQRM campos_l_Page_45.tif
b2cf72292af48da61338a1e25cf16d52
be60ca54c0ec7c4b6d4364713017fd7c0a67bfe1
22031 F20101117_AABRDI campos_l_Page_72.QC.jpg
5479ff66982509549207c92815160af7
9dfc8732c7a07d61ace18aaa5cf361ff644fcb72
81402 F20101117_AABQMQ campos_l_Page_68.jpg
16f5ebf004c1d3f11b560d37bc23ce89
41e505aa10a46fb1d09c78ab7aeec18eb00e706a
940 F20101117_AABQWL campos_l_Page_32.txt
a454c82b1b79ef4a04c9952e2de068e5
73fefd8de2b109f33cef05e835489d0b6abe62d3
F20101117_AABQRN campos_l_Page_46.tif
1b301d08ffec039946c3ecfcd932d998
86c73be4687f9144e29349bbcd9ebf21e8fa98be
6000 F20101117_AABRDJ campos_l_Page_72thm.jpg
5908175518db69d8cede7f58f50fb987
e95c48430e31e708472dec4c185c129507967f12
86021 F20101117_AABQMR campos_l_Page_69.jpg
d3426d7583b2c4964733173df340f661
346d421006ee2142ee1364c3ece6d4296084851c
247 F20101117_AABQWM campos_l_Page_33.txt
6f5a08a062d23a440562490eb19e0fd3
9d7a3f0d7f1dd0a532c4ec7556e1405131659e2d
F20101117_AABQRO campos_l_Page_47.tif
069c99dac55a3900e4c1115cbdebc2f8
2d3661bf786c37135b380f461a27036db8756f4d
23200 F20101117_AABRDK campos_l_Page_73.QC.jpg
0a4676d29fd6949f016c63869fbcae5a
3209ad0618094935daba2c6a376b259ec7549735
80049 F20101117_AABQMS campos_l_Page_70.jpg
ae0ac0924423e5bed94231c078990158
940f7026028f8f2088cee9e93e3a291063ed5dbc
498 F20101117_AABQWN campos_l_Page_34.txt
c577929aceafb544308018a110e8c7f8
2e37abe929ddd2f416dd8212c9d29ba8ce13b980
F20101117_AABQRP campos_l_Page_48.tif
dbea67f4435f71df9f9926d923c75c8d
2921bd9a0ee21270e5b0df7a9baf878d4db5f987
6168 F20101117_AABRDL campos_l_Page_73thm.jpg
8fca78f278db5e04a95b32bc16eddeaa
7529d4729c481141a1f7b562592dd38f99d444f6
85469 F20101117_AABQMT campos_l_Page_71.jpg
55932b9eecef07ede63ee29888e8c34e
f74af1de9df1abd690675330a730258a6a3212a1
287 F20101117_AABQWO campos_l_Page_35.txt
603964357fe80117bf3f7b634f880210
b38dcadd7aac0ea7ba34c8b70e94832b94981355
F20101117_AABQRQ campos_l_Page_49.tif
27d46fe3d34492af6df700740f951eb8
1532d09cfb44cd42b426a0deafff3e25978ea0cc
10988 F20101117_AABRDM campos_l_Page_74.QC.jpg
93134e5c7ee7c2c9f19df20e979bf4b6
7e51163a1bc6e820a829b10748a0ee3950093099
80854 F20101117_AABQMU campos_l_Page_72.jpg
1beb14af9bcde91a833cd53d15e2fd86
6cb81e2b9b478c942f0840883cbcb2f51ff6b805
1878 F20101117_AABQWP campos_l_Page_36.txt
b45bd233ca390009a736060c4aea3e63
6dccd8179e80ec3a29a3b82ef660c43ecfed249f
F20101117_AABQRR campos_l_Page_50.tif
354822fa924d627f279e921f882bf7c1
8eb51544d14af328266518472cf95de938b78f85
3678 F20101117_AABRDN campos_l_Page_74thm.jpg
d9f3b0490b791b2b39795521457f6330
feb04532da048c6aedbd7688c996a302b8c8884b
85936 F20101117_AABQMV campos_l_Page_73.jpg
c586a2e99140af655cdaf7b62ed85c57
6a0b01da5f00df3f30ac8e42b9a320620eadd6bc
F20101117_AABQWQ campos_l_Page_37.txt
280716aedf8c15eb651a0e7338bc2b69
218c36a155fa1714bc50b05fc9d87b8731c72470
F20101117_AABQRS campos_l_Page_51.tif
f0fc20ac76bdf985a23dee5d75c52153
912c0d53de1a74c438223d8e07daeb22ddd78a45
11252 F20101117_AABRDO campos_l_Page_75.QC.jpg
aef7b8329305ed8829364d4a562dba71
4966592dfec5549d75717eb951ef4483c7473471
39296 F20101117_AABQMW campos_l_Page_74.jpg
b59e5ada379f2e9e55a070bc0909e9a7
5a06752df491d778d38b3845113d2794b0d2c2c3
F20101117_AABQRT campos_l_Page_52.tif
fd017e544a9c8718b817de0cb39c47f9
2f56a1b0c7344b983f4d5516162e730514bc2795
3822 F20101117_AABRDP campos_l_Page_75thm.jpg
a0bf8625cd2f9deeb8be5488c83108b0
ba1616bb3b0bc2d3b730a3d9502d115cee65552c
2006 F20101117_AABQWR campos_l_Page_39.txt
c7926d98b003e172e59be4dea97e1b08
f860c03a3462482e5f76d274c75e23e28c98039d
F20101117_AABQRU campos_l_Page_53.tif
22d7c8b54c3c0f0c62ea53c7b0c51869
0e849cf2b87a5fa96c3cb32dce3a9c2d7c2a8ef7
39673 F20101117_AABQMX campos_l_Page_75.jpg
9513878393d16f95700d7dd8057e1ab9
d60ff9d94ffdbb2dceeb84344800932e4f1be8cc
14075 F20101117_AABRDQ campos_l_Page_76.QC.jpg
3d1a5d51c9df8a72698331d49d983cfb
ebefcd2b356ccfde6ef32ee392338717f25aa454
1928 F20101117_AABQWS campos_l_Page_40.txt
b9ef26dff11e61fca5a50a6e3edc0322
a888da784683fda9772d47862c21d8a3cd79935c
F20101117_AABQRV campos_l_Page_54.tif
da33cb43d32147623e1a345728971b65
99617057922e475235109ecd989e97fe76b72f03
14132 F20101117_AABQKA campos_l_Page_60.pro
962803e65f4e1a5ab6b8a675a02a7af9
a7616d60b6ac672ebdff71c9aca96818e8826a41
73401 F20101117_AABQMY campos_l_Page_77.jpg
d974c38df555cdbb9da8d02e461bbedb
c3224c435b7af1e5c979f4449d641770110a8c6b
4353 F20101117_AABRDR campos_l_Page_76thm.jpg
a9509f35308c5b6627a51b301d472140
7384aeb014adc70eab74073faa3ff538c105473c
1265 F20101117_AABQWT campos_l_Page_41.txt
3feeed1784c8a14e59d71b400f671dc9
eeacaeb8724392d34dfb9357de27debb6823810d
F20101117_AABQRW campos_l_Page_55.tif
0857aae3253eb4050f7243b06efd002d
01551811f74186143267a24953b3a709561e303e
119689 F20101117_AABQKB UFE0021855_00001.xml FULL
31886c137636bb29422d245431000809
45fffba23c7612773985c193bfa539e0d37615d0
50628 F20101117_AABQMZ campos_l_Page_78.jpg
a4f6f6a187769ebc73ad26e604e6aa0c
41087db0dcdd51401caba3270346aa3e596e4b6d
20308 F20101117_AABRDS campos_l_Page_77.QC.jpg
3b731142c027fef87a5bfcd98fcb54aa
5df731c60953357aeb81659fbf9809bde4f0c1c3
2381 F20101117_AABQWU campos_l_Page_42.txt
cd21f14260c0964b54bc4075a03993cc
7401e60290aec1b0bf1b159e3e591e8c83bce3fd
F20101117_AABQRX campos_l_Page_56.tif
6ad7c3b2a2a9c50c60bc3acc0a6148fa
1514043352dc0b25d30df9b1681f54bf1ca37924
6082 F20101117_AABRDT campos_l_Page_77thm.jpg
e4dc838a34e61b49d817c659e7250015
30d0bd8f2d112c9e87355d70a6aa14bc5703aa5e
1224 F20101117_AABQWV campos_l_Page_43.txt
853ff6843d6a033c1682268d38c5c042
8a0460660e2a686570075a560da0dee4b2485455
420911 F20101117_AABQPA campos_l_Page_56.jp2
593c776a7b4daabbc0ab50cb4c2d2fbf
f9bda667fee2f2e2363b9ae12f1d3f7ef30900a5
F20101117_AABQRY campos_l_Page_57.tif
05cf19634003514870c17314a47e4907
04ca07eefe188713517dc85aa3275763c5acaf36
14441 F20101117_AABRDU campos_l_Page_78.QC.jpg
2df659468fd02cc4898096f1bea6740d
e08d8f40becb56a8cde5d045783b1f8d5a2d2827
831 F20101117_AABQWW campos_l_Page_44.txt
4a4b28271c40fc3aaa175c70327fa848
5508a7de2c9cadd9eea209c23cbe3778adec9be8
433303 F20101117_AABQPB campos_l_Page_57.jp2
dede73c1e090e0dd72ad5cb064f4663c
2e929ea752eb6b67953920b9ea00488e9739f35c
F20101117_AABQRZ campos_l_Page_58.tif
7c6f18132e63e5c10c73b534ba25ffec
8d6ce360d03bb4eab1d2e0f3962e3f1e76efe931
25423 F20101117_AABQKE campos_l_Page_01.jpg
0d61507ce7b854898e550e47eb4334ee
bc62b009289d52fc1cbc0bced0e08a05dcbef8a8
4134 F20101117_AABRDV campos_l_Page_78thm.jpg
41e22e81845b8ece9a618b88633afcf1
64b63bae43a12f7ff9afd8efe768405730f2c70e
783 F20101117_AABQWX campos_l_Page_45.txt
0bec948f0a16384b6467d4b68d8aa5ef
bdc7a8fecabf0ce39be7d534323787d9652f69b6
428180 F20101117_AABQPC campos_l_Page_58.jp2
7618f26bb0c193bc41f6eb99f9ca6246
0d782c6ebe2c5a58fe080556bce898bedb86da61
11094 F20101117_AABRDW campos_l_Page_79.QC.jpg
50d0c8b71fa2cec7e37ec55fc4929038
4162a6f9fe06c0543ad05c3d57495d850b0c6556
733 F20101117_AABQWY campos_l_Page_46.txt
69d3e1bc40e74b98e2a7f2f3eddd49fa
ae683c161dfb49dc33982a3a218de80fafa971a8
229655 F20101117_AABQPD campos_l_Page_59.jp2
838529ee30d5269d61bb3a9bc474d55e
225ace60715d3cb2d167ce8929854f95d8569cb5
10176 F20101117_AABQKF campos_l_Page_02.jpg
7f27a82d3e5d27bc0a4e0b3a2ad49972
7078e86aa88b64b45c4731e51ce0f16b0ade894e
50145 F20101117_AABQUA campos_l_Page_38.pro
0bcee965531c17161cd1a1978423dcf6
10fe79564606f6fb38a60d4e43c409fe210ba809
3526 F20101117_AABRDX campos_l_Page_79thm.jpg
a7f9e3b565b18a8283c91b7b18e3d6d8
4952125f4c9968667af832a825b73bac3d35e969
397 F20101117_AABQWZ campos_l_Page_47.txt
027c765564291aa2ce4ef154ff7737f4
6c3270afeb3d6ae15f7c2df0e98584c1abe6700b
1051872 F20101117_AABQPE campos_l_Page_60.jp2
427d873efe123ddad0b71a0330101921
aca79f0f075b69ea15fe5d0e5c4b04429bbe6a05
10499 F20101117_AABQKG campos_l_Page_03.jpg
37a7436682cd313e6e8864febbabebee
639d832af0ab666c8f2dca12781c6728e1f77315
50939 F20101117_AABQUB campos_l_Page_39.pro
6daf710341b27f33ea8873e8ae218c2b
3266752b624d0fedee477e3cf57edcd261295566
92707 F20101117_AABRDY UFE0021855_00001.mets
0be7154980a091b279fbd3a936b835fd
a42f47fe88b726bf2a018822598f095608c14949
809920 F20101117_AABQPF campos_l_Page_62.jp2
17f5a2e93561ae8200bb11da9a094b31
f70574cea7e5e46e6f2c9a3360fef095be274561
62680 F20101117_AABQKH campos_l_Page_04.jpg
21b4bd49a56b32b39f1e7d83b4e0ece8
56ef9c23c5948a8902bd6d4955cd1b942399d88c
47904 F20101117_AABQUC campos_l_Page_40.pro
1403ab592f9359b6c0892b1287f7ad25
a993dbfe2b126c6218757ffe972716c6904c845e
6973 F20101117_AABRBA campos_l_Page_39thm.jpg
8634b0c3897671485ccb804fee399c3c
145fcfec7f9e38e3eb68b3a762e630d2624089c5
19764 F20101117_AABQZA campos_l_Page_12.QC.jpg
f800c151a84629b900ec47927522336d
48763ee5ba8b7091b5f62d836b01bae341d71d42
958248 F20101117_AABQPG campos_l_Page_63.jp2
f0cc337d56f85125729012f2837632fa
d6d0582cbc24651154859836f183c12c79bc4ba6
76844 F20101117_AABQKI campos_l_Page_05.jpg
626e1b336f18ad20a61b94c3b904d773
3af50b74e1b7c5a2e475ce44ec6070efe99b61d9
37377 F20101117_AABQUD campos_l_Page_42.pro
a0b4698693e8f2905f66b996fbade723
e7dc05cd4c4d4375b9ba2272eaf3e8fabb2413f1
23633 F20101117_AABRBB campos_l_Page_40.QC.jpg
456e7a4f31e987465d033a8104b8e7f1
490901f75f5013c6edc585960076cd1b642426f4
5477 F20101117_AABQZB campos_l_Page_12thm.jpg
a7edecb6248f5bd85d2aa2e2ace6799e
fb87e90a66268a87a77b986bd8f1adafa6f4060d
322388 F20101117_AABQPH campos_l_Page_64.jp2
e8805a192bf4d3edf83f81d13e0bec8a
e77789eb244161e5d828bb622b79a2f40f3ba735
27389 F20101117_AABQKJ campos_l_Page_06.jpg
6f3c20ad36aa357e063e9d543f761637
539e44f4b6302819d4ad1bb5671a9008c8b27f71
18934 F20101117_AABQUE campos_l_Page_43.pro
bfa730998d7d2896816a3a694c89e54d
987defd0ce9c6bce97734ba3cd450d62ea0b21c0
6820 F20101117_AABRBC campos_l_Page_40thm.jpg
f205762eddd746b4ffbb1c2b74da26c7
6fe1a092be8ad30ec01da588d8773c295ac6e140
23584 F20101117_AABQZC campos_l_Page_13.QC.jpg
2a9bd20839cd314a8a41f9957a37ab23
3338368168ae2fd64304e01e3d6e377fae563dee
885389 F20101117_AABQPI campos_l_Page_65.jp2
c2b05f4320d22387914214f6127d1103
bf7fe268f9be7be73419d67d5f4c28222c6e0a33
59150 F20101117_AABQKK campos_l_Page_07.jpg
3dd22bf1e3ce42adb2b6729385b61877
b1b2e2eb2cf705e62b515364db0b5b45607fdbc6
12666 F20101117_AABQUF campos_l_Page_44.pro
a7dafddf26eeb385f5bdb6f5e8307685
8a29904d6710ce603253c9ad015b704979417ed2
16470 F20101117_AABRBD campos_l_Page_41.QC.jpg
69c03a5522f2d4939a1c176d4dc7347f
c114bf9b272dad5e6ec4c8e99d7a579892192630
6717 F20101117_AABQZD campos_l_Page_13thm.jpg
257cf505dbf662cfbe1c87c7775088bf
59163ea8fae1672995b57b6fea468d5601089c33
F20101117_AABQPJ campos_l_Page_66.jp2
bea072a6ac6bf0ccddbae924bf83b67c
c04aee99ff7b5968ccbc6d08f0637a9ce4f37b8c
80501 F20101117_AABQKL campos_l_Page_08.jpg
2b1282b1164ac0e58997ce6750c56826
5b9ecb62db4be0af857d76ff0825572b644d643c
15603 F20101117_AABQUG campos_l_Page_46.pro
1759027b83d100e57259a5317130a770
f68b53f52aaf636672d846ba8c4644aac563848d
4743 F20101117_AABRBE campos_l_Page_41thm.jpg
296a234111ce50639ab87e9a7d88d271
2c3e1594328f15ae41de14b05242e5c629510fb2
12861 F20101117_AABQZE campos_l_Page_14.QC.jpg
adb063dd440b73ac7d3c568e10d72d49
201975553a3836ee1555627a93ed3da271a78f1e
75189 F20101117_AABQKM campos_l_Page_09.jpg
f0d03b6a72862b4cff9bcf61bad5288e
e2ad4cfc21fc62ede236dc5d99ac843818c8da2c
4913 F20101117_AABQUH campos_l_Page_47.pro
5a0db9a37775bcbd22727e82b6f321c5
dc962b07e7dbe919c185278aebec68f9b69e451f
15208 F20101117_AABRBF campos_l_Page_42.QC.jpg
34aa836cacbeb9c31a8f7c06086f9a8a
4f72654db22ed24a2b83114c5265a190fe01762f
3911 F20101117_AABQZF campos_l_Page_14thm.jpg
6e9bb13eb66e4b82ae5c4e07f2cbb1e2
ebae54188c90273dc1994d08cc8e3925759214d2
1051969 F20101117_AABQPK campos_l_Page_67.jp2
f58e7f02508324af509c44817a92966f
3b872767ab5d1886ca0b1dc41e2c6f311a772803
59253 F20101117_AABQKN campos_l_Page_10.jpg
fb854ab32a70416d8a308af67d9f431e
66bc2e78d6058dabd2ce5492cba4feb5d43ba77c
3053 F20101117_AABQUI campos_l_Page_48.pro
dfc23c02f9dc69bfecca92403d3b87ea
4d0962dffaf86aabe74f1c8edd9e0342f558627e
8842 F20101117_AABRBG campos_l_Page_43.QC.jpg
f76398d67a6c24005aa56c8b34d8826c
dde7a3106933e59c9913d590d14623a11f6cdf93
21682 F20101117_AABQZG campos_l_Page_15.QC.jpg
bc4aa7d2396ae4e4aec55b18a49df453
ec97ca4236947f60394d9013f7f1f955fb11745e
1051916 F20101117_AABQPL campos_l_Page_68.jp2
c81ff0d3ffed2f62b480a02fe898fc25
61419325c6caaf348bb2dc63d77ac7d002f0a70c
33713 F20101117_AABQKO campos_l_Page_11.jpg
a1076ae91e348a9eb6e75d6dd3bf8fc9
fbf93c706bcb568c1c1eb89cb5763d78c7a740cb
6112 F20101117_AABQUJ campos_l_Page_49.pro
2a77ab64da7aa91d089c6638c39597ad
3f75aaf31b414c384e17f6d0db9050abc1bca442
F20101117_AABRBH campos_l_Page_43thm.jpg
9eafd3a5249aec0901e1f806e501cb50
9c0d8a61b1423d99a3165b55ba6288b9c77cbe65
26252 F20101117_AABQZH campos_l_Page_16.QC.jpg
77c58fe4fd0b400543b9420584271f65
9d6aa49a35b4644203e4d2d339d8ff0ac01366e2
1051980 F20101117_AABQPM campos_l_Page_69.jp2
fb79c7608c4191e8bc1410b7a4476c8f
e3395ff797e1d5adcfbec9c2041a3d79b445226d
75395 F20101117_AABQKP campos_l_Page_13.jpg
f96a1c842e972d08d41275c27eb7d7bf
e4837e1cbe1f56b95b418d22c3a93e5762e93fdd
4037 F20101117_AABQUK campos_l_Page_50.pro
915a3d2c255ebea757dda1ee4b32924b
5450907483b076b5f72fb4769c566640933692dc
12487 F20101117_AABRBI campos_l_Page_44.QC.jpg
56f1ef1eac740ed6e65b551b7d33bfe2
363c784deb60ae8e0f811d3e3f51b375a948da7f
7092 F20101117_AABQZI campos_l_Page_16thm.jpg
938bb57bc147d568597ed213f1ec0584
e9ed9a4e2408eeee569f727b796832e6e732505e
1051956 F20101117_AABQPN campos_l_Page_71.jp2
6652ffaff8410b002e6ff6f49fa2fa76
cd44ff7c847fd41844be7cd9144870b71b6e0c90
40550 F20101117_AABQKQ campos_l_Page_14.jpg
4d3e0c94593b3d45a96a55a9d18dc24f
e37401a0c5a75053864239d18f561187bc135566
5323 F20101117_AABQUL campos_l_Page_52.pro
3495122512c35ecbdebe28511be366fb
e58c86cc3839ab2bb928dcb573ab8545beec79f4
4110 F20101117_AABRBJ campos_l_Page_44thm.jpg
505dbcb3af93a73911c6322966164c9a
a12125a3535c14fdd6addd1444115236884c3579
23299 F20101117_AABQZJ campos_l_Page_17.QC.jpg
eedd6b44ebf2fbe22672abe71da89541
712b290779f98dbbf4835d2e51fb987aab8881bd
F20101117_AABQPO campos_l_Page_72.jp2
159921fbda8743378936de77888b7261
0f21a0313a03fd3564859c23e9e0e395142a8c23
69368 F20101117_AABQKR campos_l_Page_15.jpg
38b6309e38a769b4a656285e023b9bb9
26468385739f2a5226fb2d9f77630405571953cd
37726 F20101117_AABQUM campos_l_Page_53.pro
f4fbf1c7b99aac6d0466689ceade2a18
e9fdc334c1d04736f57af6f24b2851a5ed5c9b76
12628 F20101117_AABRBK campos_l_Page_45.QC.jpg
9e9e93f741250d2e45f938f59a22c9fd
4b6c8b86d194d27de17afa2c7916517b1af2847c
6357 F20101117_AABQZK campos_l_Page_17thm.jpg
6709ae4cd2e6e3128afa987a4dcf5cec
bd380d9a9507fb683351a672816ca2e97b985ac9
F20101117_AABQPP campos_l_Page_73.jp2
2f3cea7fd5e07c1a784ed7adc8788a56
76f09257ea527fe9ace6303d2de6de63b4789bc6
81226 F20101117_AABQKS campos_l_Page_16.jpg
185ebed4c330c82c4acc59ef27f55f28
0fd94cf06f8cb57def4d42d64a40ed43465f3b69
11463 F20101117_AABQUN campos_l_Page_54.pro
bfd0c5eb7a25d9086d78985115383e6e
344463388dc07531b7e6ee69c747435fe7a623ea
4227 F20101117_AABRBL campos_l_Page_45thm.jpg
bed52d8712665f19420e70b197992688
be0028104b1f6c8004fec82f6a997a525cea9560
22806 F20101117_AABQZL campos_l_Page_18.QC.jpg
cbcb60b2c637966c10acbb2f45f4ca98
7fedafafb8a3b36cfab629e143ec21f69640d50e
523996 F20101117_AABQPQ campos_l_Page_74.jp2
fbac8a12bf2c0918ca29fd5e7cf9e854
f94f7f37a69b5dc76c8204e10f5614095d4887cb
73137 F20101117_AABQKT campos_l_Page_17.jpg
a731ccb4b21db311c5ae38cbef911c32
46bb19be3316e0a0786114e98a81805b689ba845
16363 F20101117_AABQUO campos_l_Page_56.pro
7fa3e947ead5f2918e1effc7937c21f9
5ccffae7587c337411012cacd07c53caeb8a7ffa
13293 F20101117_AABRBM campos_l_Page_46.QC.jpg
173d93b8988d6a14ff661f87d29581c3
7ceafa5cf1429e4e7445271484448613ff39c11b
16384 F20101117_AABQZM campos_l_Page_19.QC.jpg
7ec32ac64581c0f075606930c51a1e0a
92ab433adad84434fc9ded48905db7cd493645e9
528987 F20101117_AABQPR campos_l_Page_75.jp2
a43c30807c6ee3201ef06040286190c7
c97657f850acb4ac981b7e6eac29e4cbba294184
73032 F20101117_AABQKU campos_l_Page_18.jpg
55552a3c47f6b2b79c9291368e5565f4
86727cdf421424370f798ec315715c0ae93f51aa
3991 F20101117_AABRBN campos_l_Page_46thm.jpg
1953d938a207ef3b371be17bc2e85d50
4361a4b6867ff33a98dad95204711573039cf51d
4728 F20101117_AABQZN campos_l_Page_19thm.jpg
27ce12308d28e5df86d4c8083ae17f9a
f57a52ad87decfd16edb6ac85d2b4d2da8d9391f
590641 F20101117_AABQPS campos_l_Page_76.jp2
59ef5dde5d4ae3bb977c82e1a1e4d3cd
14ea6f8e6d142df4b2341e6a9ba3050b9b70b789
49622 F20101117_AABQKV campos_l_Page_19.jpg
5e7bde9e411665cfb10527ed56e81b2f
61cc28b82ad9fabb1f1b19229bab9d8e81880f5a
16326 F20101117_AABQUP campos_l_Page_57.pro
fbd4f0189c52d42219e4dd19c34144cb
cba1f2794f69e69888b0c427fcae8a843e3df25a
20138 F20101117_AABRBO campos_l_Page_47.QC.jpg
93cfa5a1e1e8397bd8366dc987d45a4b
02961eda1052815763a3b16ee65087bd4eec8b58
11529 F20101117_AABQZO campos_l_Page_20.QC.jpg
ff5a63df89b92f514eb3b66bf157a527
2c96de9a603f3d76f97793f34c6af923c1f28bce
33893 F20101117_AABQKW campos_l_Page_20.jpg
e6afa456bc81dc7c2ae85709e7df8bbc
b31333b263025b58872f715648806cef320fd794
14393 F20101117_AABQUQ campos_l_Page_58.pro
a05b7ae89ec27e64c48150258d9c96c5
272c5033b60c786772810b494659cca9e9c329e5
1051973 F20101117_AABQPT campos_l_Page_77.jp2
286f2f3d23dc84f315fdf2df0a03870f
8320cfdc6ccd49133b1e2d2454a1b8e3eb98d68a
5927 F20101117_AABRBP campos_l_Page_47thm.jpg
7be64ac1322b55387cc59be0851f0e91
1edae6d7974b590a06f17cd55e60d0c2e36cc3bb
4093 F20101117_AABQZP campos_l_Page_20thm.jpg
a3491078c003d024ef82af97e0e9402a
ac416f459936efe3638843ef71c6ebbcef85b87a
21889 F20101117_AABQKX campos_l_Page_21.jpg
1628964de71dd220c3d98d6194e961ed
20ae94c3bd9ef0804db6cff3b49b68acb8f28900
7731 F20101117_AABQUR campos_l_Page_59.pro
264ccbc13023ff87900ad6589849aafa
c10d9c114b68a573df702e6f83e749832a05511a
698110 F20101117_AABQPU campos_l_Page_78.jp2
3e6ebec727623288f86e7476adb96b08
249998fba80ff39248803800dcfbbc342e1cb099
20269 F20101117_AABRBQ campos_l_Page_48.QC.jpg
eaacd0bd110ae0530f72fd0ab16dd255
5c5ac4922c63af3f7256983dcb11495cd1f77240
7954 F20101117_AABQZQ campos_l_Page_21.QC.jpg
0761e36abbaee1c98a5ead0d1c5c0a4a
fef411466d1ba5b9fb4ef0a7e8756383f2001ffb
70024 F20101117_AABQKY campos_l_Page_22.jpg
a2373f2eec831824120a8840b4d3dccf
a3e55a1201969ba24189455bbe03e336d6426716
35848 F20101117_AABQUS campos_l_Page_62.pro
20397b5112e86fd77c31275b2f4b2add
8de5e984a848e11153b824ee8e71fdcc5ed4258c
416086 F20101117_AABQPV campos_l_Page_79.jp2
968fbdbc56bb97ccbdc1d80459ca01f5
b6bbe2c692a64d40d3e8462ae5f637ec161ab87b
6016 F20101117_AABRBR campos_l_Page_48thm.jpg
daa5cb10ee86c17d0f48dd519a88278c
e28b3f4d5dd3c3d52f4ac1ba5f4adae12b30bc3d
2613 F20101117_AABQZR campos_l_Page_21thm.jpg
a16b61f45890e8ca9e492be6ac79e4ec
8997c9e1affb4cfedac69ae13ef2eab4e06cef55
73622 F20101117_AABQKZ campos_l_Page_23.jpg
03a8f0fdfd44ba5f90574d3e18fdba16
375b701023edccda18c12a5d8ae0b65009db41b3
14424 F20101117_AABQUT campos_l_Page_64.pro
6a84b4b507d87b483c48784817a38c12
fbb821f8480a7c880257f7dd4df32120f7d28038
F20101117_AABQPW campos_l_Page_01.tif
6d75bbcfe26f74522f7c06a082104b8f
c006ce1d485f51023753575e3afbb1ddd5523f74
17115 F20101117_AABRBS campos_l_Page_49.QC.jpg
324a5701e11328179fa11abe03f362a5
8b4519636a4142e288ea114974dd167b7a938a94
21839 F20101117_AABQZS campos_l_Page_22.QC.jpg
f09a72cbf43d95fef81925f6238ff136
d424124419766d57eac1c41b57dcbd05c421df35
6108 F20101117_AABQUU campos_l_Page_65.pro
f07e7defaad674d27d46d03dd73219f6
95e755e069993f44b1506f6d317e7b0795fca010
F20101117_AABQPX campos_l_Page_02.tif
d85bc11ce290e910a86c1526725dcc7e
1ebccd01f0444929f7ad8e021d1d28a9d648308f
5334 F20101117_AABRBT campos_l_Page_49thm.jpg
7d21babda26de13fe1dd99b3c98a9949
bcd18c9b7691085bba9f943576b692a6b50eff91
6191 F20101117_AABQZT campos_l_Page_22thm.jpg
93245472033b6c84bd95ed9a4fc35278
2d1253b52ceaca0c801404e6f473c852cdcef7bf
4677 F20101117_AABQUV campos_l_Page_66.pro
c58e6cf2041f86eddab82aa455aa3763
4fc634a88c69a07c076b6224cc11e27548d670dd
35396 F20101117_AABQNA campos_l_Page_79.jpg
a1c25cda19695fc68ef5f2bd29f485a9
e8a15052668f861c27ed6130158f89355fd81f00
F20101117_AABQPY campos_l_Page_03.tif
7b56c4cb838ed3b29b2947f2185a8f2a
633e295c3f5a9a838851efd4fa01fea906b24800
21151 F20101117_AABRBU campos_l_Page_50.QC.jpg
c59854cf2182517d0bc01aeeb1d67650
d739fad536110c9dddfcc374e343ed6ff1fa1d5c
4531 F20101117_AABQUW campos_l_Page_67.pro
8881f9b9b2fd6a5e2e481a325b743a61
1a2dd59daf15676e8cbc58098195163fee2376b5
244736 F20101117_AABQNB campos_l_Page_01.jp2
ce04dd142da04e693bc85be208bc512e
9e5e9e8a2d31258ce1e606a9359ef0a629ea2eb8
F20101117_AABQPZ campos_l_Page_04.tif
099f7a52c8324e69632dba6b8f5412ab
62c458523b8af5af7ae41e16368c8fa0cb2abe07
5967 F20101117_AABRBV campos_l_Page_50thm.jpg
03a3bf439874dfc32ca1978daa5c4295
58bfa8f40ed4faf33a364af6433bb6584c091cd0
23042 F20101117_AABQZU campos_l_Page_23.QC.jpg
0c776c502fcf32b74627bb894a0c4e85
c06525bcfc4b55ee1c478f7807622a7e67b3d2c5
60903 F20101117_AABQUX campos_l_Page_68.pro
614cc6a7fe0f922ff613396fa17a7fc7
f6d3010bb2050d4beaf316e8287ddcbcd3b7736c
26873 F20101117_AABQNC campos_l_Page_02.jp2
7cecba9a2917f800a6437e7786d3d1ea
f4e6c1efc82ef375582c270440d2c02ed9b8d896
20329 F20101117_AABRBW campos_l_Page_51.QC.jpg
b7341236c0f5d3ee23c73129909a983a
8a0c96e347fc1805f14a5e4277667aee1d6ee75b
6473 F20101117_AABQZV campos_l_Page_23thm.jpg
b6640c5d5c8bcd58add107c624eb8cac
e99bb6ffcd040bc3df0851f902780703074f7142
F20101117_AABQSA campos_l_Page_59.tif
0c3513dc280ed5a03e768518aaf1b8df
9f9e018466abf6222f8fce260c83f624103531bd
62643 F20101117_AABQUY campos_l_Page_69.pro
1bbbfb40457237235801bf21218fac97
2237389dd1e3e2e5d3f4a1a516484c4a53d694ad
32244 F20101117_AABQND campos_l_Page_03.jp2
760f592e58273f44a002db7c495f4173
e200be0391184cc3870c9092ecbf3643b4994f71
6097 F20101117_AABRBX campos_l_Page_51thm.jpg
e742b4d2f83a0fdf282cb4d535ec4ea7
cbb26da4466e8df717cd97335d9d03fb6bf6f2a5
23282 F20101117_AABQZW campos_l_Page_24.QC.jpg
940c94130e1965bcbd99394e383af4fd
7f9fa33718be69bbeb51269b5949c99d455e9751
F20101117_AABQSB campos_l_Page_60.tif
adb69d1d51a01ad3bfad83314f588d72
8dea835f34f356a839b832334d9600c4e4260aee
59573 F20101117_AABQUZ campos_l_Page_70.pro
01fc9b2c21d43ecd89c46b92fde13b31
fd7ab4d0494391d1ecd677a4dcda82f1d8a48636
827555 F20101117_AABQNE campos_l_Page_04.jp2
ee6764500de4d325c63d38a5ff41bacc
192fb58ac7e00e01fc8302d675189b59b7328fcc
21659 F20101117_AABRBY campos_l_Page_52.QC.jpg
a6fcc9f8c5318e185be4e0bb5ec7fa76
2d12921450182ed8daa88fefd375f5cf600b562d
6475 F20101117_AABQZX campos_l_Page_24thm.jpg
579801e4987d05c835eb54b2a3dd7515
ed83bfe3941b34433ca2cdab32d884bd58c2ab73
F20101117_AABQSC campos_l_Page_61.tif
2a4d2657449e693ab2e92ad58c2f9ebe
4da94b8e9617fdc9efc1bb16d17c778720b17bb2
1051933 F20101117_AABQNF campos_l_Page_05.jp2
0f7d9dcf0aacece6c5c2d8c2ebd9128a
7c0d2bd0a9688195d7f1d482c054254b58e41d1a
6155 F20101117_AABRBZ campos_l_Page_52thm.jpg
401398841bca2b7765f2dcdb32ff32e3
314b318eb6aea8945a9f0cf31de9fd5f33ce1083
23457 F20101117_AABQZY campos_l_Page_25.QC.jpg
62ffb044a0d0774a23618664c5fb6c63
8bcc436ca77fe420a09c949f17d6d5cfbd69d299
F20101117_AABQSD campos_l_Page_62.tif
f3945ea708f2fa3bfd9082b46ecfdcf2
cf34a1e3cae2ae11f7ac43bd2456195b1ab9ea90
627111 F20101117_AABQNG campos_l_Page_06.jp2
36648639bb58f5c1b7a889b98beb255a
79c30f71afaa63d2e77a20f76d9993945e0e747c
169 F20101117_AABQXA campos_l_Page_48.txt
c6e883520f687f22508309e390ee2935
83da0372650472f326c6e2b091ab2aff6857976b
6573 F20101117_AABQZZ campos_l_Page_25thm.jpg
8f4a90652cf30287dafac41a08609232
a9c22c7699172d81a43946d2815875487ab32c8a
F20101117_AABQSE campos_l_Page_63.tif
d8efa8ab2ca4f6d75e1e974559471e1c
8a5269751692a23b57d05c1ae47219356a9d8450
1051975 F20101117_AABQNH campos_l_Page_07.jp2
4a0f65ff077778d2e00aae460934ab88
bbd09ba40dee2ab5aa9862dcf42c03473bc724e2
323 F20101117_AABQXB campos_l_Page_49.txt
62d0c9cedde085e6df2cb0620a691128
f27bc824e9d682813484fcbc50956f0e76694f46
F20101117_AABQSF campos_l_Page_64.tif
763490f3834e40a416bea3cc23094225
ccd70abb0f43b5181d48a5fe0998a54a79a26c3f
166 F20101117_AABQXC campos_l_Page_50.txt
229f1e118aaa97392ce35bd96e4099e4
07b3256e2cbfdb9150f31478a1fd83dd64b75389
F20101117_AABQSG campos_l_Page_65.tif
d287252a47dee2c90f81c17a7ec3e788
22872bd177e919eb5eb1c98bbf20ddc0f21da77f
1051962 F20101117_AABQNI campos_l_Page_08.jp2
f6583763a91a3cfd8a17fc98b2542646
0913c997b5e7c35ac41df08d970479f27faea5c2
286 F20101117_AABQXD campos_l_Page_51.txt
35dcd731c741d2649b894aeee93d1a19
95857217124018d5b730c00c90aae404e35d67f8
F20101117_AABQSH campos_l_Page_66.tif
b79bf4091984712cfd3ef715a2db3e83
7825c3190178fe91281075b9a52ad2d097c6cccc
1051985 F20101117_AABQNJ campos_l_Page_09.jp2
fdbdb57f15153d290066a47caacdf80e
dd446ba2840a918c229dac979985528809639172
221 F20101117_AABQXE campos_l_Page_52.txt
34b9675f378b8a2f4ed1a1320404f0bf
e4d670977aa747eda293fba926ee3013216b0a60
F20101117_AABQSI campos_l_Page_67.tif
a5678e85e08050f4b68274b956b9357f
84cf9d6d61094aec35cab688f538c2e7008eb53a
782884 F20101117_AABQNK campos_l_Page_10.jp2
d074743a4c7516bfa92e17efc1d0b338
3cee1a66af6773fcec22574ce41c638954bedb40
1855 F20101117_AABQXF campos_l_Page_53.txt
f06795e9fd169a136a8c5389f66ceb5d
96335631fa351940bf47ef26f8fe9b8d052db7a6
15124 F20101117_AABQIN campos_l_Page_45.pro
e09292abe847baba547a05459fcabf2f
eddeb94c9ac75ba1c6876041bc1c624a7d448aa5
F20101117_AABQSJ campos_l_Page_69.tif
fb2cbb8dff368d78cd90bb348c97f39e
08702314cd488e3ec8eec18c78ce3a0f28da3c28
410948 F20101117_AABQNL campos_l_Page_11.jp2
ccdef906c498de365eecf3921d661c0a
686ea74e5f4e6dac10bc9ca9b88f800b338a4621
579 F20101117_AABQXG campos_l_Page_54.txt
f63bc378a7232eb7c5e1c15f3d4dcd5b
77395d477e05ccebdad16363e42830c677212b98
3187 F20101117_AABQIO campos_l_Page_54thm.jpg
feeb8f85d4ff0a91e79682ed81c963e2
d69833583beda2a8feb4e730c91857a4cf88f765
F20101117_AABQSK campos_l_Page_71.tif
501007dcac1d1e2789e6f644ff5cc9c4
1805acfed727117c99ed15e71019bbb1fe1acaed
844237 F20101117_AABQNM campos_l_Page_12.jp2
3ddc564fb752c0eaf404a8f2971e7951
82a3c5c7e9eb98284140c094eee499da2445fe0d
767 F20101117_AABQXH campos_l_Page_55.txt
63cb2b7ab15fa2a635c9148f6f5fb806
8f6a5eeffaf8bad9649fb61b3efa1071ccc88a99
346 F20101117_AABQIP campos_l_Page_21.txt
474a1862e768d7b882f4690b74741679
f35af73053a37c36135ec4939b9ba48c39c10768
F20101117_AABQSL campos_l_Page_72.tif
4ade324327a1c602dbd2d4f5747c8cab
48b34f93bcc55bf1c914d4a61591019ce39e4a4a
F20101117_AABQNN campos_l_Page_13.jp2
c85aa8f438a71064fedd847629acc592
892cbbfe551b7116e61a5c6fb77a7086707e2e7e
821 F20101117_AABQXI campos_l_Page_56.txt
02bbc8ed6c1e2ededec615aa3bf1b92d
a1fc24eff86f9279475cfc06193986d5ca309d07
F20101117_AABQIQ campos_l_Page_68.tif
3d85c00fbc2fd9ce97bdb6d12e5902a0
a31f3e4384224bccb394bf8d73b26699de346702
F20101117_AABQSM campos_l_Page_74.tif
c4db9292fbea7831cec093f66953a985
21bac2f7b193f73765bd2064316eb079b1a43245
517702 F20101117_AABQNO campos_l_Page_14.jp2
62191ecfdb3de1da8f7ad2c8654c76ea
7bbd8247b19a6d06bf6a7eb564ffde6e26c26164
850 F20101117_AABQXJ campos_l_Page_57.txt
d064cc84bfa2f64762109a9df3f67601
0f76534d5f01e6279dde0876fd6dae891f2046d4
4640 F20101117_AABQIR campos_l_Page_67thm.jpg
0b1d3857b1b4bef8c3c73d0c9f20b96d
bcbf9d2bed1e203bf55557bc1129f9457e0ff31d
1051950 F20101117_AABQNP campos_l_Page_16.jp2
909b05b67194189d8a756df411c8e063
2909cdb8ec7ce79a6f2f033065e2d08071e61d11
384 F20101117_AABQXK campos_l_Page_59.txt
6eb79b06a37d08e4872ca4f0c40af605
bdeb29b7c89277f2aeab5b6b5399fde22e625412
F20101117_AABQIS campos_l_Page_29.tif
8e8e5ec0f909a2809e537a8cb5683684
55ad77ca7b00c1b332308a29503b6e626c1318f1
F20101117_AABQSN campos_l_Page_75.tif
f63b8671b149d16412b7f3c2793e0183
c4f2a311ebfe60c6f5df379f2162b595c64e9d98
1013425 F20101117_AABQNQ campos_l_Page_17.jp2
dde796ddb104a27c7f9615b826764411
ab36e945d375942076d3ca712678a2941bd3ff58
946 F20101117_AABQXL campos_l_Page_60.txt
b5633c556f8d75b8fe5eedb427056af6
eb64c02d45ae3dfb05027f5ae1f78a9a6c89a184
6262 F20101117_AABQIT campos_l_Page_21.pro
fa322bad00489ffd85d8ed52c06f4f3b
45b84819bde900131f2b60e8dceab018a3d5898a
F20101117_AABQSO campos_l_Page_76.tif
9538e1431cf33ebc189c02e2a83f4889
847192183723c4088e5115d7c3d547f6cc0bc0f5
1018055 F20101117_AABQNR campos_l_Page_18.jp2
78abfe0b6a312776f6fd58f8a345c1b0
49860f3acba27b77da49fdb9f4ba636c82269db3
762 F20101117_AABQXM campos_l_Page_61.txt
9da65b140582e4be4bc6c8e2a3102d6a
af27cd59fa0d1b0b26634b490fee6414c2ee859d
675061 F20101117_AABQIU campos_l_Page_42.jp2
7c6e465bdce43195f165407aefcb47c8
b96feaff46f21d48ac069d7b05104f8baeb683b0
637077 F20101117_AABQNS campos_l_Page_19.jp2
5ea842c0fd9da35bc436d2419cb51fc0
5b067f1d1da2a38a2836fc508ff2983038615f64
1541 F20101117_AABQXN campos_l_Page_62.txt
224fcb9c0ef2b430f67df5c0437999f2
51331f490a6fb35096f1bf4df407f0ef14e6f601
3455 F20101117_AABQIV campos_l_Page_55thm.jpg
6833f85622e8fa903be239a2cefb8c8d
c1bdbd33133da5bfe01c059ca07b26ec18d23a4c
F20101117_AABQSP campos_l_Page_78.tif
7d900527e2429dfc5ef41387d43b16a9
0a26c2073f8d707a52af24dff1ea41ff2ccdc1e6
331612 F20101117_AABQNT campos_l_Page_20.jp2
274aa0c25ae45761261b3d741eb92806
46588eed4043b8189b67194cd09d2d9a965889bb
1731 F20101117_AABQXO campos_l_Page_63.txt
b750df4296490d61e008b5bd5ae335db
80424c0d4ff54930a7098dce189ca1c9101f31c2
6413 F20101117_AABQIW campos_l_Page_18thm.jpg
ef3d8e559f922728799b913cd27ccfb1
f6eacff28a41808a7d3e3e88aafb49846d0a9a87
F20101117_AABQSQ campos_l_Page_79.tif
ac4db58e4288f28eeb08fdfd615476c7
652d20f33229f49e73e80924f272a442d862fa7e
183654 F20101117_AABQNU campos_l_Page_21.jp2
cf83624977f8e7bd8a46e95cb10bbda9
f2f9febd3773a7204b88b516c7ce882c8c2fbd4e
624 F20101117_AABQXP campos_l_Page_64.txt
c0e4d481a486cb8dc5a00526e65485cc
dac2a566272a120a365b1872405ffe2a38812f9d
3144 F20101117_AABQIX campos_l_Page_32thm.jpg
d93c869a1f45db6b8bbf1ebfed2fb748
dfdde2bcbb7f394de9bf3cc3dea6123c983869ea
8254 F20101117_AABQSR campos_l_Page_01.pro
569eedaa4b35fa4af56b947fa7c1c337
953e67444de9965fce148969597545126ea138f8
974459 F20101117_AABQNV campos_l_Page_22.jp2
8d441267e2209ee9f2ea5cd97c464f53
19dec9b2bf6e9ac790bf4d985a8cbbcf97a062a9
280 F20101117_AABQXQ campos_l_Page_65.txt
a01afcb0b81c50e7901eec02b2b1986d
9bd1782a2754d7d51b4f56ab10c12cf1c003cfee
F20101117_AABQIY campos_l_Page_43.tif
a8af9b4badbe5fc2c26e3d0ff29b44e1
5d0503e1469d69a18925252d6df3741ab0f94998
964 F20101117_AABQSS campos_l_Page_02.pro
1ae637f0d6f24db34cd96293a95ee750
70cc0069a3866a19cd06bf8c86c3d40266fa796d
1025951 F20101117_AABQNW campos_l_Page_23.jp2
873ba75c5c0728e5bbc24c85d871358c
66c8111424f21785945f7c307a606a138e16a4ba
294 F20101117_AABQXR campos_l_Page_66.txt
e8f83d7ad1082b0280faf010558edccd
9416c6a0037a099a82171e603fa0043adf9b2433
1772 F20101117_AABQIZ campos_l_Page_77.txt
923d20193cfc47edf48f160de3f85584
020ae61796a8710234e55e7b55ef1676974670aa
1300 F20101117_AABQST campos_l_Page_03.pro
949990f91d928d052fb2d3102bc793aa
1159df976fae93c35b312b2ab91b78dcb699ae55
1051967 F20101117_AABQNX campos_l_Page_24.jp2
6e97869cd3984d4c373e0d2ccbba4a5b
5d814cf565367c6ed42645ee2da554d662c21031
36410 F20101117_AABQSU campos_l_Page_04.pro
aa9c53c6b3083900c7571bf2c9feb1f1
413682437c7f0e345b96d69159575da9f7644c82
76095 F20101117_AABQLA campos_l_Page_24.jpg
9f888614e3f05cd0735a74ded51bd1d5
dbb0f82a1fc4beaca9e58040e4d1f012bd586ba6
1051974 F20101117_AABQNY campos_l_Page_25.jp2
2d3fdd99dd06d4ffbcb2cd205f27bb58
715050261e4428ad7fc4fcb7ee1a7492704d9454
289 F20101117_AABQXS campos_l_Page_67.txt
e211c134a1b8a0cdcca612d674bc029c
85a60af156e2721e3c70445c4064ea441d332dff
95925 F20101117_AABQSV campos_l_Page_05.pro
5e3da140c8de56d46142f77e9244d7a4
0e2c76a37a4c5df034a5da73f6412765895437a4
78690 F20101117_AABQLB campos_l_Page_26.jpg
f3d231b1d2c984a59b972912ece10884
126ab608928c41aefef06c90877aef2536812ece
F20101117_AABQNZ campos_l_Page_26.jp2
86a8d759bab23eeb7620c8f7da192833
5ec30ecd4bb11a9181ae061b07f97a95bfc6d1ff
2815 F20101117_AABQXT campos_l_Page_68.txt
e35102079c0495800e38802d134ee7ad
0017ffaef3d2f8ccaa4c0d11e44af225ff3a608c
26369 F20101117_AABQSW campos_l_Page_06.pro
ba6cf10218f8f69d8c3a4fc385523dd7
eef26d209233f72bd63c243d43dfb925d03f13fb