Mackay311 Hunter

M IN N
LIBRARY
7 #r5T/S
3 5£0
University of Nevada
Reno
The Geochemistry of Lime-Induced Heave in
Sulfate Bearing Clay Soils
A dissertation submitted in partial fulfillment of
the requirements of the degree of Doctor of Philosophy,
in Geology
by
Robert Dalton Hunter
August 1989
©1989
Robert Dalton Hunter
All rights reserved
The dissertation of Robert Dalton Hunter is approved
University of Nevada
Reno
August 1989
ii
ACKNOWLEDGEMENTS
Where do I start? Bob and Robbie Hunter taught me to do
my best and finish what I started. Anyone who reads this thing
will notice that it took guite awhile. My parents gave me the
gift of tenacity, among other things. Dr. Roger Jacobson of
the Desert Research Institute provided outstanding technical
and moral support throughout this lengthy ordeal. His efforts
and patience are greatly appreciated. SEA, Consulting
Engineers, Inc., has been very supportive of this project and
is gratefully acknowledged. Adrienne Frederick of Adrienne's
Office, a long-time friend, typed this beast, including the
dreaded "big nasty awful table" and numerous chemical
equations. Thanks Adrienne— you probably saved my marriage.
Finally I want to thank my family: Candace, my wife, for
her support and patience; and my children, William and Susan,
who, to this date, have never known their father when he wasn't
in school.
iii
ABSTRACT
Clay soil is commonly stabilized in-place by mixing with
anhydrous (CaO) or hydrated (Ca(OH)a) lime. The resulting
chemical disequilibrium causes various cementing and exchange
reactions between the lime and clay. On Stewart Avenue, Las
Vegas, Nevada, unusual reactions between lime, clay, and
sulfate minerals caused severe swelling in lime-treated
subbase. Reconstruction costs approached $3,000,000. Lime-
induced heave has also occurred in California, Utah, Kansas,
Texas, Tennessee, and Paris, France. On Stewart Avenue, heave
resulted from growth of thaumasite, a complex multi-hydrated
calcium silicate-carbonate-sulfate mineral. Thaumasite forms
a solid solution series with ettringite, a multi-hydrated
calcium aluminum sulfate mineral. At temperatures above 15 C,
ettringite probably forms first and later converts to
thaumasite. At least 50% of the sulfate migrated to the
nucleation centers, mostly in capillary water derived from
ponding in utility trenches. Mass flux estimations indicate
that the needed ions could probably have reached the nucleation
sites within the observed time frame of two years.
Solubility determinations were made on ettringite
synthesized during this research. Study results, which
considered ion pairs, are reasonably represented by the
equation log Ket = 196.429 - 1.6699T + 0.002846T2, and
corresponds to —48.49 at 25 "C. The logarithmic expression

iv
leads to AG° = -66.14 ± 0.27 kcal/mol, AH” = -11.0 ± 0.3
kcal/mol, ACP° = 2.4 ± 0.1 kcal/mol, and ASr° = -196 ± 52 cal/deg
mol for the dissociation of ettringite at 25°C. Using this
data, ettringite was found to be the stable phase at high pH
and sulfate concentrations above 15 mg per kg of soil. On
Stewart Avenue approximately 25% of the heave was due to added
mineral mass with the remaining 75% resulting from density loss
and increased soil voids. Complete reaction of 10,000 mg
sulfate/kg soil should induce a one-inch (2.5 cm) heave from £ , ~ # /
a 12-inch (30.5 cm) thick lime-treated soil. Because of ion
mobility, lime treatment of soils containing measurable sulfate
is risky. Swelling can probably be held to tolerable levels
by careful control of drainage and capillarity. Costs of
preventing chemical heave in soils containing sulfate minerals
may exceed the potential savings from lime or cement
stabilization.
V
TABLE OF CONTENTS
ACKNOWLEDGEMENTS ii
ABSTRACT iii
LIST OF FIGURES viii
LIST OF TABLES xi
LIST OF APPENDICES xiii
1 INTRODUCTION 1
2 THEORY AND PRACTICE IN LIME STABILIZATION OF CLAY

SUBGRADES 10
Historical Background 12
The Chemistry of Normal Lime-Soil Reactions 14
Cation Exchange 16
Flocculation/Agglomeration 20
Carbonatation 23
Pozzolanic Reactions 24
Design of Lime Stabilized Subbase for
Pavements 30
Basic Construction Methods 32
3 LIME-INDUCED HEAVE OF SULFATE BEARING CLAY SOILS:

CASE HISTORIES OF STEWART AVENUE AND OWENS AVENUE
LAS VEGAS, NEVADA 34
Site Conditions 34
Stewart Avenue 34
Owens Avenue 37
Geology and Soil Conditions 38
General Geology 38
Project Soil Conditions 40
Exploration 44
Field Observations 57
Laboratory Analysis 63
Soil Testing 63
Index Testing 63
Moisture-Density Curves 63
Volume Change and Expansion 64
Chemical Testing 66
Soluble Salts 66
Cation Exchange Capacity 69
Mineral Identification 69
Analysis and Conclusions 71
4 OTHER CASES OF LIME-INDUCED HEAVE AND RELATED

LABORATORY RESEARCH 85
Other Cases of Lime-Induced Heave 85
Previous Laboratory Research on
Lime-Clay-Sulfate Reactions 91
vi
TABLE OF CONTENTS (Continued)
5 THE MINERALOGY OF THAUMASITE AND ETTRINGITE 93

Thaumasite 94
Ettringite 96
Synthetic Ettringite and Thaumasite 98
Ettringite 98
Thaumasite 99
6 METHODOLOGY FOR EXPANSIVE POTENTIAL AND MINERAL

SYNTHESIS EXPERIMENTS 103
Objectives 103
Sulfate Leaching 104
Expansive Potential 106
Expansive Pressure 106
Volume Change Experiments 107
Experiment One 110
Experiment Two 110
Experiment Three 111
Experiment Four 113
Experiment Five 114
Experiment Six 116
Summary of Experiments on Expansive
Potential 118
Ettringite/Thaumasite Growth in Other Soils 122
Ettringite/Thaumasite Concentration
by the Heavy Liquid Method 125
Ettringite/Thaumasite Concentration
by Elutriation 126
Synthesis of Ettringite and Thaumasite 128
Synthesis of Ettringite 128
Experiment One 129
Experiment Two 130
Synthesis of Thaumasite 134
Experiment One 134
Experiment Two 138
Experiment Four 141
Experiment Five 142
Experiment Six 143
Summary 145
7 THE THERMODYNAMICS OF ETTRINGITE DISSOCIATION 146

Experimental Methodology 146
Evaluation of the Analytical Data from the
Solubility Experiments 154
Summary 159
The Solubility of Gypsum 160
The Solubility of Ettringite 164
The Thermodynamics of Ettringite Solubility 167
vii
TABLE OF CONTENTS (Continued)
8 ANALYSIS AND EVALUATION OF EXPERIMENTAL

AND FIELD DATA 170
Laboratory Simulation of Lime-Induced Heave 170
Expansive Pressure 170
Volume Change 170
Thaumasite/Ettringite Growth in Other Soils 176
Synthesis of Thaumasite 178
Synthesis of Ettringite 178
Mass-Volume Relationships 179
Mass-Flux Calculations 189
Geochemical Reaction Model 191
9 CONCLUSIONS AND PRACTICAL APPLICATIONS 198

Stability Diagrams 199
Portlandite (Ca(OH)2) 199
Gypsum (CaS04-2H20) 201
Ettringite and the Saturation Index 202
Evaluating Susceptibility to
Lime-Induced Heave 207
Engineering Considerations 211
REFERENCES 215
APPENDICES 220
viii
LIST OF FIGURES
1 Photograph of heaved pavement on Stewart

Avenue, Las Vegas, Nevada 3
2 Photograph of heaved median on Stewart

3 Diagram of the structure of kaolinite 17
4 Diagram of the structure of montmorillonite 19
5 Diagrammatic representation of the fixed and

diffuse layers 22
6 Diagram showing effects of pH on silica

solubility at 25°C 27
7 Diagram showing effects of pH on dissolved

aluminum species in equilibrium with
gibbsite at 25°C 28
8 Location map for Stewart and Owens Avenues,

Las Vegas, Nevada 35
9 Photograph of typical distress along Owens

10 Generalized soils map in the area of

Stewart and Owens Avenues,
Las Vegas, Nevada 41-43
11 Location of test pits along Stewart

Avenue 45-49
12 Location of test pits along Owens Avenue 50
13 Typical test pit profiles for Stewart

Avenue 52-55
14 Typical test pit profile for Owens Avenue 56
15 Photograph showing concentration of large

crystals along contact between native soil
and subbase from test pit S-7 60
16 Photograph showing specimen of undamaged

subbase from test pit S-26 61
17 Photograph of test pit S-10 showing lens

shape of damaged subbase 62
ix
LIST OF FIGURES (Continued)
18 Trilinear diagram from untreated soils from

Stewart Avenue 73
19 Trilinear diagram from lime-treated soils of

Stewart Avenue 74
20 Typical stiff diagrams from treated and

untreated soils on Stewart Avenue 76
21 Graph of soluble calcium versus soluble

sulfate 78
22 Trilinear diagram for lime treated and

untreated soils along Owens Avenue 79
23 Graph showing percentage of clay sized

particles along Stewart Avenue 83
24 Graph of expansive pressure from growth of

ettringite/thaumasite 108
25 Results of volume change experiment five 117
26 Results of volume change experiment six 119
27 Graph showing estimated percentage of

calcite in synthetic ettringite 133
28 Graph showing the change in the equilibrium

constant of gypsum as a function of
temperature 162
29 Graph showing the change in the equilibrium

constant of ettringite as a function of
temperature 166
30 Diagram showing relative changes in soil

volume from growth of ettringite/
thaumasite 188
31 Diagrammatic representation of the

mechanism of lime-induced heave 195-197
32 Stability diagram for portlandite and

ettringite 200
33 Stability diagram for gypsum and ettringite 203
34 Graph showing untreated and lime treated

soils from Stewart Avenue relative to
ettringite stability field 205
X
LIST OF FIGURES (Continued)
35 Graph showing changes in geochemical

equilibrium induced by treatment with
4.5% CaO 208
36 Graph of calculated maximum volume change

as a function of initial soil sulfate 210
XI
LIST OF TABLES
1 List of Minerals Identified in Stewart

Avenue Samples 70
2 Mineralogic Properties of Thaumasite 95
3 Mineralogic Properties of Ettringite 97
4 Initial Chemistry (in Grams) for

Volume Change Experiment Five 115
5 Summary of Experiments on Expansive

Potential 120
6 Sample Designations and Loctions of Various

Soils for Ettringite/Thaumasite Growth 122
7 Mechanical Analysis of Various Soils

for Ettringite/Thaumasite Growth 123
8 Results of X-Ray Analysis of Other Soils

for Ettringite/Thaumasite Growth 127
9 Summary of Ettringite Synthesis Experiments 134
10 Thaumasite Synthesis
Initial Chemistry of Experiment One Group 135
11 Estimated Percentage of Thaumasite

in Experiment One Samples 137
12 Thaumasite Synthesis
Initial Chemistry of Experiment Two Group 138
13 Estimated Percentages of Thaumasite in

Remaining Samples of Experiment One and
Experiment Two 139
14 Thaumasite Synthesis-Initial Chemistry of

15 Results of Thaumasite Synthesis

16 Results of Thaumasite Synthesis

Experiment Five 143
17 Initial Chemistry of Thaumasite Synthesis

Experiment Six 144
18 Composition of Solutions Used in

Determining Ettringite Solubility 147
Xll
LIST OF TABLES (Continued)
19 Conductivity (in Micromhos) and pH of

Ettringite Solubility Experiment at 10 "c 149

Ettringite Solubility Experiment at 25 °C 150

Ettringite Solubility Experiment at 4 0 °C 151
22 Chemical Analysis of Preliminary Sample

for Ettringite Solubility 152
23 Analytical Results of Ettringite

Solubility Samples 154
24 EPM Balance of Analytical Data 156
25 Stoiciometric and Measured Mole Ratios 157
26 Calculated Equilibrium Constants for

Ettringite 165
27 Summary of Thermodynamic Values for

Ettringite at 2 5 ° C (298.16°K) 169
28 Data for Mass-Volume Calculations 181
29 Data for Estimation of Mass-Flux on

Stewart Avenue 189
xiii
LIST OF APPENDICES
1 Summary of mechanical test results for

Stewart and Owens Avenues 220
2 Unified soils classification 232
3 Typical volume change and expansive

pressure curves for Stewart Avenue 233
4 Trail dilution ratios for extract of

soluble ions, Stewart Avenue 234
5 Summary of soluble ion chemistry from

extraction of Stewart Avenue soils 235
6 Summary of test results of cation exchange

capacity for Stewart Avenue soils 243
7 Typical x-ray diffraction patterns,

Stewart and Owens Avenues 244
8 Comparison of thaumasite and ettringite

x-ray patterns 249
9 Typical scanning electron microscope

patterns, Stewart and OwensAvenues 250
10 X-ray diffraction pattern from U.S.

Highway 41, Davidson and Sumner
Counties, Tennessee 252
11 Description of experiments on lime-induced

heave in progress, University of
California, Berkeley 253
12 List of x-ray diffraction peaks for

thaumasite 256
13 List of x-ray diffraction peaks for

ettringite 257
14 X-ray diffraction pattern for experiment

VC-5C 258
15 X-ray diffraction pattern for experiment

VC-6A 259
16 X-ray diffraction pattern for sample CS 260
17 X-ray diffraction pattern for sample ES-2 261
18 X-ray diffraction pattern for sample ES-3 262

XIV
LIST OF APPENDICES (Continued)
19 X-ray diffraction pattern for sample

TS1-3A 264

TS3-C 265

TS6-ED 266
22 WATEQDR ion activity calculations for

gypsum, sample G-25 267
23 WATEQDR ion activity calculations for

ettringite, sample ET-25C 269
1
CHAPTER 1
INTRODUCTION
Lime treatment of clay-bearing soils has been in common
use as an effective means of stabilizing low-strength roadway
subgrade for over 40 years. The procedure involves thoroughly
mixing fine-grained native soils with 3-10 weight percent
hydrous (Ca(OH)2) or anhydrous (CaO) lime. stabilization
proceeds through a combination of four mechanisms, three of
which are chemical reactions directly involving clay minerals
in the soil. A fourth reaction mechanism combines calcium from
lime with carbon dioxide in the water and atmosphere to form
calcium carbonate.
When the ideal lime-soil-water mixture is properly mixed
and compacted, increase in subgrade strength is dramatic. In
addition, the shrink-swell potential of any high plastic,
expansive clays in the soil is virtually eliminated. The rate
of strength increase is rapid at first and then declines. The
net result is a continued increase in strength that approaches
some maximum value asymptotically for the life of the pavement
structure. This maximum is a function of lime content, clay
mineralogy, soil chemistry, moisture, and temperature.
Lime treatment has not always produced the dramatic
stabilization anticipated or even necessary for adequate

2
performance of the pavement system. Under certain conditions
failure occurs through heave induced by reaction between lime
and soluble sulfate in the treated soil (SEA INC., 1983;
Mitchell, 1986; Hunter, 1988). In 1975, a 2.75 mile section
of Stewart Avenue in Las Vegas, Nevada, was reconstructed and
improved to a 100-foot right-of-way. Three years later Owens
Avenue, parallel to and one mile north of Stewart, was also
reconstructed. Both roadways incorporated lime-treated subbase
into their pavement structural sections using 4.5 weight
percent quicklime (CaO). Within one year of completion, both
Stewart Avenue and Owens Avenue began showing major signs of
distress. Over the next few years, the damage steadily
increased, particularly along Stewart Avenue. This distress
included severe cracking and bulging of asphaltic concrete
pavement (Figure 1) as well as cracking and uplift of concrete
medians (Figure 2). Sidewalks were generally undamaged but did
not overlie lime-treated soil. Along Stewart Avenue bulges in
the pavement often reached a height of 12 inches above adjacent
areas of pavement. At Owens Avenue the maximum magnitude of
the heave is approximately 8 inches.
The original 1975 cost to widen and improve Stewart Avenue
was approximately 1.4 million dollars. Two thirds of the
pavement section was reconstructed in 1985 at a cost of 2.7
million dollars. The worst areas of Owens Street have been
repaired; however, it has not yet been reconstructed. Recent

3
Figure 1 View west along Stewart Ave. from test pit

S-7 Heave in this area exceeded 12 Inches. Note
6 inch wide crack in pavement.
Figure 2 View north along Stewart Awe., just east of
Mojave Blvd. Concrete median has heaved over 6 inches.
5
reevaluation (SEA INC., 1988) indicates that the Owens Avenue
distress has become more extensive since 1983.
Forensic investigations by three consultants, including
the soils engineer responsible for the design, were
inconclusive and conflicting. The reported cause of heave
ranged from expansive clay to growth of gypsum induced from
chemical reactions between lime and sulfate in the native soil.
Without a thorough understanding of the distress mechanism, it
was impossible to evaluate the potential for further damage and
make appropriate geotechnical or legal recommendations. In
1982 SEA Engineering, Inc., contracted with the City of Las
Vegas to perform a geotechnical investigation of Stewart
Avenue. The objective was to establish the cause of the
distress and make recommendations for reconstruction or salvage
of the roadway. During that study it was found that the heave
resulted from lime-induced growth of thaumasite, a rare
hydrated calcium-silicate-carbonate-sulfate mineral.
Thaumasite forms a complex solid solution series with
ettringite, a hydrated calcium-aluminum sulfate mineral. Under
the geochemical conditions of Stewart Avenue ettringite
probably grew first and later converted to thaumasite.
The SEA investigation (conducted by this writer in 1982-
1983), and the many questions it necessarily left unanswered,
form the basis for this dissertation. During the SEA study an
extensive literature review found no published cases of lime

6
induced heave and few laboratory studies that considered the
effects of sulfate on lime-treated soil. Telephone
conversations with highway departments in the Western United
States, however, indicated that the problem was not unique.
Since this dissertation was initiated, and an interim
publication completed (Hunter, 1988), other major occurrences
of lime-induced heave have been documented. Problem areas have
included Southern California; Wichita, Kansas; Interstate
Highway 70, Grand County, Utah; U.S. Highway 10, Texas;
Davidson County, Tennessee, and even a warehouse foundation and
floor slab in Paris, France. Experiments performed as a part
of this research have demonstrated the potential for this
problem in many other areas.
In 1985, James K. Mitchell presented a lecture to the
American Society of Civil Engineers as the invited speaker for
the Twentieth Annual Terzaghi Lecture. This prestigious
lecture is in honor of Karl Terzaghi (deceased) who is
generally recognized as the father of modern soil mechanics.
In this lecture, entitled "Practical Problems from Surprising
Soil Behavior," Professor Mitchell discussed four newly
recognized and surprising problems related to geotechnical
engineering. One of the surprises involved the lime-related
distress on Stewart Avenue in Las Vegas, Nevada. The lecture,
which was later published (Mitchell, 1986), was the first
mention of the phenomenon in U.S. literature. The paper
correctly diagnosed the cause of the distress as being growth

7
of ettringite and thaumasite, but recognized that much
additional research would be needed to learn where, why, and
how the problem can occur.
The overall objective of this dissertation was to develop
a detailed understanding of the geochemical mechanism of
ettringite/thaumasite growth in lime-treated soils. Clearly
there is scientific need for this information in that, as
Professor Mitchell pointed out, it is one of the newly
recognized mysteries in soil mechanics. From a practical
standpoint, the need is even more apparent. Lime treatment of
Stewart Avenue saved, perhaps, $300,000 in initial costs over
other techniques commonly used to stabilize clay roadway
subgrade. Subsequent evaluation, repairs, and reconstruction
necessitated by the swelling reactions, however, cost the City
of Las Vegas nearly ten times that amount. It was expected
that the understandings gained from this research could be
applied to other soils in other areas to prevent similar costly
mistakes. Although lime treatment of clays containing any
sulfate could simply be avoided, this would preclude many soils
that respond well to the technique. As a consequence, the
potential cost benefits of lime stabilization would be
sacrificed out of fear rather than on the basis of sound
technical judgement.
The dissertation research can be divided into three main
segments, beginning with a thorough review of published, and

8
other available, literature on lime stabilization. The review
considered the geochemistry of lime/soil reactions, design of
lime stabilized pavement sections and construction methods.
Detailed case histories of Stewart and Owens Avenue were also
provided. Other cases of lime-induced heave were uncovered and
described, demonstrating the widespread nature of the problem.
The physio/chemical mechanism by which ettringite/
thaumasite causes swelling in lime treated soils is detailed
in the second segment. The evaluation involved experiments to
duplicate the swelling in the laboratory and measure the
maximum volume change and pressure generated by the mineral
growth. Mass volume relationships were analyzed confirming
that the in situ sulfate was, at best, capable of generating
only one-half of the heave observed in the field. Mass flux
estimations were developed to verify that sufficient sulfate
and other ions could reach the system within the observed time
frame. On the basis of the overall analysis, a series of
stepped equilibrium reactions were proposed to describe the
geochemical changes in the soil system that result in
precipitation of ettringite/thaumasite.
The final segment of the research involved determination
of the solubility thermodynamics of ettringite. Under most
conditions ettringite probably occurs first, and in the
presence of carbonate and at temperature below 15 C, slowly
converts to thaumasite. Solubility determinations required

9
synthesis of ettringite. Although this has been performed by
previous researchers, synthesis of ettringite pure enough for
thermodynamic work is difficult and required considerable
experimentation. The solubility study was used to calculate
the dissociation (equilibrium) constant, standard state Gibbs
free energy, enthalpy, entropy, and heat capacity for
ettringite. These data, which were not available prior to this
research, were used to generate phase diagrams depicting
geochemical conditions under which ettringite becomes the
stable phase. Such diagrams are the basis for making an
educated evaluation of the potential for a given soil to be
damaged by lime-induced heave.

10
CHAPTER 2
THEORY AND PRACTICE IN
LIME STABILIZATION OF CLAY SUBGRADES
Lime stabilization of roadway subgrades has become common
engineering practice, particularly during the last 25 years.
The relatively simple procedure can be performed with readily
available construction equipment and greatly improves the load-
bearing capacity of certain soils. As a consequence,
thicknesses of the more expensive pavement components,
asphaltic or Portland cement concrete and crushed aggregate
base, can be significantly reduced. Although lime treatment
is expensive, reductions in pavement and base, in many cases,
more than offset the cost of stabilization. The net result is
an economical alternative to increasing the thickness of the
structural section to compensate for weak or expansive subgrade
soils. Lime treatment can also be an effective solution where
existing utility lines preclude increasing the thickness
(depth) of the structural section. This was partially the case
for reconstruction of Stewart Avenue in Las Vegas.
Lime treatment modifies the physical characteristics of
clay-rich soils in a variety of ways and to varied degrees.
These changes are summarized below (National Lime Association,
1976) :
11
1. Decrease plastic index as much as fourfold. This
occurs through an increase in liquid limit and
decrease in plastic limit.
2. The soil is agglomerated, i.e., the percentage of
particles passing the No. 40 mesh sieve are
substantially decreased.
3. Accelerates the breakdown of clay clods increasing
the soils workability.
4. Aids in drying out wet soils— particularly when
anhydrous (quicklime) is used.
5. Greatly reduces the shrink-swell characteristics of
expansive clays thereby minimizing the potential for
heave or settlement.
6. Greatly increases the unconfined compressive strength
of the soil. In some cases lime-treated soils have
forty (40) times the unconfined compressive strength
of untreated soils.
7. Load bearing capacity, as measured, by various tests,
increases substantially. For example, R-values
(ASTM D 2844) often increase by a factor of ten (10) .

12
8. The stabilized material develops significant tensile
strength which is a critical factor in pavement
performance.
9. Forms an impermeable horizon that resists penetration
of gravity water from above and capillary water from
below.
10. Provides a stable working base and prevents pumping
of soft, underlying subgrade.
HISTORICAL BACKGROUND
Lime treatment was used early in man's history to improve
a soils workability and potential for cultivation (Eades and
Grim, 1960). Lime stabilization of clay soils dates back, at
least, several thousand years to roadways constructed by the
Roman Empire (McDowell, 1959). Since the end of World War II,
lime stabilization has been used throughout this country and
the world with increasing regularity.
As commonly happens, the technique was put into practice
long before its physio-chemical mechanisms were understood, or
even of concern. Some of the earliest, modern, lime
stabilization projects involved reconstruction of paved parking
lots and roadways on military bases in Arkansas, Louisiana, New
Mexico, Oklahoma, and Texas during the late 1940's. A follow

13
up investigation conducted 25 years later demonstrated the long
range durability of the procedure (Kelley, 1977).
Not all of the early attempts at lime stabilization were
successful, however (Taylor and Arman, 1960). It was likely
the failures rather than the successes that brought lime
stabilization to the attention of the engineering and academic
communities. The years from approximately 1959 through 1976
saw a tremendous surge of research and development in the field
of soil stabilization. State highway departments throughout
most of the United States as well as the Federal Highway
Administration and Army Corps of Engineers became involved in
laboratory experiments, test sections, and major lime
stabilization projects. Often this work was conducted in
collaboration with local universities. As a consequence of
these efforts, we now have a reasonably good understanding of
normal lime-soil reactions.
In the past decade, there has been relatively little
research in lime stabilization. There have also been very few
pavement failures that were not the direct result of poor
workmanship during construction. The most remarkable
exceptions are Stewart Avenue and Owens Avenue in Las Veg a s ,
Nevada. Both of these pavements were badly damaged by adverse
chemical reactions between lime and salts in the native soils
(SEA INC., 1983, Mitchell, 1986; Hunter, 1988).

14
THE CHEMISTRY OF NORMAL LIME/SOIL REACTIONS
Stabilization using pure lime is generally restricted to
soils with a moderately high content of clay minerals. In
addition to increasing the bearing strength, lime treatment
decreases the plastic index of the soils, greatly reducing the
shrink-swell characteristics of high plastic clays. Fine
grained soils with low clay content are better stabilized with
lime-fly ash mixtures or Portland cement.
Lime is a rather broad term for a variety of calcium
bearing compounds used in soil stabilization, cement, and
numerous other products. Pure lime is available in either
hydrated (Ca(OH)2) or anhydrous (CaO) form. Anhydrous lime is
commonly called quicklime. In the United Stats, hydrated lime
tends to be favored, largely because it is a safer compound to
work with. Quicklime is generally used in Europe and offers
several advantages. Chemically, quicklime has approximately
25% more available reactant (CaO) than hydrated lime so that
3% quicklime is as effective as 4% hydrated lime. The
significant advantage lies in lower transportation costs— an
important consideration on-large scale projects. In addition,
the reaction of quicklime with water:
CaO + H20 = Ca(OH)2

15
is spontaneous and strongly exothermic. This is useful in
drying wet soils and for working at near-freezing temperatures.
Heat from this reaction also accelerates the various other
reactions involved in stabilizing soil.
The major disadvantages of quicklime are its higher cost
per ton and its highly caustic nature. Application of
pulverized quicklime during hot, humid, windy conditions is a
significant hazard and should be avoided.
Reagent grade lime is not used in construction for obvious
reasons of cost. Commercial grade, high-calcium lime typically
contains a minimum available lime (CaO) of 90%. High dolomitic
quicklime containing at least, 95% total oxides (MgO + CaO) is
also available. A high calcium quicklime with 94% available
CaO was used on Stewart Avenue and Owens Avenue.
Numerous additives have been tried with lime in attempts
to improve its properties of stabilization. The most commonly
used additive is fly ash, however, virtually every reasonably
common salt, oxide, or silicate has been researched (California
Division of Highways, 1967).
Stabilization of lime treated soils occurs through a
combination of four mechanisms (Thompson, 1966):

16
1. Cation exchange
2. Flocculation/Agglomeration
3. Carbonatation
4. Pozzolanic reactions
The first two increase soil workability and are the result of
changes in the electrical charges of the clay minerals. The
second two mechanisms involve cementation reactions which
generate the stabilization and conseguent increase in bearing
strength.
Cation Exchange
The common clay minerals are comprised of alternating
sheets of ions of two basic types. The octahedral or gibbsite
sheet consists of the anions 02' and OH' in octahedral
coordination around Al3+. The second layer, known as the
tetrahedral or silica sheet, is made up of 02' and OH' in
tetrahedral coordination around Si‘

,+.
Two layer clays, such as kaolinite, consist of a
repetition of a combined octahedral and tetrahedral sheet unit
cell (Figure 3). Such clays are held together by Van der Waals
forces acting between the unit cells. The attraction is
relatively strong so that the silica-gibbsite unit cells do not
readily separate from one another. As a consequence, two layer
clays do not absorb large amounts of water between the layers

18
and are not expansive. In addition, cations are not easily
absorbed between the layers so their cation exchange capacity
is very low (Grim, 1968 Berner, 1971).
Unit cells in three layer clays, such as the smectite
(montmorilIonite) group, consist of octahedral sheets
sandwiched between two tetrahedral sheets, as shown in Figure
4. Again, the structural units are bonded by Van der Waals
forces. In this case, however, the attraction between two
tetrahedral layers is less than that between the octahedral
sheet and silica sheet observed in kaolinite. In addition,
with montmorillonite, there is some substitution of Al3+ for Si4+
in the tetrahedral sheet and considerable substitution of Mg2+
for Al3+ in the octahedral sheet. This results in a large net
negative charge which is balanced, to some extent, by
absorption of cations between each unit cell. Since these
cations are loosely held, they are readily replaced by other
cations with more favorable bonding characteristics (Lambe and
Whitman, 1969). Typically, the order of exchange is
Na+ < K+ < Ca2+ < Mg2+ where each cation will tend to replace any
to its left (Thompson, 1966). Because water is a polar
molecule, it is also easily absorbed between the unit cells of
montmorillonite. This gives rise to the shrink-swell
characteristics of certain clay minerals, particularly
montmorillonite and vermiculite.

19
20
The cation exchange capacity of two layer clays is
relatively low while that of three layer clays, particularly
the smectites, is quite high (Grim, 1968; Berner, 1971). As
a consequence, the benefits of cation exchange in lime treated
soils are far more dramatic in expansive clays. In these
clays, divalent calcium ions typically replace monovalent
sodium or potassium ions in the interlayer positions. This
results in much stronger bonding between the unit cells and a
remarkable drop in the soils shrink-swell characteristics. The
cation exchange process is generally complete within 24 hours,
however, significant improvement is immediately apparent. Two
layer clays are generally lime-treated only to increase bearing
strength since they are not severally expansive.
In "real world" soils, the situation is somewhat more
complicated since pure, well-ordered clay minerals are not
common. More often, the clays are of "mixed layer" structure
consisting of random or orderly alternations of various two-
or three-layer unit cell types. The behavior of lime treated
soils is, therefore, difficult to predict from simple tests of
cation exchange capacity. Test specimens mixed, molded, and
cured are normally required.
Flocculation/Aaalomeration
All soil particles carry a net electrical charge. In
theory this charge can be either positive or negative, however,

21
only negative charges have been measured. By virtue of their
small size (less than 0.002 mm), clay minerals have a high
specific surface and hence, a high net charge. Although other
factors are involved, this negative charge is largely the
result of isomorphous substitution within the crystal lattice.
Typically this consists of Al3+ replacing Si4+ or Mg2+ replacing
Al3+.. The clay particle then attracts loosely bonded,
exchangeable cations to neutralize the net charge (Lambe and
Whitman, 1969). The result is an electrical double layer
consisting of a negatively charged surface surrounded by a
diffuse cloud of cations. The structure of this double layer
has been modelled mathematically and is thought to consist of
a fixed layer of cations essentially attached to the solid
surface and a diffuse layer in which the ions are free to move.
The inner, fixed layer is known as the Stern layer while the
diffuse cations lie within the Gouy layer (Figure 5).
When two clay particles approach they are repelled from
one another by the like charges of their Gouy layers. When the
ionic strength of the pore water is increased, as happens with
lime treatment, the Gouy layer is compressed, closer to the
solid surface. The electrostatic repulsion keeping the
particles apart is then no longer sufficient to counteract the
Van der Waals forces which tend to bring them together (Drever,
1982). As a result, the clay minerals flocculate forming
agglomerations of particles and a net increase in the effective
grain size of the soil.

22
Layer of
fixed
cations Diffuse layer
Stern Gouy
Figure 5 Diagrammatic representation of the fixed (stern)

and diffuse (Gouy) layers. (Source: Drever, 1982, p. 80.)
23
In reality, the mechanisms of flocculation/agglomeration
are extremely complex and, perhaps, the least understood
component of lime stabilization.
Carbonation
Reactions between calcium (or magnesium) and carbon
dioxide are the lesser of the two groups of cementation type
reactions involved in lime stabilization. The reaction
proceeds through one of the most common and best understood
mechanisms in geochemistry:
C02 + H20 = H2C03
H2C03 = 2H+ + C032' (at pH > 10.5)
Ca2+ + C032' + 2H+ + 2 (OH)* = CaC03 + 2H20
In this case both calcium and hydroxyl ions are supplied by the
dissolution of lime:
Ca(0H)2 = Ca2+ + 2 (O H )"
Carbon dioxide is available directly from the atmosphere, from
C02 dissolved in water added to the soil-lime mixture and from
biogenic C02 present in the soil itself.

24
In reality, calcium carbonate cementation is simply an
unavoidable by-product of the lime-soil-water system and not
altogether desirable. Calcium tied up in calcite is
unavailable for the pozzolanic reactions that produce a
considerably stronger cementing agent (Mateos, 1965; Thompson,
1966; Zube, et. a l . , 1966). Laboratory tests with lime-treated
bentonite cured in a vacuum have shown a 68% increase in 28-
day unconfined compressive strength compared to specimens cured
in a C02 saturated atmosphere (Mateos, 1965). Indeed, care
must be taken in the storage of lime to prevent carbonation
and decrease of reactivity.
Pozzolanic Reactions
By definition (ASTM C-593-762) a pozzolan is "a siliceous
or alumino-siliceous material that in itself possesses little
or no cementitious value but that in finely divided form and
in the presence of moisture will chemically react with alkali
and alkaline earth hydroxides at ordinary temperatures to form
or assist in forming compounds possessing cementitious
properties." Pozzolanic recations are the major sources of the
cementation and are the dominant factor in stabilization and
increased strength in lime treated soils (Thompson, 1966).
Research has demonstrated that significant pozzolanic
reactions may not occur until enough lime is added to satisfy
the potential for cation exchange and flocculation/

25
agglomeration reactions (Taylor and Arman, 1960; Hilt and
Davidson, 1960). This natural affinity of the soil for calcium
ions is termed lime fixation. Lime fixation is a function of
clay mineralogy and grain size (Hilt and Davidson, 1960).
Once the soil is sufficiently saturated with lime, the pH
of the soil-water system stabilizes at 12.3. This value
exceeds any known in nature and is sufficiently high that
silica becomes extremely soluble (Krauskopf, 1979). Silica
solubility is strongly affected by both temperature and pH
(Barnes, 1980). At surface temperatures, however, pH is the
dominant factor. More recent research has demonstrated that
silica solubility also increases in the presence of various
salts (Fournier, 1983). In all cases, silica is thought to
dissolve through the following series of stepped reactions:
Si02 + 2H20 = H4Si04 ; log K, = -3.8
H4Si04 = H+ + H3Si04" ; log K2 = -9.9
H3Si04 = H+ + H2Si042- ; log K3 = -11.7
At a pH of 12.3, H2Si04" is the dominate species. Most natural
waters have a pH between 6 and 9. From pH 2 to 8, the
solubility of quartz (Si02) and silica gel (Si02) remain nearly
constant at, approximately, 6 ppm and 120 ppm respectively.
Solubility of both forms of silica increases exponentially
above a pH equal to 8.5. At pH 12.3, silica solubility is
quite high (Figure 6).

26
The solubility of aluminum is also largely controlled by
pH, however, the behavior is somewhat more complex than that
of silica. Nevertheless, at high pH levels, the solubility of
aluminum also becomes relatively high (Figure 7).
Lime stabilization research has shown that clay minerals
become unstable and begin to deteriorate at pH levels above
10.5 (Eades and Grim, 1960; Davidson, Demirel and Handy, 1966).
The breakdown of these clays provides the siliceous and
aluminous pozzolans for reaction with calcium (Thompson, 1965).
Lime stabilization of clay-poor soils has been effectively
accomplished by adding fly ash or volcanic ash (pozzolanic
materials) to the lime-soil mixture (California Division of
Highways, 1967). Portland and other hydraulic cements
typically consist of pozzolanic material and a few minor
additives. As a consequence, the basic chemistry of the
reactions involved in lime and hydraulic cement are very
similar.
When calcium reacts with silicon and/or aluminum at high
pH, numerous compounds form (Taylor, 1964). In general they
are difficult to study since they are present in small amounts
relative to the mass of the soil. In addition, most of the
compounds are initially amorphous and become more crystalline
through aging or increased temperature. The combination of
small mass and lack of an ordered internal crystal structure

2 4 6 8 10 12 14
PH
Figure 6 Activities of dissolved silica species in equilibrium with quartz at 25 C.
(Source: Drever, 1982, p. 92)
with gibbsite at 25 C. (Source: Drever, 1982, p. 95.)
makes the compounds difficult to identify since they are not
easily recognized by x-ray diffraction.
The most commonly cited pozzolanic reaction product is a
complex hydrated calcium silicate (Taylor, 1964; Ruff and
Clara, 1966). Its formation in lime-treated soils can be
represented by the following series of stepped reactions:
5CaO + 5H20 = 5Ca(OH)2
5Ca (OH) 2 = 5Ca2+ + 10 (0H‘)
Clay minerals = 6H3Si04‘ + 6H* (at pH 12.3)
/ /
5Ca2+ + 6H3Si04" + 10 (OH') + 6H+ = Ca5(Si018H2) • 4H20 + 12H20
The compound is chemically similar to the mineral tobermorite,
however, tobermorite is fully crystalline. The semi
crystalline "tobermorite-like" compound is generally considered
to be the main cementing agent in both lime and cement treated
soils and in concrete (Taylor, 1964; Ruff and Clara, 1966).
The compound forms as a gel and actually goes through several
transitions with increasing crystallinity (Ruff and Clara,
1966) ;
CSH(gel) = CSH (II) = CSH(I)
where CSH abbreviates calcium-silicate-hydrate. This slow
transition from gel to semi-crystalline accounts for the steady

30
strength increase of concrete and cement or lime treated soils
that continues for many years.
Numerous other hydrous calcium-silicate, calcium-
aluminate, and calcium-aluminum-silicate compounds have been
identified in lime or cement treated soils and concrete
(Taylor, 1964; Ruff and Clara, 1966).
DF.SIGN OF LIME STABILIZED SUBBASE FOR PAVEMENTS
Over the years, many laboratory test methods have been
employed to evaluate the strength and load bearing capacity of
lime treated soils. These have ranged from simple methods
involving only the plastic index of the soil (McDowell, 1966,
1972) to elaborate schemes of triaxial shear testing (Taylor
and Arman, 1960). The most commonly used test procedure,
however, has been unconfined shear strength of test cylinders
molded under various conditions. All of these tests, however,
have serious limitations in that they are not routinely used
to evaluate subgrade strength of pavement design. Most modern
design methods use Resistance (R) value testing (ASTM D-2844)
as the measure of subgrade strength for asphaltic pavements and
K values (modulus of subgrade reaction) for Portland cement
pavements. Since K-value testing (ASTM D-1196) is a rather
arduous field chore, K—values are usually approximated from
R-values which are easily measured in the laboratory.

31
In the R-value test, 2 1/2-inch high, 4-inch diameter soil
samples are compacted in a metal mold using a kneading
compactor. The R-value is determined from a combination of the
pressure at which water exudates from the sample under a
specific uniaxial load and a modified measure of its triaxial
shear strength. The test is normally run at 3 or more moisture
contents and the R-value arbitrarily assigned to be that
occurring at an exudation pressure of 300 psi. R-value testing
can also be conducted with different percentages of lime mixed
with the soil to determine the weight percent lime needed for
adequate stabilization. Since the test is generally completed
within a 48-hour period, increases in R-value do not reflect
all of the longer term pozzolonic reactions so important to the
stabilization process. Even so, weak clay soils with initial
R-values on the order of 5 usually show increases to the 50 to
60 range (California Department of Transportation, 1976). Such
values would be typical for silty sands and gravelly sands— a
significant strength increase.
Unfortunately, none of the test methods commonly used for
evaluating lime-treated subbase would indicate the potential
for lime induced heave. Such tests normally last only a few
days. In most cases, weeks or months might be required before
any distress becomes apparent.

32
BASIC CONSTRUCTION METHODS
The basic steps of lime stabilization involve
scarification, partial pulverization, lime spreading, mixing,
curing and compaction. This can be accomplished satisfactorily
by a variety of methods, however, specialized equipment is
preferred for major projects.
For small-scale projects the lime is often mixed in place.
The subgrade is thoroughly scarified to the appropriate depth
with rippers on a grader or bulldozer. The lime can then be
spread out from bags in the required amount and mixed with the
soil by further scarification. During mixing, water is added
to raise the moisture of the soil-lime mixture to at least five
percent (5%) over optimum for hydrated lime (Ca(OH2) and even
higher for quicklime (CaO). The treated soil is then cured for
24 to 48 hours prior to compaction. This allows the cation
exchange and flocculation/agglomeration reactions to occur,
greatly improving the soil's response to compactive effort.
The curing period is sometimes extended to as much as seven
days for highly expansive clays.
In larger projects, the initial scarification is generally
performed with a disc harrow and the lime brought in bulk
trucks, rather than bags. Since thorough mixing of lime and
soil is crucial to the process, it is generally preferable to
further pulverize and blend the materials with a rotary mixer.

33
For projects requiring the maximum possible stabilization, a
two-step application of the lime is commonly used. In the
first application, approximately one-half of the required
percentage of lime is thoroughly mixed with water and the soil.
Following a curing period of approximately one week, the
remaining lime is added. The first treatment preconditions the
soil making it much easier to mix and compact with the
remaining lime. The second application supplies the lime for
the major stabilizing pozzolanic reactions (National Lime
Association, 1976).
Numerous variations in the methodology have been tried.
In all cases, the most critical factors are thoroughness of
mixing, proper moisture conditioning, curing time and
compaction. Lime treated soils are generally densified to
either ninety or ninety-five percent (90-95%) compaction
relative to ASTM D-1557-78).

34
CHAPTER 3
LIME-INDUCED HEAVE OF SULFATE BEARING CLAY SOILS:
CASE HISTORIES OF STEWART AVENUE AND OWENS AVENUE
LAS VEGAS, NEVADA
SITE CONDITIONS
Stewart Avenue
Stewart Avenue is a major east/west trending roadway
through downtown Las Vegas. The section covered by this
investigation extends approximately 2.75 miles (4.44 km)
eastward from 28th Street to Nellis Boulevard (Figure 8). The
street includes four twelve-foot (3.66 m) traffic lanes, two
parking lanes, and a concrete or asphalt median. Left turning
lanes have been provided at all intersections.
As designed and constructed in 1976, Stewart Avenue used
two separate structural sections. Between 28th Street and
Pecos Road four inches (10.2 cm) of asphaltic concrete, five
inches (12.7 cm) of Type II aggregate base, and a twelve-inch
(30.5 cm) thickness of lime-treated native soil (subbase) were
required. From Pecos eastward to Nellis Boulevard, the

NELLIS I BLVD.
35
36
aggregate base thickness was increased to eight inches
(20.3 c m ).
The Stewart Avenue distress consisted of severely damaged
asphaltic pavement, concrete and asphalt medians, as well as
occasional curbs and gutters. Damage to sidewalks, which were
not intentionally lime treated, was rare. The most badly
damaged asphalt pavement occurred between Mojave Boulevard and
Pecos Road. In this area a major ridge paralleled the roadway
in the south parking lane (refer to Figure 1). The ridge rose
as much as twelve inches (30.5 cm) above the adjacent pavement
and ranged from one to two feet (30.5 to 61 cm) in width.
Often the adjacent pavement had also been heaved so that the
maximum uplift was hard to gauge. The ridges generally
displayed large fractures in the asphalt— typically one to
three inches (2.5 to 7.5 cm) in width.
The remaining asphaltic pavement and medians between
Mojave and Pecos showed extensive damage with the pavement
exhibiting a generally uplifted and undulating surface.
Concrete median slabs were displaced three to six inches (7.5
to 15.2 cm) (refer to Figure 2). From 28th Street to Mojave
and from Pecos to Sandhill the distress was very similar in
form but of a somewhat lower magnitude. Damage was
predominately in the median and on the south of the street.

37
Between Sandhill and Lamb Boulevard the heaving was
generally confined to isolated areas on the south side of
Stewart or in the median. East of Lamb damage became more
isolated but occurred on both sides of the street as well as
in the median.
In 1986 the area of Stewart Avenue between 28th Street
and Lamb Boulevard was reconstructed, without lime stabil
ization. Damaged areas east of Lamb Boulevard were repaired.
Owens Avenue
Owens Avenue was reconstructed between Eastern Avenue and
Pecos Road in 1978 (refer to Figure 8). This segment
incorporated an eight-inch (20.3 cm) lime treated base which
was directly overlain by ten inches (25.4 cm) of asphaltic
concrete.
Distress along Owens Avenue is similar in form to that
of Stewart Avenue but of a considerably lesser magnitude.
Maximum heave along linear ridges is six to eight inches (15.2
to 20.3 cm). The ridges are also less continuous than at
Stewart Avenue and occur about equally on both sides of the
street. The majority of the roadway is undamaged or only

38
slightly damaged, often limited to cracking of the pavement.
No displacement of sidewalks, curbs, or gutters was observed,
however, damage to the median is common. A photograph typical
of the Owens Avenue distress is presented as Figure 9. As of
late 1988 the roadway had not been reconstructed. Some repair
work, however, has been performed in the most seriously
damaged areas. A follow-up study (SE&A, Inc., 1988) showed
that the aerial extent of the damage has increased since 1983.
GEOLOGY AND SOIL CONDITIONS
General Geology
The Stewart Avenue and Owens Avenue alignments lie on the
eastern side of the Las Vegas Valley in an area of thick basin
fill sediments. These materials typically consist of fine
grained sandy silts and sandy clays originally deposited in
marshy or playa environments during the Plio-Pleistocene
(Bell, 1981, Mifflin and Wheat, 1979). The deposits were
derived from a variety of source rocks which, for the most
part, are dominated by carbonates. Some of the source areas
contain abundant bedded gypsum and possibly other evaporites.
A considerable sequence of undifferentiated, Tertiary volcanic
rocks lie along the southeast rim of the basin (Longwell, et
al, 1962).
40
Project Soil Conditions
A generalized soils map of the area has been included as
Figure 10. Soils underlying the two roadways are of Recent
Age, derived from reworking of the older basin fills by
drainages along the Las Vegas Wash (Dinger, 1977). They are
poorly to slightly stratified and, on a gross scale, fairly
homogeneous. On a much finer scale, they are complexly
interbedded and contain areas with significant differences in
engineering and chemical properties. Dinger (1977) used
groundwater chemistry to divide the Las Vegas Valley into
carbonate and sulfate geochemical lithofacies. Stewart Avenue
and Owens Avenue both lie in the sulfate lithofacies, slightly
east of the boundary with the carbonate lithofacies.
The soils in the project area contain abundant soluble
salts indicative of playa environments. In most soil samples,
salts were visible to the unaided eye. The upper soils unit
typically consists of moist, slightly stiff to stiff, brown
to tan, low plastic sandy clay or sandy silt with seventy to
ninety percent (70-90%) fines. Thickness of this horizon
varies from three-and-one-half feet (106.6 cm) to over eight-
and-one-half feet (259.1 cm).

N ellis Blvd
(Source: USDA, 1967.)
DESCRIPTIONS OF SOIL UNITS
r,M^ araîsc siIt loani> drained, slightly saline (Pa)— proved by means of drainage ditches and by pumping
Uns soil occurs as a small area in the central part of Las ground water. RunolT is very slow. Permeability is me
Vegas valley. It adjoins and extends into the city of dium as far down as the hardpan and slow through the
Las Vegas. pan. I ho inherent fertility and the water-holding capac
Representative profile: ity arc high. The erosion hazard is slight.
Surface soil— I(or tho most part, this soil is under natural vegeta
0 to 2 inches, clark-gniy silt loam; weak, medium to fine,
granular structure; slightly hard when dry, friable when tion. If irrigated and properly managed, it would he
moist; p I [ S.4.
2 to 7 inches, gray loam; massive; hard when dry, friable
well suited to crops. It would need fertilizer containing
when moist; p ll S.4. nitrogen and phosphorus, even though its surface soil is
Subsoil— high in organic matter. Also, it would need deep leaching
7 to 14 indies, lifiht-gray silt loam; massive; slightly hard
when dry, friable when moist; p lf 8.2. and drainage to remove the excess salts. The slow perme
14 to 31 inches, light-gray silt loam; massive; slightly hard ability of the hardpan and the pressure of artesian water
when dry, friable when moist; pH 8.2. are likely to interfere with tho installation of an artificial
Substratum—
31 to 52 inches + , white, weakly lime cemented silt loam;
drainage system. Irrigation, unless carefully controlled,
m any extremely firm lime nodules; massive; very hard is likely to result in a perched water tabic above the
when dry, firm when moist; p it 8.4. hardpan, waterlogging of the soil above tho hardpan,
The thickness of the surface soil ranges from 2 to 12 and accumulation of excess salts in the surface layer.
inches, depending on the amount of leveling. The depth The surface soil and subsoil have severe to very severe
(o the lime-cemented horizon ranges from 21 to more limitations as foundation-bearing material; the substra
than GO inches. This horizon is several feet thick in tum has moderate limitations. The shrink-swell potential
spots and is harder and more cemented with increasing is moderate to high, depending on the sodium sulfate
depth. & concent ration. (Capability unit IIw-G)
Tho natural drainage was poor, but it has been im
Figure 10b Generalized soils map for the S tew art/O w ens Ave. area.
DESCRIPTIONS OF SOIL UNITS
Glendale silt loam, slightly saline (Gf).—This soil Land silty clay loam, wet, strongly saline (|_h).—This
occurs as large'tracts in ah area that extends along Las soil occurs mainly in Las Vegas Wash. Excess water
Vegas Wash from a point east of Las Vegas northeastward from the sewage disposal plant has seeped into the soil
toward Nellis Air Force Base. and raised the water table, and the soil is saturated
[Representative profile: at a depth of 2 to 3 feet. All of this soil is in natural
Surface soil— vegetation. It is unsuitable for cultivation and is best
0 to 5 inches, pink silt loam ; moderate, medium to coarse,
platy structure; slightly hard when dry, friable when used as native pasture. No attempt should be made
moist; pH 9.0. to cultivate it or to alter the native vegetation. The
Subsoil and substratum — forage is adequate for grazing but could be improved
5 to GO inches + , very similar to the surface soil, but stratified
w ith either slightly finer textured or slightly coarser
by water spreading. (Capability unit VIw-36)
textured m aterial; massive; pH S.4.
The color ranges from pink to very pale brown. The
texture of the strata in the subsoil and substratum ranges
from fine sandy loam to light silty clay loam, and the
strata vary in thickness and in amount of deposition. Land very fine sandy loam, wet, strongly saline (Ln).-—
There is some mica in the profile and, in most places, This soil occurs at the lower extremities of Las Vegas Wash,
some gypsum. where a geologic barrier..forces ground water upward
Natural drainage is good, runoff is slow', permeability into the soil profile. It is saturated below a-depth of
is moderately slow, and infiltration is slow. Both the 12 inches during most of the year. In winter the -water
water-holding capacity and the natural fertility are high. table is likely to rise to the surface, and the soil becomes
This soil is poor or unsuitable for most engineering swampy. It is unlikely that this soil could be leached
purposes. The shrink-swell potential is low to high, de of excess salts unless it is drained. The native vegetation
pending upon the concentration of sodium sulfate salts. should be maintained. Preferably, it should be used as
The sulfate hazard to concrete is severe. (Capability unit food and cover for wildlife, but it would provide some
I-A) ' forage for livestock. (Capability unit VlIw-6)
Figure 10c Generalized soils map for the S tew art/O w ens Ave. area.
U)
44
The upper horizon grades downward into a white to gray,
gravelly sandy clay. Because the test pits were generally
shallow this horizon was not frequently observed. The clay
shows a definite increase in calcium carbonate, however, a
hard caliche layer was not encountered during exploration.
A lens containing up to fifty percent (50%) gypsum and
approximately two feet (61.0 cm) in thickness was encountered
on Stewart Avenue near Mojave Road.
EXPLORATION
Thirty-four test pits and three borings were placed along
Stewart Avenue. Six test pits were excavated along Owens
Avenue. The location of each Stewart Avenue test pit and
boring is shown on Figure 11, while those of Owens Avenue are
presented on Figure 12. Test pits typically ranged from three
to four-and-one-half feet (91.4 to 137.2 cm) deep and reached
a maximum depth of eight-and-one-half feet (259.1 cm) on
Stewart Avenue just east of Mojave Road. The three Stewart
Avenue soils borings were advanced to depths ranging from five
to fifteen feet (152.4 to 457.2 cm).
Test pits were excavated through the asphalt in severely
damaged, moderately damaged, and undamaged areas of travel
lanes, turning lanes, shoulders medians, gutters, and curbs.

otoo 6t 00
T
NTS
I T E S T PIT L O C A T IO N
Figure 11a L o c a tio n of te s t pits along S te w a rt Ave.
00
38 TOO
NTS
I T E S T PIT L O C A T IO N
Figure 11b L o ca tio n of te s t pits along S te w a rt Ave.
IIO +OO M2 tOO IK too
id
S-30
iEli
: t 00
IT E S T PIT L O C A T IO N
Figure 11 d L o c a tio n of te s t pits along S te w a rt Ave.
51
Control test pits were placed along Stewart Avenue in unpaved
areas, adjacent to badly damaged sections of road as well as
adjacent to undamaged sidewalks.
In paved areas asphaltic concrete was sawcut and
carefully removed with a backhoe. A sand cone density test
(ASTM D1556) was then taken in an undisturbed portion of
aggregate base. At Owens Avenue, where aggregate base was not
used, this step was eliminated. The base section was then
gently removed and a sand cone density test taken in the
underlying lime treated subbase. The lime treated subbase was
next removed to expose the native soils. In undamaged areas,
the subbase was extremely well-cemented and could only be
removed with a jack-hammer. The native soils were density
tested and the test pit extended to its full depth. A density
test was occasionally taken at the bottom of the test pit,
particularly where a change in the soil was noted. The
results of the density testing are presented in Appendix 2.
Typical descriptions of the soils encountered as well as
test pit profiles are presented as Figure 13 for Stewart
Avenue. Figure 14 presents typical soils descriptions and a
test pit profile for Owens Avenue.

DESCRIPTION
<8>
0 -0 .4 6 ' A s p h a lt ic Co n c ra ta
0 .4 6 -1 .0 ' A p ora oa ta Basa w ith 1B1

n o n p la s t ic fin a s ^ 491 sa nd, 331 g re v a l
1 .0 - 2 .O' Lima T ra a ta d Subbasa c o n -

sI s t i n g o f w a t, s o r t , l ig h t g r a y , Sandy
SI I t w ith 541 s l i g h t l y p la s t i c f i n a l ,
2AJ sa n d s , 221 camantad g ra v a ls t o 3/4"
d lo m a ta r. M a ta rle l d is p la y s a m o rrlad
appaaranca and Is com prlsad o f 50-601
w h lta m ln a ra ls up t o */2" d la m a ta r. Soma
c r y s t a l s t r u c t u r a v l s l b t a unoar m a g n ifi
c a tio n .
3 .0 - 4 .5 ' M o is t , s t i f f , l ig h t brown,
Sandy Claw w it h 671 maclim p la s t i c
T T n e s T - T 7 T w a ry fln a se nd. M inor s a lts
v l s l b l a uncar m a g n if ic a tio n , a s p a c le lly
from 3 - 4 ' .
2 ■I VERTICAL EXAGGERATION A SAMPLE LOCATION
Figure 13b Test pit p ro file S t e w a r t Ave. S - 8 .
Ol
U>
DESCRIPTION
0 -0 .5 ' A s p h a lt ic C o n c ra ta
1761
0 . 5 -1 .0 8 ' Ao gra qa ta Beta w it h 4J
noop la s t I c t fn a s , j t in a -c o a r s a sand.
3 2 J g ra va f t o !■ d l a r a t a r .
1 .0 8 -1 .8 3 * Lima Tra<_______________
'a d Subbasa c o n -
s i s t l o g o f m o is f , v a r y cans* (s x c a v a tlo n
ra p u lra d Jaekham m ar), brow n, C w a o ta d
1760 S o *1 la c k in g th a » o t t I ad apparanca of
a Is rra s s a d a ra a s . W hlta c r y s t a l s up to
Y 2 " d la a a ta r com prlsa lass than 2 S of
s o i l m s s . M a t a rla l shows a w h lta s a l t y
s u rfa c a whan d r y . D i s t i n c t l y s o f t a r In
, °**r 0 . 2 ' , su g g a s tln g soata chaailcal
ra e c t lo n has o c c u r ra d .
1 759 1 .8 5 -3 .8 3 ' M o is t , s o f t , brow n, Sandy

S n * T C la y w ith 86 f low p la s t i c Y l n a s ,
14J v a r y f l n a s a n d . V a ry p o r o u s , no
s a l t s v l s l b l a un d a r m a g n if ic a t io n .
1758
1757
8 10 12
DISTANCE (F E E T )
2 ' I VERTICAL EXAGGERATION
A SAMPLE LOCATION
Figure 13c Test pit p ro file S t e w a r t Ave. S - 2 2 .

U1
U1
D«T *EwAT./E WOShmE CLAV
DESCRIPTION
0 ~ 0 .9 2 ' A s p h a lt i c C o n c re te
^ • 9 2 - 2 . OB' Lim a T r e a te d Subbase c o n s is t in g

100 o f m o is t , s o f t , 1 1 g'h+ g r a y , SI l t v Sandv
G re v a l w it h 1 9X n o n p le s t lc f i n e s , 2 B I
sa n o , 5 2 t g r a v a l t o 2 " d la m a t a r . w h it*
m in a r e ts up t o 1 /2 " d la a > a ta r c o m o rls a 50-401
o f th a t o t a l s o i l mess g i v in g The m e r e r le I
a m o tt le d a p p e a ra n c e . Sum* c r y s t a l s t r u c
t u r e v i s i b l e u n d e r m a g n !f Ic e t J o n .
2 . 0 5 -2 .5 ' U t i l i t y b a c k f i l l c o n r ls t in o o r
Sandy C -raval c o v e r s m ost o f th e tr e n c h
boTto m . N a t! v s s o l i in n o r th * .* :
c o n s is t s o f a m o is t , s t i f f , brown, Sandy
C la y a l t h 8 5 J s l l g n r t o low p l a s t i c f in e s ,
151 v e ry f i n e sa nd. M ino r s a l t s v i s i b l e
In n a t iv e under m a g n if ic a tio n .
EAST SIDEWALL
10 12
DISTANCE (F E E T )
Z-\ VERTICAL EXAGGERATION A SAMPLE LOCATION
Figure 14 Test pit p ro file Owens Ave. 0 - 5 .
Ol
Q\
57
Representative samples for mechanical and chemical
testing were collected from the aggregate base, lime treated
subbase, and native soils. Bulk samples for mechanical
testing were collected from trench sidewalls and sealed in
plastic containers. Samples for chemical testing were also
collected from trench sidewalls and were placed in air tight
jars. Soil temperatures were measured to accuracies of plus
or minus 0.5 degrees centigrade at various levels within
selected test pits to give an indication of the temperature
range appropriate for geochemical modeling.
Field Observations
The effects of lime treatment on the native soil varied
drastically between two extremes. In badly damaged areas the
subbase consisted of soft, light gray mineral aggregate with
the mechanical properties of a plastic silt (Figure 13a). In
undamaged areas lime treatment resulted in an extremely hard,
cemented, medium brown material that could not be described
as soil (Figure 13d). All gradations between the two extremes
were observed in the test pits. Often, the extremely hard
material graded to the soft, wet subbase in the length of a
single exploration trench. Vertical gradation was also
observed in some instances.

58
The undamaged subbase was medium brown in color and
generally contained less than five percent (5%) white
crystals. These white minerals were clearly of secondary
origin with a maximum size of approximately three-fourths inch
(19.1 mm). The damaged subbase was a light gray to almost
white color, and showed very little of the brown coloration
typical of the native soils or undamaged subbase. In the most
severe cases the subbase consisted of an estimated 30-60%
light colored secondary minerals grown subsequent to the lime
treatment process. Maximum size for individual minerals was,
again, approximately three-quarters inch (19.1 mm), however,
the majority was much smaller. Large crystals were
occasionally concentrated along the contacts between base and
subbase or subbase and native soil (Figure 15).
The contacts of undamaged subbase with the overlying
aggregate base and the underlying native soils were straight
and parallel to each other. The layer was of uniform
thickness, typically twelve inches (30.5 cm) on Stewart Avenue
and eight inches (20.3 cm) on Owens Avenue. These thicknesses
are in good agreement with the design. The material contained
obvious, darker brown fragments of native soils that had not
been mixed with lime. These fragments reached a maximum size
of approximately two inches (5.1 cm). When air dried in the
sun, the undamaged subbase developed a white salty appearance

59
attesting to the abundance of dissolved salts in the soil pore
water. A photograph of this material is shown in Figure 16.
Areas of major damage were almost always found adjacent
to an obvious source of water. This included permeable
utility trench backfill (Figure 14), yard drainage, areas of
poor surface drainage, and construction joints such as occur
at the concrete median and asphaltic pavement intersection.
In most instances the worst damage was found to be adjacent
to or overlying trench backfill. Occasionally, damage vras
observed on both sides of a utility trench, but not directly
over the trench.
The damaged subbase was distinctly lens shaped, thickened
in the most distressed areas and thinning progressively with
lower degrees of damage. This is clearly visible in Figure
17. The maximum measured thickness was 2.25 feet (68.6 cm)
on Stewart Avenue— more than twice that of the undamaged
material. The lower contact was often slightly convex
downward indicating some expansion into soft, native soils.
The upper contact was sharply convex demonstrating that the
expansion was predominantly upward (refer to Figures 13 and
17). Figure 14 from Owens Avenue is a rather unusual case
where upward and downward deflections were about equally
divided.
Figure 16 Photograph of undamaged subbase from test pit S-7.
Note salty appearance.
63
t.
&ROT? ATOR Y ANALYSIS
Soil Testing
Index Testing
Samples of aggregate base, lime treated subbase, and
native soil from each test pit on Stewart Avenue and Owens
Avenue were analyzed in the laboratory to determine their
grain size distribution and plasticity characteristics.
Testing included sieve analysis, hydrometer analysis, liquid
limits, and plastic limits. The results of these tests are
summarized in Appendix 1 for both Stewart Avenue and Owens
Avenue. Index testing allows the soils to be classified in
accordance with the Unified Soil Classification System
(Appendix 2) and correlated with the range of mechanical
properties that could be expected for each soil type.
Moisture-Densitv Curves
Moisture density curves were developed in accordance with
ASTM D-1557-78 for most of the native soil and lime treated
subbase samples. The results of these tests are summarized
in Appendix 1 and were used for many of the other tests and
experiments.
64
Volume Change and Expansion
Volume change tests were conducted on remolded samples
of lime treated subbase and native soil to determine the
potential volume change of the soil in accordance with AASHTO
Designation T-116. The purpose of these tests was to evaluate
the expansion potential of the native clays since previous
consultants had implicated swelling clay in their distress
analysis. In addition, it was hoped that the tests would give
some indication of the potential for continued expansion in
the lime treated subbase.
Samples were tested at four different moisture contents:
in place, five percent (5%) below optimum, optimum, and five
percent (5%) over optimum in accordance with the appropriate
moisture-density curves. Samples of native soil were tested
at ninety percent (90%) compaction relative to ASTM D1557-78.
Samples of lime treated subbase were tested at ninety-five
percent (95%) relative compaction in accordance with the
construction recommendations of the original soils report
(Converse-Davis and Associates in 1974). Lime-treated subbase
and native soil samples were tested with surcharges
appropriate for the overlying structural section.

65
Expansion tests were also conducted on the native clays
and lime treated subbase using an FHA swell meter. This test
provides a measure of the potential expansive pressure of the
soil sample. Tests were run at various moisture contents in
order to evaluate the relationship of moisture content to
expansive pressure. Again, the native soils were run at
ninety percent (90%) and the lime treated subbase at ninety-
five percent (95%) relative compaction. Typical volume change
and expansive pressure curves are presented as Appendix 3 for
Stewart Avenue.
Samples of native soil obtained from subbase grade in
unpaved shoulder areas adjacent to badly damaged pavement
(Sample S-9B) were mixed with 4.5 weight percent quicklime
(CaO) at a moisture 4% over optimum moisture and quicklime
contents of our laboratory mixture were selected in accordance
with those reported by Converse Davis and Associates in their
field inspection summary dated 1975. The laboratory mixture
of lime treated soil was allowed to cure for 24 hours and then
separated in three six-inch (15.2 cm) high, three-inch (7.6
cm) diameter, clear lexan, cylinders. Soil was placed m the
cylinders in five uniform layers densified to approximate the
original field density of ninety-five percent (95%) relative
compaction (ASTM D1577-78). The three cylinders of lime
treated soils were each placed in a 500 ml glass beaker. One

66
beaker was filled with a magnesium sulfate solution containing
20,000 ppm S042' and another a sodium sulfate solution
containing 20,000 ppm S042". The third beaker was filled only
with de-ionized water. A fourth test cylinder containing
untreated native soil at ninety-five percent (95%) relative
compaction was placed in a beaker containing the 20,000 ppm
magnesium sulfate solution. Temperatures were allowed to
fluctuate diurnally between 3° and 18° centigrade. After a
period of only 48 hours all three of the quicklime-treated
specimens had expanded, developing semi-vertical cracks in the
lexan cylinders. Increased damage and cracking could be
observed on a daily basis. After a period of three weeks the
damage to the three cylinders was severe. Cracks had
increased to one—half inch (12.7 mm) in width. The cylinder
containing untreated native soils showed no damage after 120
days. It is important to note that the experiment was set up
so as to require the water to move upward through the soil by
capillarity.
chemical Testing
Soluble Salts
Samples of aggregate base, lime treated subbase, and
native soils from various depths were analyzed for total

67
extractable ions of calcium, sodium, potassium, magnesium,
sulfate, chloride, carbonate, and bicarbonate. Selected
samples were also analyzed for manganese, aluminum, and
silica.
In order to remove most of the soluble ions, initial
samples were extracted at trial dilution ratios of 5:1, 10:1,
20:1, and 50:1. Curves generated from these data (Appendix
4) demonstrated that soluble ions could best be extracted from
native soils and lime treated subbase using dilution ratios
of 50:1. Even at this ratio, not all of the calcium carbonate
dissolved. Dilution ratios of 5:1 were used for aggregate
base samples which contained a much lower concentration of
soluble salts.
For the fine grain soils, 400 gram samples were oven
dried at a temperature of 30-35 degrees centigrade in
accordance with the methods recommended by the Soil
Conservation Service (USDA, 1972). Dried samples were
screened through a No. 40 sieve, thoroughly mixed and split
into four fractions. A 70 gram sample from one of the splits
was added to 500 milliliters of de-ionized water and mixed for
five minutes using a high speed soil dispersion mixer. This
soil-water suspension was transferred to a one-gallon plastic
storage vessel and the stainless steel mixing cup thoroughly

68
rinsed into the vessel with 700 milliliters of de-ionized
water. An additional 2300 milliliters of de-ionized water was
then added to complete the soil dilution and the vessel
sealed. For the coarse grain aggregate base samples 200 grams
of dry soil were added directly to 1000 milliliters of de
ionized water in the storage vessel. Accuracy of preparation
was double checked by weight and found to be within plus or
minus 0.05%.
Storage vessels were periodically shaken and then allowed
to equilibrate for a minimum of 48 hours. A 300 milliliter
water sample was obtained by filtering the soil-water solution
into a sealable glass vessel. These samples were analyzed by
atomic absorption in accordance with the method described in
Standard Methods for Examination of Water and Wastewater, 15th
Edition, 1980. The results of the extraction analysis are
tabulated in Appendix 5 for Stewart and Owens Avenues.
The extraction solution of each sample was measured for
pH. In addition, all lime subbase samples and selected
samples of native soil were measured for pH. This was
accomplished by mixing the soil with enough de-ionized water
to form a thick slurry and then making the measurement with
a Hach Model 1975 pH meter. Typical soil pH values are shown
on the test pit logs (Figures 13 and 14).

Cation Exchange Capacity
Ten samples of the native soil were tested for cation
exchange capacity using the sodium acetate method described
by the Soil Conservation Service (USDA, 1972). The cation
exchange capacity of a soil is function of the types of clay
minerals it contains and the geochemical environment. The
more expansive clays such as those of the smectite and
vermiculite groups generally have a higher capacity for cation
exchange. The results of this testing are presented in
Appendix 6.
MTNERAT, IDENTIFICATION
Representative samples of damaged lime treated subbase,
undamaged subbase, and native soil were analyzed by x-ray
diffraction to determine their constituent mineralogy.
Typical diffraction patterns and the indicated minerals are
presented in Appendix 7.
Analysis of selected samples was also conducted using a
Scanning Electron Microscope. The SEM uses energy dispersal
analysis to identify the constituent elements of a compound.
This is particularly useful for differentiating minerals such

as thauxnasite and ettringite which, as shown in Appendix 8,
have very similar x-ray patterns. Typical energy dispersal
analyses from the Scanning Electron Microscope are presented
in Appendix 9. The analysis was performed at the University
of Nevada, Mackay School of Mines laboratory.
The minerals identified in the samples are summarized
below in Table 1.
Table 1
I.ist of Minerals Identified in Stewart Avenue Samples:
Mineral Composition
Native Soil
gypsum (primary) CaS04-2H20
calcite (primary) CaC03
quartz (primary) sio 2
lime Treated Subbase
thaumasite (secondary) Ca6[Si(0H)6]2-(C03)2- ( S 0 J 2-24H20
gypsum (secondary) CaS04 •2H20
quartz (primary) Si02
polyhalite (secondary?) K2HgCa2(S04)4*2H20
The x—ray work shows a significant increase of calcite
and gypsum in the subbase, relative to the native soils. This

71
indicates that secondary calcite and gypsum have formed as
reaction products of the lime/soil system.
ANALYSIS a n d c o n c l u s i o n s
Results of the analysis for soluble salts at a 50:1
dilution ratio have been summarized in Appendix 6 both in
units of milligrams per 1000 grams soil and milliequivalents
per liter. This information was plotted on trilinear and
stiff diagrams in order to interpret the original soil
chemistry and the chemical effects of lime treatment.
Figure 18 shows a trilinear diagram of native (untreated)
soil soluble ion chemistry from Stewart Avenue. The soluble
ions are dominated by calcium and sulfate with variable ratios
of sodium + potassium and total carbonate, HC03' + C032 . The
percentages of magnesium and chloride are very uniform
throughout the soils. The most significant factor demon
strated by the diagram is the broad range of soluble ions
shown by the native soils. There is no distinctive grouping
of soils from undamaged versus damaged areas. This indicates
that the lime/soil reactions were not noticeably affected by
variations in initial soluble ion chemistry.

72
As would be expected lime treatment resulted in major
changes in the soil chemistry. These changes are apparent in
Figure 19, a trilinear diagram of the lime treated soils. The
diagram shows a pronounced relative migration of anions toward
the S042" apex. The cations show a significant increase in
relative percent calcium, however, it is far less than would
be expected from the addition of massive amounts of lime.
Calcium added by lime treatment is two to ten times that
contained in the native soil so that the points should all
plot very near the Ca2+ apex. The fact that they do not
indicates that either the calcium has been leached away or
that it is tied up in insoluble minerals. The grouping of
points on the cation diagram from undamaged samples (24, 25,
29, 33) is critical in this regard. These soils contain
abundant secondary calcite which is relatively insoluble and
is clearly tying up some of the added calcium. The grouping
of these samples in the anion triangle and the composite
diamond also indicate that these areas contain abundant
insoluble calcite.
The relative increase in sulfate indicates that either
additional S042' has migrated into the soil or that total
carbonate and chloride have decreased. In fact, additional
carbonate had to be introduced into the soil to form secondary
calcite. Likewise, secondary gypsum is also present and,

73
rooO
CATIONS PERCENT OF T O T A L
M I L L I E Q U I V A L E N T S PER LITE R
Figure 18 Trilinear diagram for untreated

soils from S tew art Ave.
soils from Stew art Ave.
75
consequently, the shift toward the S042' apex must represent
an influx of sulfate. This is readily apparent from stiff
diagrams, examples of which are presented as Figure 20.
The remaining calcium, sulfate, and carbonate, are
thought to be tied up in thaumasite. The solubility of
thaumasite was inferred from the diagrams and mineralogy, to
be slightly less than that of calcite, and considerably less
than that of gypsum. For example, sample S-10B shows abundant
gypsum in the x-ray pattern. The corresponding stiff diagram
shows a large increase in both soluble sulfate and calcium
relative to the untreated soil (S-10C). Sample S-27B shows
very little gypsum, but abundant thaumasite and calcite in the
x-ray pattern. A relatively minor change in the stiff polygon
is noted after lime treatment. The most significant change
is a slight decrease in the amount of soluble carbonate. The
x-ray pattern for S-30B shows only traces of thaumasite and
gypsum, but a very high content of calcite. A small increase
in the sulfate and calcium axis of the stiff polygon is
observed, largely attributable to dissolution of gypsum.
Again, a slight decrease in soluble carbonate is observed.
The decreased solubility of carbonate in the lime treated
soils is a general but not infallible trend throughout all the
chemical data. The relationship is complicated somewhat by
the increase of carbonate with depth shown in the control test

MILLIEQUIVALENTS/LITER MILLIEQUIVALENTS/LITER
CO2
3
and u n tre a te d S te w a r t Ave. soils.

77
pits. This effect is probably minor over the distance
separating the samples of subbase and native soils. Clearly,
if thaumasite was more soluble than calcite the damaged
subbase would show increased soluble carbonate. As a
consequence thaumasite was inferred to be no more, and likely
somewhat less, soluble than calcite.
The calcium-to-sulfate-to-carbonate ratio in thaumasite
is three to one to one (3:1:1). This accounts for the
distinctive difference in the relative migration of ions
toward the calcium and sulfate apexes of the stiff diagrams
after lime treatment. Three times more calcium than sulfate
is tied up in thaumasite, which is relatively insoluble.
Figure 21, a graph of calcium versus sulfate, shows that both
of these ions, before and after lime treatment, are mostly
derived from dissolution of gypsum. If thaumasite was near
gypsum in solubility the lime treated points would plot well
above the "gypsum line."
Figure 22 is a trilinear diagram for both lime treated
and untreated soils obtained along Owens Avenue. Here the
trends are not as clear as those observed for Stewart Avenue,
however, there is still no obvious association with damaged
areas and native soil chemistry.

79
•LIME TREATED SOIL

°UN TREATED SOIL
Figure 22 Trilinear diagram for untreated and

treated soils from Owens Ave.
80
The damaged subbase was extremely soft and contained an
unusually high moisture content— often ranging from thirty to
fifty weight percent (30-50%). In-place dry densities
measured in damaged subbase typically ranged from 65 to 85
pounds per cubic foot for relative compactions of 50% to 80%.
During construction this material was densified to at least
ninety percent (90%) relative compaction (Converse-Davis and
Associates, 1975). This sharp decrease in density can be
directly correlated to increase in volume and growth of
minerals with a low specific gravity.
The results of this investigation clearly demonstrate
that the distress on Stewart Avenue and Owens Avenue was due
to chemical reactions between quicklime and the native soils.
The new minerals grown include thaumasite, polyhalite, gypsum
and calcite. The seemingly sporadic occurence of distress
along Stewart Avenue was found to be the result of two primary
factors. Neither of these factors relate significantly to
native salt chemistry or the construction process. In all
cases the critical factor was the ability of water to enter
the soil/lime system. Both ettringite and thaumasite are
highly hydrous minerals. Without an abundance of water they
simply cannot form. Virtually all of the distress occurred
near an obvious water source.

81
Typically, heave paralleled a utility trench backfilled
with highly permeable material. Localized (non linear) areas
of damage could generally be traced to specific houses which
channeled roof and yard drainage to the street. Storm drains
in Las Vegas are often intentionally undersized and the street
itself expected to carry the bulk of the water during
occasional thunderstorms. During one small thunderstorm
(November 1982) water was observed running well above
sidewalks on Stewart Avenue. Ponded water exceeded a depth
of four feet (122 cm) in some places. It was concluded,
therefore, that stormwater entered the subsurface along
construction joints and migrated through the permeable
aggregate base and into the utility trench backfill. After
ponding in low lying areas of the trench, capillarity and
diffusion supplied saline solutions to ettringite/thaumasite
nuclei. Damage also was common along the construction joints
themselves, especially between the asphalt and the concrete
curb and the asphalt and the median. As the swelling
progressed construction joints widened and the pavement
cracked. This condition made it increasingly easier for water
to enter the system, doubtless accelerating the heave.
Although the availability of water is the dominant
factor, it does not explain the distinctive decrease in
observed damage on Stewart Avenue east of Lamb Boulevard.

82
Analysis of the hydrometer data, however, demonstrated a
dramatic drop in the percentage of clay sized particles east
of Lamb Boulevard. These data are shown graphically as Figure
23. It was concluded that the decrease of clay sized
particles correlated with a decrease in clay minerals
available for reaction. Where sufficient silica and alumina
could not be generated from dissolution of clay, the calcium
reacted to form calcite, gypsum and, presumably pozzolanic
compounds, rather than large quantities of thaumasite/
ettringite. Although minor thaumasite is present in undamaged
subbase, it is apparently not of sufficient quantity to cause
distress.
Thaumasite is a rare mineral forming a solid solution
series with the more publicized mineral, ettringite (Kollman
and Strubel, 1981):
Thaumasite: Ca6[Si (OH)6]2*(S04)2* (C03)2-24H20
Ettringite: Ca6[Al (OH)6]2* (S04)3*26H20
In theory, this means that any composition between the
two end members is possible and that the pure minerals might
be uncommon. The x-ray diffraction patterns of thaumasite and
ettringite are nearly indistinguishable, as shown in Appendix
8. The two minerals can, however, be distinguished by energy

dispersal analysis on the electron microscope (Appendix 9).
The thaumasite identified during this study very closely
approaches the composition of the pure synthetic end member
and contains very little aluminum.

85
CHAPTER 4
OTHER CASES OF LIME-INDUCED HEAVE AND
RELATED LABORATORY RESEARCH
OTHER CASES OF LIME-INDUCED HEAVE
Deterioration of concrete in high sulfate environments
through ettringite growth has been recognized as a problem for
many years (Taylor, 1964; Lukas, 1975). Considerably less
attention has been given deterioration of lime and cement
treated soils through adverse reaction with sulfate. Although
the Stewart/Owens cases are the most severe examples known,
other cases of lime-induced heave have been documented.
An early reference to sulfate—lime distress (Sherwood,
1962) states: "An instance has been recorded in South
Australia where the presence of calcium sulfate in the soil
resulted in disintegration of a soil cement road." This single
sentence description references an unpublished report which
could not be located.
A lime-treated school parking lot in the east Las Vegas
area has suffered extreme heave subsequent to the Stewart
Avenue distress. A lime treated parking lot in Wichita,
Kansas, is also reported to have failed through growth of
ettringite sometime after 1980 (Mitchell, 1986). In 1975

86
(Gouda, Roy, and Sarkar, 1975) thaumasite, and an intermediate
phase between thaumasite and ettringite, were described in a
deteriorated soil cement. The soil cement was from a seven-
year-old pavement section in Pennsylvania. In this case no
significant heave was mentioned. The pavement simply failed
prematurely due to loss of support in the cement treated base.
Conversations with the State of Texas Highway Department
(Gerald Peck, personal communication, 1983) revealed the
occurrence of lime-induced heave on U.S. Highway 10 between
Amarillo and Fort Worth, in 1975. Here lime treatment of
native soils produced isolated swelling after placement of
asphalt treated base, but prior to paving. The base material
was removed from the damaged areas and the underlying lime-
treated subbase was simply recompacted. There has apparently
been no report of recurring or additional damage. Damage was
blamed on the growth of gypsum and it was stated that it was
an occasional problem where lime reacted with sulfate in the
native soils. Maximum heave was on the order of 1/2 inch (12.7
mm). No further investigation of the phenomena was undertaken;
the entire documentation of the event being limited to a memo
to the file.
The Utah Department of Transportation (Loren Rausher,
1983, personal communication) experienced lime-induced heave
on Interstate 70 in Grand County, eastern Utah. Swelling
occurred in lime treated subgrade prior to paving. Subgrade

87
was rerolled and no further incident has been reported. The
growth of the mineral ettringite was thought to have been the
cause. Maximum heave was less than one inch. No testing was
conducted and no written documentation is available.
In both the Texas and Utah cases swelling occurred prior
to placement of pavement. Repair was limited to recompacting
isolated areas of the subgrade which was not alarming enough
to make the occurrence any more than a curiosity. No
additional cases of lime-induced heave were known by the main
offices of state highway departments in Arizona, New Mexico,
California, nor Nevada.
In 1972 the Orange County Road Department (Santa Ana,
California) observed severe cracking of asphaltic concrete
pavement on a street with lime stabilized clay base. An
expansion study initiated soon thereafter used laboratory
specimens of the native clay soil treated with three percent
quicklime (CaO). The treated soil was compacted at optimum
moisture and allowed to swell against a surcharge load equal
to the weight of the overlying pavement, approximately 46
pounds (101.2 kg). One specimen was soaked in tap water and
the other in high sulfate water. After 20 days both specimens
had expanded approximately one percent. After 600 days the
sulfate specimen had expanded 10.4 percent while the tap water
specimen had a volume increase of 6 percent. Neither specimen
showed any sign of a declining expansion rate. The same clay,

88
untreated and soaked in tap water expanded 8.8 percent in 20
days and 9.6 percent in 300 days (Graf, 1986; personal
communication). Although it will never be known whether the
pavement distress was caused by ettringite/thaumasite, the
laboratory experiments were such that ettringite should have
grown, at least in the sulfate specimen.
A recent paper (Hunter, 1988) presented the early findings
of this dissertation. The response to that paper uncovered
several other major cases of lime-induced heave. The Tennessee
Department of Transportation (TDOT) forwarded an in-house
report (Gaffron, et. al., 1988) describing pavement distress
on U.S. Highway 41 in Davidson and Sumner Counties, Tennessee.
The aggregate base for this roadway had been blended with a
mixture of lime and fly ash which normally results in a product
much like cement treated base. Fly ash provides the highly
reactive (metastable) silica necessary for the pozzolanic
reactions. A description of the distress is quoted from the
TDOT report:
rin-v-i noroinhpr 1987 a number of distortions of
l i n e a r b u lg e s w e re a ls o n o te a
w ith th e ro ad w ay. C o n cre te
s ta b le th ro u g h o u t th e p r o je c t .
89
The investigation by TDOT was fairly extensive and
included field measurements of the distress, test pits, core
samples, density testing, and a variety of physical testing in
the laboratory. No chemical or mineral identification tests
were performed. As a result of their evaluation, the following
conclusion was reported:
The bulging of the pavement began in December. An

increase in moisture during this period changed the
strength of the subgrade and the base since the base
was still in a somewhat plastic state. Hydration
and strength gain of the lime fly-ash base is known
to be sensitive to temperature. The cooler ground
temperatures of late fall may not have been
sufficient to totally cure the base. The base acting
as a plastic material began to displace under traffic
or expansion loading. When the material displaced,
it became less dense and gained volume. The bulges
in the pavement are thought to be the result of
plastic displacement. Some bulges occur in wheel
paths and many occur in the center turn lane. There
is also little sign of rutting in the wheel paths.
This may indicate that the bulges are related to
expansions of the base and are not totally of load
or traffic origins.
As can be seen from the above statements, the evaluation
was somewhat inconclusive. However, the distress described
was strongly suggestive of lime-induced heave. Telephone
conversations with the TDOT (Gaffron, 1988, personal
communication) produced a set of samples for further analysis.
Native subgrade soil and material from a core of the damaged
base were subjected to x-ray diffraction. The results of this
analysis (Appendix 10) revealed the presence of significant
quantities of ettringite/thaumasite in the matrix of the lime
fly ash-base mixture. Since there was no indication of sulfate

90
bearing minerals in the subgrade, it was assumed that the
sulfate source was most likely in the aggregate itself. The
aggregate is rock derived from coal mining in the area and
might be expected to contain some sulfur. As an alternative,
sulfur could be supplied by sulfate reducing bacteria in the
soil. In this case the sulfur would migrate into the base as
a gas, H2S, and oxidize to sulfate in the high pH environment
(Garrels and Christ, 1965). The linear nature of the bulges
is thought to be a surface reflection of the pathway of water
entering the aggregate base.
On the basis of the TDOT report, photographs of the
damaged roadway, and the x-ray diffraction work, it was
concluded that the distress was clearly the result of lime-
induced heave caused by growth of ettringite/thaumasite. Since
no calcite (or other carbonate) occurs in the native soil or
base, the swelling mineral is probably near the end-member
composition of ettringite. In addition to being a well-
documented case of lime-induced heave, the damage to U.S.
Highway 41 represents the first known case where gypsum was not
involved. Previously it was assumed that the phenomenon was
restricted to arid climates where gypsum and other sulfate
bearing evaporate minerals are common. The Tennessee
occurrence greatly expands the set of geochemical conditions
under which lime-induced heave can occur. Another similar
situation reportedly occurred in Kentucky (Gaffron, 1988,

personal communication), however, the details are not readily
available at this time.
A third and somewhat different case of lime-induced heave
was presented in a publication received from France. In this
paper (Habib and Aversenc, 1988) described an industrial
building in Paris that was damaged by lime-induced heave.
Subgrade fill beneath the concrete floor slab had been mixed
with both lime and cement in an effort to increase the subgrade
modulus (bearing strength) of the material. Gypsum in the fill
reacted with the lime and/or cement producing ettringite. The
resulting volume change produced heave along the edges of the
floor slab in the range of 5 to 20 millimeters. The swelling
occurred slowly over the course of two years and was continuing
at a steady rate at the date of the publication. Deflection
of the floor slab also resulted in uplift of the foundation and
deformation of the exterior walls.
PREVIOUS LABORATORY RESEARCH ON LIME-CLAY-SULFATE REACTIONS
Several researchers have investigated the effects of
sulfate on lime and cement stabilized soils in the laboratory.
Lambe, Michaels and Moh (1960) and Ladd, Moh, and Lambe (1960),
Hollis and Fawcett (1966) concluded that small amounts of
sulfate produced a significant increase in the strength for
certain soil types. Evidence for detrimental effects of high
sulfate concentrations on cement and lime treated soils

92
presented by Mehra, et. al. (1955), Sherwood (1958, 1962),
Lambe, Michaels and Moh (1960) and Cordon (1962). A report
published in 1974 by the California Division of Highways
stated: "Sulfates can be detrimental to lime-treated soils
because they enhance swelling and may induce disintegration
when the mixture is saturated." In a major laboratory study
of lime stabilization, they demonstrated that potential for
swell increased with the sulfate content of the treated soil.
Maximum volume increases were on the order of 4% and attributed
to growth of ettringite.
A major laboratory study of ettringite/thaumasite growth
in various soils is presently in progress at the University of
California, Berkeley (Mitchell, 1988, personal communication).
The writer was asked to review the proposed experiments
(Appendix 11) and provide suggestions that might improve the
outcome or answer additional questions. The experimental
results are not yet available, however, they are expected to
be very helpful.
93
CHAPTER 5
THE MINERALOGY OF THAUMASITE AND ETTRINGITE
Thaumasite and ettringite are both complex hydrated
calcium sulfate minerals. The two minerals are relatively
rare, occurring in scattered locations throughout the world.
Commonly, but not necessarily, thaumasite and ettringite are
found in association with one another. As previously noted,
they form a complete solid solution series which makes their
association considerably less surprising (Kollmann and Strubel,
1981). Several minerals with compositions between the end
members have also been identified (Edge and Taylor, 1971;
Murdoch and Chambers, 1985; Hurlbut and Baum, 1960; Kollmann
and Strubel, 1981). Another mineral, jouravskite
(Ca6Mn2(S04)2(C03)2(O H )2•24H20 ) , is also isostructural with
ettringite and thaumasite (Edge and Taylor, 1971). Although
jouravskite is apparently found only on the dumps of the
Tachgagalt No. 2 vein, Anti Atlas, Morroco, under certain
geochemical conditions, a more complex solid solution series
involving jouravskite, ettringite and thaumasite might be
possible. In jouravskite, manganese replaces aluminum or
silica in the ettringite/thaumasite structure.
Ettringite and thaumasite are most often found in zones
of hydrothermal alteration or low temperature thermal
metamorphism. Both minerals are commonly associated with

94
zeolites and are clearly of supergene origin (Hurlbut and Baum,
1960; Kollmann and Strubel, 1981). No reference to either
mineral occurring naturally in low temperature agueous
environments has been found. There is no indication that
either ettringite or thaumasite occur in playas or in
association with evaporite minerals. Synthetic ettringite, in
minor amounts, is a normal reaction product of Portland cement
and some expanding grouts. Excess ettringite, such as occurs
from sulfate attack, causes rapid mechanical deterioration of
concrete (Taylor, 1964). Synthetic thaumasite probably occurs
in many concretes but has yet to be recognized. Again, this
may be largely due to the similarity of the thaumasite and
ettringite x-ray diffraction patterns. In concrete an
intermediate phase would be a likely end product.
THAUMASITE
Thaumasite comes from a Swedish word meaning to be
surprised— doubtless referring to the mineral's remarkable
composition (Dana, 1919). In this regard, the hydrated
calcium-silicate-carbonate sulfate-hydroxide is unparalled
among minerals (Dana, 1919). Thaumasite was first described
by A. E. Nordenskold in Langban, Sweden in 1878 (Nordenskold,
1878, Kollmann, 1978). Some of the samples Nordenskold
examined had been collected as early as 1802 (Dana, 1919).
Since that time, the mineral has been recognized at numerous
locations including Crestmore, Riverside County, California,

95
Beaver County, Utah; Cochise County, Arizona; Paterson and West
Paterson, New Jersey; and Fairfax County, West Virginia (Dana,
1919; Font-Altaba, 1960).
Thaumasite has been reported with various compositions,
largely due to its tendency toward solid solution with
ettringite. The true composition of the pure thaumasite end
member is Ca6[Si(0H)4]2-(C03)2* (S04)2-24H20 (Welin, 1956; Edge and
Taylor, 1970; Kollmann, 1978; Kollmann and Strubel, 1981). The
following crystalographic and physical properties have been
ascribed to thaumasite (Roberts, et al., 1974; Dana, 1919).
Table 2
MineraJocric Properties of Thaumasite
Crystal System Hexagonal

Class: 6
Space Group: P63
Z: 2
Lattice Constants: a = 21.80 c + 20.58
3 Strongest Diffraction Lines: 9.66 (10) 3.792 (75)
4.582 (65)
Optical Constants: w = 1.500-1.507
e = 1.464=1.468 (-)
Hardness: 3.5
1.91 (measured)
Density:
1.916 (calculated)
(101-1) in traces; brittle
Cleavage:
Crystals acicular to
Habit: filiform; usually massive,
compact
Colorless to white;
Color: transparent to translucent
Vitreous to somewhat silky
Luster:
or greasy
diffraction peaks has been

* The complete list of x-ray
included as Appendix 12.
96
Differential thermal analysis of thaumasite shows a large
endothermic peak at 206 °C corresponding to loss of H 20 and C02.
Between 200° and 550°C, thaumasite changes to a glass-like
amorphous state (Kirov and Pouieff, 1968). A weak endothermic
peak at 709°C occurs as the mineral recrystallizes to a mixture
of anhydrite and larnite. Above 900°C calcium silicosulfate
and anhydrite are the thermal decomposition products (Fonta-
Altaba, 1960).
The thaumasite structure is based on columns of empirical
composition (Ca3Si(0H)6'12H20)4+ running parallel to the C axis.
Groups of C022' and SO<2' occur between the columns. Thaumasite
was the first structure in which octahedral groups of Si(OH)6
were proven to exist (Edge and Taylor, 1971).
ETTRINGITE
The type locality for ettringite is near Ettnngen, Rhine
Province, Germany. The mineral occurs there in cavities of
metamorphosed limestone inclusions in volcanic flows.
Ettringite was first described at that location by J. Lehmann
in 1867. In the United States ettringite has been reported m
Crestmore, Riverside County, California, Cochise County,
Arizona; and Franklin, New Jersey.
Like thaumasite, ettringite of varied composition has been
reported, largely because of the solid solution phenomena

97
(Murdoch and Chalmbers, 1958, 1960). The actual, pure end
member composition is Ca6[Al(OH)6]2* (S04)3*26H20 (Moore and
Taylor, 1968; Kollmann, 1978; Kollmann and Strubel, 1981).
Ettringite has the following crystallographic and physical
properties (Roberts, et al., 1974).
Table 3
Mineraloaic Properties of Ettringite
Crystal System: Hexagonal

Class: 6/m 2/m 2/m
Space Group: P63/mmc
Z: 8
Lattice Constants: a = 22.46 c = 21.44
3 Strongest Diffraction
Lines*: 9.65 (100) 5.58 (75) 3.21 (65)
Optical Constants: w = 1.491 e = 1.470 (-)
Hardness: 2-2.25
Density: 1.77 (measured) 1.79 (calculated)
Cleavage: (101 - 1 )
Habit: Flattened hexagonal dipyramids;
also prismatic, usually without
terminal faces; also as thin
fibers
Color: Colorless and transparent; also
milky white
Luster: Vitreous
* The complete list of x-ray diffraction peaks has been

Ettringite occurs as columns of empirical composition
(Ca3(A l (O H )6) *12H203+, which run parallel to the C axis. Between
the columns lie the sulfate ions, along with the remaining
water molecules (Kollmann, 1978).

98
gVNTHETir: ETTRINGITE AND THAUMASITE
Ettrinaite
The synthetic preparation of ettringite was discovered in
1874 by J. Lehmann. Lehmann simply mixed an aqueous calcium
sulfate solution with an aqueous solution of calcium aluminate
at room temperature. The immediate white precipitate was found
to be ettringite. Since that time at least 15 other chemical
combinations have been found to yield synthetic ettringite at
temperatures between 5 and 50 C. The simplest technique
(Michaelis, 1892) precipitates ettringite through aqueous
reaction of calcium hydroxide and aluminum sulfate:
6Ca (OH) 2 + Al2(S04)3*18H20 + 6H20 =

Ca6(A1 (O H )6)2•(SO,)3•2 6H20
(Kollman and Trost, 1977; Kollman, 1978).
Synthetic ettringite is produced in minor amounts as a
normal reaction product in Portland cement concrete. The
addition of gypsum in the manufacture of Portland cement must
be controlled such that ettringite formation is completed
before the time the initial concrete set. Excessive gypsum (or
other soluble sulfate compounds) leads to internal expansive
forces larger than those that can be absorbed by pore spaces
in the concrete. The result is a decrease in both flexural and
compressive strength whenever the optimal sulfate content is
exceeded (Taylor, 1964).

99
Thaumasite
Thaumasite is considerably more difficult to synthesize
than ettringite. This appears to be primarily the result of
two nearly mutually exclusive reactions that must occur in
order for thaumasite to form. The formation of synthetic
thaumasite can be represented by the following series of
stepped reactions:
1. 2Ca(OH)2= 2Ca2+ + 40H' (raises pH to 12.3)
2. Si02 + 2H20 = H4Si04 (formation of silicic acid)
3. 2H4Si04 = 2H2Si042‘ + 4H+_

(dissolution of silicic acid, at high pH)
4. 2CaC03= 2Ca2+ + 2C032" (dissolution of calcite)
5. 2CaS04•2H20 = 2Ca2+ + 2S042‘ + 2H20 (dissolution of

gypsum)
6. 6Ca2+ + 2H2Si04" + 2C02‘+ 2S02'+ 28H20 =

Ca6[Si (OH) 6]2*(C03)2*(S04)2*24H20
The difficulty lies in the need for carbonate and silica
both to be soluble in the same solution. Both silica and
carbonate solubility are strongly pH dependent, however, they
are affected in an opposite manner. Crystalline silica is
soluble in pure water at 60 ppm below pH—9. Above a pH of
the solubility increases dramatically and exceeds 6000 ppm at
the pH of lime saturation, 12.3. Amorphous silica, while
significantly more soluble than crystalline silica, behaves in
a similar way (Krauskopf, 1979). The relationship between
silica solubility and pH is shown graphically in Figure

100
To the contrary, calcite is highly soluble in acid
solutions and nearly insoluble under alkaline conditions. In
aqueous solutions, calcite dissolves through attack of carbonic
acid, as represented by the reaction:
CaC03 + H2C03 = Ca2+ + 2HC0f = Ca2+ + 2H+ + C032'
The log of the dissociation constant for the bicarbonate
reaction:
HC03' = C032' + H+
is -10.3 indicating that precious little C032 should be
available in the solution. From Le Chateliers rule, any
increase in the chemical potential of calcium will tend to
drive the calcite dissolution reaction back toward the left,
precipitating calcite.
It is also possible to produce thaumasite using C02
derived from the atmosphere as a source of carbonate (Kollman,
1978). Although this eliminates the necessity of dissolving
calcite the problem remains. Carbon dioxide dissolves in water
through the reaction:
C02 + H20 = H2C03,

101
the formation of carbonic acid. Carbonate is then released
through the dissociation of carbonic acid which, at a pH
greater than 10.5, occurs predominately through the reaction:
H2C03 = 2H+ C03‘.
This can be seen to be the same net reaction involved in the
dissolution of calcite. Again, any increase in the chemical
potential of calcium, such as from the dissociation of lime or
gypsum, should result in immediate precipitation of calcite.
Thaumasite is not known to have been prepared
synthetically prior to 1973 (Bensted, et. al., 19730. The
original synthesis was achieved from a stoichiometric solution
of gypsum, calcium silicate and calcite. The experiment was
conducted between 1°C and 4°C and required many months to
complete. The reaction products were thaumasite, calcite, and
aragonite. The secondary carbonate minerals formed from
reaction of atmospheric carbon dioxide with the solution.
Since that time, several other workers have synthesized
thaumasite through similar methods (Van Aaudt et. al., 1975,
Kollmann, Strubel, and Trost, 1976). The major differences in
technique are the source used for the silica. These range from
spurrite which gives a very slow reaction, to silica gel, the
fastest of the known procedures. Generally, any clay mineral
works well as clay minerals are broken down at pH greater
10.5 (Eades and Grim, 1950; Davidson et. al., 1965; Thompson,
102
1966). Even using the more soluble silica gel, however,
reactions require several months to reach equilibrium and
produce reasonably well-crystallized thaumasite.
Thaumasite does not appear to form at temperatures above
15 °C (Kollmann, 1978). This is likely a function of the
retrograde solubility of calcite. As discussed, calcite is
nearly insoluble at the pH required to dissolve appreciable
silica. This situation is apparently improved by decreasing
the temperature of the reactions which raises the solubility
of carbonate. Silica solubility, however, decreases with
temperature but remains considerably more soluble than
carbonate at lower temperatures and high pH.

103
CHAPTER 6
*v
METHODOLOGY FOR EXPANSIVE
POTENTIAL AND MINERAL SYNTHESIS EXPERIMENTS
nR.TECTIVES
Lime-induced heave through crystallization of ettringite
and/or thaumasite is a complex geochemical phenomenon. A
series of laboratory experiments were conducted under
controlled, repeatable conditions in order to further the
understanding of the physio/chemical mechanisms involved. The
experiments selected are listed below:
1. Concentration of sulfate in water leaching through soil

from Stewart Avenue
2. Measurement of expansive pressure
3. Laboratory duplication of the expansion observed on

Stewart Avenue
4. Growth of ettringite/thaumasite in soils from other areas
5. Synthesis of ettringite
6. Synthesis of thaumasite
7. Determination of approximate solubility of ettringite
8. Determination of approximate solubility of thaumasite
These experiments included attempts to synthesize and
isolate pure ettringite and thaumasite end members for use m
determining the approximate solubility of each mineral.
Solubility data can be used to calculate the mineral s

104
equilibrium constant, enthalpy of formation, heat capacity, and
free energy of formation. From these data the phase
relationships to other minerals can be determined and stability
diagrams can be calculated. Experiments were also designed to
investigate volume change under several geochemical conditions,
thaumasite/ettringite growth in various soils, nucleation, and
other supporting factors.
All of the water used in the experiments was de-ionized,
doubly distilled and had a conductivity of approximately 18
micro mhos. This water will be referred to herein as purified
water. All high (>8.0) pH solutions were mixed and Stored in
polyethylene containers. Glassware becomes significantly
soluble at a pH greater than 9. The ionized silica could
affect the reactions and would actually substitute for aluminum
in the ettringite structure.
GIJLFATE LEACHING
During the initial investigation of Stewart Avenue
(Chapter 3), it was postulated that water moved to
ettringite/thaumasite nucleation sites by capillarity. The
trilinear and stiff diagrams (Figures 18, 19, 20, and 22)
indicated an influx of sulfate ions, presumably carried m the
capillary water. In order to calculate the ion flux and
mass/volume relations it was necessary to obtain an estim

105
of the concentration of sulfate ions carried in the pore water
of the soil.
For this experiment soil sample S-9C from Stewart Avenue
was selected. This sample was collected at subbase elevation
in the unpaved shoulder adjacent to an area of severe damage.
Chemical analysis of the soil extract (50:1 water to soil
extraction) showed 6500 milligrams of soluble sulfate per
kilogram of soil which is not unusually high.
The soil was compacted into a one-inch (2.54 cm)

diameter, 24-inch (61 cm) long PVC plastic tube. The
soil mass was sufficient to provide a dry density of
107 pounds per cubic foot (pcf; 1.72 gm/cc) or 90-s
compaction relative to ASTM D1557-78. Moisture at
compaction was 10% which was optimum for this soil.
The tube was capped on both ends. One end was
attached to a source of purified water while the
other was connected to a tube draining to ^
collection flask. The system was pressurized at 5
pounds per square inch and maintained at that,
pressure for 20 days. During that time approximately
100 ml of water flowed through the tube.
The water sample was analyzed at the Water Resources
Laboratory of the Desert Research Institute, Reno, Nevada, and
found to contain 5710 mg/liter of sulfate. Since sulfate from
gypsum would only be soluble in pure water at approximately
1250 mg/1, it was hypothesized that most of the sulfate had
been derived from a more soluble sulfate bearing mineral. No
other sulfates had been noted in the original x-ray pattern.
For sample S-9C, however, such minerals would likely be present
in quantities too small for detection. As a check a sample of
soil s-9C was moistened to slightly above optimum and allowed

to air dry in a 250 ml beaker. After a period of a few days
a white efflorescence developed on the soil surface. X-ray
diffraction of this material demonstrated the presence of
thenardite, Na2S04. Sodium sulfate is extremely soluble, in
excess of 10,000 mg/1 sulfate. On this basis it was concluded
that much of the sulfate was probably derived from dissolution
of thenardite or its hydrated counterpart, mirabilite
(Na2S04•10H2O) .
EXPANSIVE POTENTIAL
Expansive Pressure
In order to roughly evaluate the potential expansive
pressure generated by growth of ettringite, a remolded sample
was placed in an Federal Housing Authority (FHA) soil swell
meter. Although the test procedure has no American Society of
Testing Materials (ASTM) or American Association of State
Highway Transportation Officials (AASHTO) sanction, it provides
a reasonably good measure of expansive pressure.
The meter consists of a rigid steel frame supporting

a proving ring and dial indicator above e
base. The soil sample is placed on a porous stone
in an aluminum ring that forms the samp e c •
The specimen, which is one-half inch (1. ^ . +-r>
and 2.5 (6.4 cm) inches in diameter, is compacted to
the desired density with a 5 -pound (2.27 kg) ramm ,
as used for ASTM D-698. Another porous ®t0"® l
placed over the compacted soil fol ov
permeable (drilled) aluminum disc. T h e proving ring
is then brought into contact with t h e disc_ by
adjustment of a threaded steel bar. Wit
107
completed, the apparatus can be submerged to allow

water to reach the soil.
The soil selected for this experiment was sample S-

22C from Stewart Street. Soil was mixed with 6.0%
hydrated lime (4.5% CaO) and densified to 105 pcf
(1.68 gm/cc) at 20% moisture. The sample chamber was
emersed in distilled water and readings taken
periodically.
After 70 days the expansive pressure had leveled off at
7535 pounds per square foot. As shown by Figure 24, the curve
of expansion pressure versus time indicates that the expansion
had reached the maximum value for the test conditions.
The soil specimen was removed from the meter and analyzed
by x—ray diffraction. The pattern indicated the presence of
a small percentage of ettringite or thaumasite. Since no other
new minerals were found it was concluded that the expansive
pressure was, most likely, the result of ettringite/thaumasite
growth. It is also possible, however, that amorphous calcium
silicate or calcium aluminum silicates were, at least, partly
responsible.
Volume Change Experiments
In order to fully evaluate and understand the expansion
mechanism it is a fundamental requirement to duplicate the
expansion measured in the field with a laboratory experiment.
The earliest attempts to measure potential volume change were
based on the assumption that thaumasite, the mineral identified

EXPAN SIVE P R E S S U R E IN POUNDS PER SQ U A R E FO O T
1000 ____________ 2 0 0 0 ____________ 3 0 0 0 ____________ 4 0 0 0 ____________ 5 0 0 0 ____________ 6 0 0 0 ____________ 7 0 0 0
of ettringite/thaumasite.
TIME IN DAYS
Figure 24 Expansive pressure from growth
109
in the field, had formed directly. Later research showed this
to be unlikely, however, the first volume change experiments
were conducted at low temperatures, in the range of 2°C to
22 °C .
The test apparatus selected was an AASHTO T-116 volume
change meter. Although this test has been replaced by more
popular methods it as the advantage of a relatively large,
thin, wide sample with a high surface area to volume ratio.
The brass volume change meter consists of a four-inch (10.2 cm)
diameter mold with a porus stone in the base. A 1 9/16-inch
(4 cm) thick soil sample is compacted into the mold with a
hydraulic press. The mass of the sample is selected so as to
attain the desired density within the given volume. Another
porous stone rests on top of the sample and is attached to a
shaft extending above the top of the mold. A fitted brass
cover slides over the shaft and caps the mold. This cover
stabilizes the shaft but still allows water to enter the top
of the mold. Water also enters the sample from the bottom
through holes in the base and the porous stone. A dial
indicator attached to a tripod rests on the lip of the mold and
measures vertical deflection of the shaft. The mold portion
of the apparatus can be submerged to allow influx of water to
the top and bottom of the sample.

110
T’vpfiriment One fVC-1'1
The four initial tests used sample S-9C taken from an area
of Stewart Avenue with moderate levels of both clay sized
particles and soluble sulfate. The grain size distribution and
soil chemistry of this material are given in Appendices 2 and
6, respectively.
The soil was mixed with 4.5% quicklime (CaO) at 4 %

over optimum moisture and densified to 90% compaction
relative to ASTM D1557. Four reaction solutions were
tried including purified water, water saturated with
Ca(0H)2, water saturated with CaS04, and water
saturated with Ca(0H)2 and CaS04. In all cases the
volume increase was initially rapid and then
gradually stopped within a few weeks. _ _ The
temperature of the experiment was initially
maintained at 2 to 4°C and later raised to 22 C.
Finally the temperature was brought to 45 C.
significant temperature related effects were
observed. The volume changes all were in the range
of 4% to 5.5%. The experiments were then postponed
until a better understanding of the geochemical
mechanism was developed.
Experiment Two TVC-21
Later evaluation and analysis on other aspects of the
research suggested that CaS04*H20 might be too insoluble to
yield the large quantity of sulfate ions required for the
observed heave. Also, research in Germany (Kollmann, et. al.,
1977; Kollmann, 1978) demonstrated that ettringite should have
grown first in the Stewart Street physio/chemical environment
and then slowly changed to thaumasite when the soil temperat
dropped below 15°C. As a consequence of this hypothesis,

Ill
subsequent testing was performed at room temperature in order
to facilitate ettringite growth.
Two experiments were set up for the second phase of

volume change testing. Again, a highly reactive soil
sample from Stewart Avenue (S-9C) was selected and
mixed and compacted with quicklime (CaO), as
previously described. One test apparatus was
submerged in purified water and the other, prepared
identically, was placed in a solution containing
13,450 ppm S042" from sodium sulfate.
After one month the sample in the sulfate solution had
stabilized at a volume increase of 1.5%. The sample saturated
in pure water had only expanded half that amount. At that time
the pure water bath was saturated with Ca(0H)2 and both samples
were allowed to react for another month. No significant volume
increase was observed in either sample and the experiment was
discontinued. X-ray analysis showed only a hint of ettringite,
or possibly thaumasite, in either sample.
Experiment Three fVC-31
The third phase of volume change experiments was an
attempt to reduce the number of variables involved. For this
purpose the mineralogically complex Stewart Street soils were
replaced by "synthetic soil."
The soil test specimen consisted of reagent gr

kaolinite clay blended with 6 . 0 weight percent
C a (OH)2 which is equivalent to 4.5* CaO. Two
specimens were then prepared by blen ing ^ ^
weight percent S0 42'. One sample used CaS04 2H20 an
the other Na2S04 as the sulfate source. ^he y
material was then thoroughly mixed with 40 „ water
112
(by weight) and allowed to cure in a sealed container

for 24 hours prior to compaction. Compaction was to
a dry density of 90 pounds per cubic foot (1.44
gm/cc). The samples were next allowed to rebound for
24 hours. During this time period, a rebound volume
increase of 5.7% occurred in each sample during the
first 11 hours and then stabilized.
The volume change meter containing the calcium

sulfate treated sample was submerged in water
saturated with CaS04-2H20 and Ca(0H)2. In this sample
the concentration of S042' was approximately 1350 ppm.
The Na2S04 bearing clay sample was submerged in an
aqueous Na2S04 solution containing 5500 ppm SO/' and
also saturated with Ca(0H)2. The 5500 ppm was
selected on the basis of the soil leaching
experiment.
This third volume change experiment was kept at a constant
temperature of 22°C for 60 days. By that time both samples
were continuing to expand, however, the rate of change had
become extremely slow. During the first thirty days the Na and
Ca sulfate samples had grown in volume 20.2% and 20.5^;
respectively. In the following thirty days the total volume
increase for sodium and calcium respectively, reached only 20.6
and 20.9%. After the experiment was terminated both specimens
were analyzed by x-ray diffraction. Both samples showed minor
ettringite or thaumasite. Although significant, neither sample
appeared to contain sufficient mineral growth to account for
all of the observed volume increase. Since kaolimte, and
particularly lime-treated kaolinite, is not expansive, it was
concluded that the rapid portion of the volume increase was,
at least, partially the result of overcompaction.

113
TCypariment Four (VC-4)
The fourth volume change experiment used a mixture

(by weight) of 64.46% 30 mesh Monterey sand, 28.2%
kaolinite, 6.6% Ca(OH)2 and 0.74% Na2S04. The sand
was added to simulate the ratio of sand to clays
observed in lime-treated native soil on Stewart
Avenue. The change greatly increases the effective
concentration of lime and sulfate relative to the
reactive (clay) components of the soil. The mixture
was blended with 25% (by weight) water and allowed
to cure in a sealed container for 24 hours prior to
compaction. Compaction was performed hydraulically
in a 2.50-inch (6.35 cm) diameter mold. The mass of
sample used resulted in a dry density of 110 pcf
(1.76 gm/cc) for a sample height of 2.0 (5.08 cm)
inches. The specimen was extruded from the mold and
placed in the 4-inch (10.2 cm) diameter volume change
test meter. The space between the mold and the
specimen was filled with hand—compacted 20 mesh
Monterey sand. The sand had previously been brought
to optimum moisture with an aqueous solution of
Na2S04 (5500 ppm S042') . No significant rebound was
noted in the 24-hour period between placing the
sample in the volume change meter and addition of
the 5500 ppm S042‘ (Na2S04) solution.
Initially the apparatus and the surrounding container of
reactant solution were placed in a constant temperature bath
at 25 ± 0.05 °C . After a period of 63 days the total volume
change was 3.1%. At that time the temperature of the bath was
increased to 40 ± 0.05°C and allowed to react for an additional
30 days. Virtually no additional expansion occurred beyond
that which could be attributed to thermal effects. Analysis
by x-ray diffraction showed only a hint of ettrmgite or
thaumasite.
114
yvpfiriment Five (VC-51
Since ettringite and thaumasite can readily be synthesized
and have been demonstrated to form in lime treated soils, it
was not clear why they could not be easily grown in the volume
change meter. This was especially curious in light of the fact
that ettringite/thaumasite was induced to grow in the previous
test for expansive pressure. For these reasons, it was
hypothesized that the problem might involve a chemical reaction
between the brass (copper and zinc alloy) test apparatus and
the sulfate or hydroxyl ions. A blue efflorescence had been
noted on the mold and was most likely a copper sulfate
compound.
Experiment five of the volume change testing was

conducted in non-reactive devices. Three 2 . 5 - m c h
(6.4 cm) cubes of clear styrene plastic were bored
with a 1.010-inch (2.565 cm) diameter round hole
a depth of 2.0 inches (5.08). A 1.00 inch (2-54 )
diameter PVC piston was then machined to a length
2.5 (6.4 cm) inches. A 0 .0 6 2 - m c h (0.15 £
diameter hole was drilled through the four sides of
the cubes to allow water access to the sample.
Sample charges containing lime-treatedkaolinite were

mixed with sodium sulfate (sample V C-SA), cabci
sulfate dihydrate (VC-5B), and both sodium and
calcium sulfate with calcium carbonate ( .
initial chemistry of the Phase 5 e x p e n m
summarized in Table 4.
115
Table 4
Initial Chemistry fin Grams') for

Volume Change Experiment 5
Sample
Component VC-5A VC-5B VC-5C
Kaolinite 8.75 8.61 8.18

Ca(OH)2 0.50 0.50 .50
Na2S04•10H2O 0.75 0.00 0.37
CaS04•2H20 0.00 0.89 0.45
CaC03 0.00 0.00 0.50
Total Mass 10.00 10.00 10.00
The charges were mixed with 40% doubly distilled,
deionized water and densified in a hydraulic press to 85 pcf
(1.26 gm/cc). The height of the compacted samples was one-half
inch (.13 cm). Each of the three samples were allowed to
rebound for 24 hours prior to being placed in the reaction
solution. Samples VC-5A and VC-5C were submerged in a covered
container filled with a 5500 ppm sulfate solution derived from
sodium sulfate. Sample VC-5B was placed in a sealed container
with a solution saturated with CaS04-2H20. Volume change was
monitored daily with a tripod-mounted dial indicator that
straddled the cube and measured the piston deflection. The
sodium sulfate reaction solution was kept at a nearly constant
ionic strength by monitoring conductivity and making the
necessary adjustments. The calcium sulfate solution was always
saturated by excess gypsum in the container. The temperature
of the experiment was allowed to fluctuate between 15°C and
25 C
116
The three samples were monitored for a period of 100 days
on one- to five-day intervals. The results are shown
graphically on Figure 25. The expansion ranged from a minimum
volume change of 28.8% for sample VC-5C to a maximum of 49%
for VC-5B. Sample VC-5B had the most rapid expansion but
slowed and was surpassed by VC-5A at 31 days. However, by
approximately 55 days the growth of sample VC-5A ceased at
41.4% while sample VC-5B continued to expand. Sample VC-5B was
monitored for another 56 days and finally ceased expansion at
a volume change of 55.0%. X-ray diffraction verified the
presence of significant ettringite/thaumasite in the three
samples. The x-ray pattern for sample VC-5C is included as
Appendix 14.
Experiment Six ('VC-6')
Samples VC-5A and VC-5C were removed after the 100-day
period. These were replaced by two native soil samples from
Stewart Avenue. Test specimen VC-6A consisted of soil from
Test Pit S-15. The soil was collected from native subgrade
beneath damaged lime-treated subbase. Test specimen VC-6B was
soil collected from Test Pit S-18. These soils were selected
because of their high percentage of clay and colloid sized
particles. The grain size distribution and chemistry of the
two soils (S-15C and S-18C) are presented in Appendices 1 and
6, respectively.
PERCENT VOLUME IN CREASE
118
Both soils were mixed with 4.5% by weight CaO and

compacted into the plastic volume change meters at
95% relative compaction and 4% over optimum moisture.
The compaction was performed hydraulically in two
lifts brought to equal pressure of approximately 248
psi. The meters were allowed to rebound for 8 hours
and were then placed in sealed containers containing
purifed water. After two weeks of no response, the
water was replaced with a solution saturated with
gypsum and calcium hydroxide. Response was sluggish
but both samples began expanding at a nearly steady
rate of approximately 1% a week. The temperature
fluctuated between 10°C and 25°C with little effect
on the reaction rate.
The expansion was monitored for over 6 months. The
results of the Phase 6 expansion testing are shown graphically
on Figure 26. The x-ray pattern for experiment VC-6A is
Summary of Experiments on Expansive Potential
The expansive pressure experiment was immediately
successful and demonstrated the ability of ettringite/
thaumasite to generate pressure sufficient to damage pavements
and lightly loaded structures. Volume change experiments,
while initially hindered by unexpected chemical reactions with
the test apparatus, also succeeded. The results are summarized
in Table 5.
PER CEN T VOLUME IN C R EA SE
120
Table 5
Sumarv of Experiments on Expansive Potential
Expansive Pressure
Added Enersion Tenp. Days Expansive Ettringite1

Soil Line Solution Range Duration Pressure Thaunasite
61 Ca(OH)j Distilled 20-25'C 106 7535 psf Weak

S-22C2
H,0
Volune Chanae
Added Enersion Tenp. Days ? Volune Ettringite1/

Line Solution Ranqe Duration Increase Thaunasite
Exoerinent2 Soil
4.5? CaO Distilled H,0 25-32'C 26 4.3 ND

VC-1A 2S-9C
4.5? CaO *Ca(0H)2 25-32'C 26 5.1 HD

VC-1B 2S-9C
2CaS04 25/32'C 26 5.5 ND

VC-1C 2S-9C 4.5? CaO
‘CaS0,+Ca(0H)j 25-32'C 26 5.4 ND

VC-ID 2S-9C 4.5? CaO
Distilled 20-22'C 63 <1 Trace

VC-2A 2S-9C 4.5? CaO
h 2o /
*Ca(0H)j
*HajS04 20-22'C 63 1.5 Trace

VC-2B 2S-9C 4.5? CaO
CaS04.2H304 22'C 60 20.9 Weak
VC-3A Kaolinite + 6.0? Ca(OH)2
0.05? + Ca(0H)j
so2; -
(CaS0.-2H20)
60 2 0 .6 Weak
VC-B Kaolinite + 6.0? Ca(OH)a *Ca(0H)a+5500 22‘ c
0.05? ppn S024

S02;(Na2S04) (N3aS04)
93 3.1 Trace
VC-4A 64.46? Sand + 6.6? Ca(OH)a 5500 ppn 25/40'C
28.2? S042“(Ha2S04)
Kaolinite +
0.74? KajSO,
100 41.4 Koderate
VC-5A 92? Kaolinite 5? Ca(OH)a 5500 ppn 15-25'C
+ 8? S02;(Na2S04)
N a jS O / lO H jO
156 55.0 Hoderate

VC-5B 90.6? 5? Ca(OH)a *CaS04.2Hj0 15-25'C
Kaolinite +
9.41
CaS04-2H30
121
Added Etersion Tenp. Days 1 Volune Ettringite /

Fxperinent3 Soil line Solution Ranee Duration Increase Thautasite1
86.11 51 Ca(OB)j 5500 ppt S0: 15-25'C 100 28.8 Moderate

VC-5C
Kaolinite (HajS04)
+ 3.91
Na2S04-10H20
S-15C123 4.51 CaO *CaS04.2H:0 10-25'C 180 26.4 Weak

VC-6A
+ Ca(0H)2
S-18C2 4.51 CaO ‘CaS04.2H20 10-25'C 180 20.6 Weak

VC-6B
+ Ca(OH)a
1 Relative intensity of Bain x-ray diffraction peak. ND = not detected.
2 Stewart Avenue soil sanple.

3 Experinents VC-1 through VC-4 used AASHTO T-116 brass volune change seter. VC-5 and VC-6 used non-reactive plastic devices.
* Solution aaintained at saturation with these conpounds.

122
■ETTRINGITE/THAUMASITE g r o w t h i n o t h e r s o i l s
Previous research has demonstrated that any clay mineral
will provide an adequate source of aluminum and silicon for
growth of ettringite and thaumasite (Kollmann, et. al., 1977;
Kollmann, 1978). Since numerous areas in the west and midwest
are known to have saline soils, the obvious question is why
there have been so few reported cases of lime-induced heave.
In order to study this problem 14 soil samples from various
locations were mixed with lime to see if thaumasite or
ettringite would grow. The sample locations of these soils are
described in Table 6. Grain size analysis, liquid limit and
plastic index for each of these samples is presented in
Table 7.
Table 6
sample Designations and Locations

of Various Soils for Ettrinaite/Thaumasite Growth
Samole No. nescriotion of Location
BR Black Rock Desert, Humboldt County, Nevada
BS Bonneville Salt Flats, Tooele County Utah

East of Wendover, Nevada, on Interstate 80
CS Carson Sink, Churchill County, Nevada, near

junction of Interstate 80 and U.S. Highway 95
MF Malheur River Floodplain, near Vale, Malheur

County, Oregon
ML Mono Lake, Mono County, California, south shore
NC Near Statesville, Iredell County, North Carolina
NR Northwest Reno, Evans Subdivision, Washington

Avenue, Washoe County, Nevada
123
Pyramid Lake, near Sutcliffe, Washoe County,

Nevada
SF Snake River Floodplain, Homedale, Owyhee County,

Idaho
SA Stewart Avenue, sample S-3C, native soil from

Test Pit No. 3., Las Vegas, Clark County, Nevada
SB Stewart Avenue, sample S-7B, native soil from

Test Pit No. 7, Las Vegas, Clark County, Nevada
SC Stewart Avenue, sample S-27B, native soil from

Test Pit No. 27, Las Vegas, Clark County, Nevada
WL White Lake (Playa) north side, Washoe County,

Nevada
YC Yolo Causeway, Interstate 80 overpass, Yolo

County, California
Table 7
Mechanical Analysis of Various Soils

for Ettrinaite/Thaumasite Growth
a* NC M PL SF SA SB SC WL YC
Sample m BS CS MF
Sieve
Size Percent by Weight Passing
100 100
3/4 97
1/2 93
86 100 95
3/8 94
100 100 100 72 98
No. 4 100 91
100 94 98 100 98 55 95 100
No. 10 100 100 100 100
92 86 95 93 96 94 83
No. 40 99 99 99 99 81 78
80 77 90 42 92 81 83 82
No. 100 98 97 94 98 60 66
73 65 80 38 86 66 74 81
No. 200 97 95 90 94 59 50
Hydrometer
Analysis
22 25 21 15 5 38 44
0.005mm 72 49 35 29 12 14 39
7 6 2 40 1 11 23
0.001mm 31 26 22 11 4 3 21
Liauid 21 47
36 58 51 37 57 52 53
Limit 46 52 44 <45
Plastic 27 6 25
19 42 2 11 43 27
Index 20 22 20 NP
* Weakly cemented with calcium carbonate

124
The soils were mixed with 5% by weight CaO. Enough water
was added to the mixtures to form a thick slurry to allow easy
movement of the ions and, presumably, accelerate the reactions.
All samples were stored in a refrigerator at a temperature of
4 °C +i° C . Each was analyzed by x-ray diffraction after a
reaction period of one year. None of the samples showed
definite thaumasite or ettringite. Seven samples showed
extremely weak peaks in the area of the main thaumasite/
ettringite peak. However, these could not be reasonably
separated from the background.
Three of the soil samples (S-3C, S-7C and S-27C) were from
areas of Stewart Avenue where thaumasite is known to have grown
and damaged lime-treated subbase. The question was, therefore,
why thaumasite or even ettringite, apparently, did not grow in
the experiment. It was hypothesized that, perhaps, these
minerals were simply not present in sufficient quantity to be
detected by standard x-ray powder diffraction. On this
assumption, the maximum percent of ettringite that could be
grown was calculated for Sample S-3C (untreated native soil)
from Stewart Avenue. Chemical analysis of this sample had
shown it to contain 24,500 mg of sulfate per 1000 grams of soil
(Appendix 6 ). On the basis of stoichiometry, specific gravity,
and molar volume it is readily demonstrated that the quantity
of sulfate present could only result in a maximum growth of 4%
by volume of ettringite. This assumes that all of the sulfate

125
is gypsum and that it all reacts to form ettringite. In fact,
the amount of gypsum present in the damaged subbase is often
about equal to that prior to lime treatment. Clearly, not all
of the sulfate reacts. It was concluded, therefore, that even
in high sulfate soils, ettringite/thaumasite may not grow to
the 3-5% by volume necessary for detection by x-ray powder
diffraction. This concept also led to a detailed analysis of
mass-volume relationships presented in Chapter 7.
TC-H-ri naite/Thaumasite Concentration
by the Heavy Liquid Method
Since ettringite/thaumasite might be present in quantities
too small to detect, an attempt was made to concentrate these
minerals in one of the samples using a heavy liquid. Sample
WL was selected as it had shown a very weak, possible peak at
d = 9 .65 X. The heavy liquid chosen was tetrabromoethane which
had a measured specific gravity of 2.95 gm/cc. This was
thinned with methanol to achieve the desired specific gravity
of 2.5. A liquid at this density would allow the lighter
minerals such as gypsum and ettringite/thaumasite to float
while letting quartz, clay, and calcite sink. The net effect
would be to increase the relative percentage of ettringite/
thaumasite in the float. As it turned out heavy liquid
separation was messy and probably contaminated the
ettringite/thaumasite anyway. Many minerals appeared to
dissolve into the liquid and particles that should have sunk
126
(such as quartz) were often kept afloat by surface tension or
trapped air bubbles.
The float was removed, rinsed, dried at room temperature
and x-rayed. The result was a distinctive ettringite/
thaumasite peak in the area of d=9.65 *. The small percentage
hypothesis was concluded to be sound, however, concentration
by elutriation was thought to be a better technique.
Ettrinaite/Thaumasite Concentration by Elutriation
The 14 lime-treated soil samples were air dried at a
maximum temperature of 48°C. Approximately 35 grams of sample
was passed through a No. 200 sieve and elutriated.
In the elutriation procedure the sample was placed

in a 36-inch (91.5 cm) long, one inch (2.5 cm) I.D.
clear plastic tube. Air pressure was applied from
the bottom until the finest particles }ust started
to exit the top of tube. Once the finest particles
were removed the air pressure was increased very
slightly. The material coming out of the tube
this increased pressure was captured on a gla
slide coated with petroleum jelly.
If all of the grains were individual minerals of the same
shape and size those exiting the tube at the lowest air
velocity would be those with the lowest density. Ettringite/
thaumasite, with a specific gravity of approximately 1.8 is
considerably less dense than the clay or other salt minerals
present. Gypsum, for example, is the next lightest min
present in significant quantity and has a specific gravity of

127
2.32. Unfortunately, the minerals are complexly intergrown and
do not separate readily. It is possible, however, to markedly
increase the relative concentration of low density minerals
using the elutriation technique.
Following elutriation x-ray diffraction showed that 6 of
the samples clearly contained ettringite/thaumasite while 4
definitely did not. The remaining 4 (very weak) probably
contained some of the mineral, however, the peaks were not
entirely separable from the background. The presence of common
sulfate minerals was also noted, as summarized in Table 8.
The x—ray diffraction pattern for sample CS is included as
Appendix 16.
Table 8
Results nf X-Rav Analysis of Other Soils

for Ettrinaite/Thaumasite Growth
Sample Ettrinai te/Thaumasite Peak Sulfate Mineral Peaks.
Very weak Very Weak

BR
Very strong None
BS
Strong Strong
CS
None None
MF
None None
ML
None None
NC
Strong Weak
NR None
PL Moderate-strong
Very weak None
SF
SA Weak-moderate
Weak None
SB None
SC None
Strong Very weak
WL None
YC Very weak
128
gVNTHESIS OF ETTRINGITE AND THAUMASITE
As discussed in Chapter 5 both ettringite and thaumasite
have been previously synthesized by a number of researchers.
The problem, then, is not how to synthesize the minerals, per
say, but how to synthesize and isolate them as the purest
minerals possible. This turned out to be a non-trivial, and
not entirely successful, pursuit. Very few of the experiments
were initially successful. The methodology had to be developed
through an evolutionary trial-and-error process. The results
of each experiment were analyzed and compared so that the next
experiment could be designed to answer a specific question or
solve a particular problem.
Synthesis of Ettringite
Ettringite is readily precipitated by mixing a saturated
solution of calcium hydroxide with an undersaturated solution
of aluminum sulfate. When the aluminum sulfate solution was
too concentrated, gypsum was found to precipitate with the
ettringite. In addition, any contact between the calcium
hydroxide solution and carbon dioxide derived from either the
water or the atmosphere resulted in co-precipitation of calci
with the ettringite. Previous researchers had addressed the
gypsum problem (Kollmann, 1978) however, the difficulty with
calcite had not been discussed. For solubility determinations
the purest possible compound is always desirable. Once

129
and/or gypsum form with ettringite the minerals are virtually
impossible to separate in a practical manner.
•Experiment One
Initially the calcium hydroxide solution was prepared

by placing 4.0 grams of Ca(0H)2 on a weighed filter
paper. One thousand milliliters of double distilled,
deionized (purified) water was then passed through
the filter under vacuum. By weighing the residual
lime it was determined that 1.8 grams had dissolved
in 1000 ml of water at 27°C. The amount of aluminum
sulfate that could be added to 1000 ml of saturated
calcium hydroxide solution was then calculated
assuming only 1.5 grams of lime had dissolved. This
lower concentration was used as a safety factor to
help prevent oversaturation of the calcium hydroxide/
aluminum sulfate solution with gypsum. From the
stoichiometry of ettringite, it was calculated that
0.00507 moles (2.89 grams) of Al2(S04)3•18H20 would be
needed to precipitate 1.5 grams of Ca(0H)2 as
ettringite. A solution containing 80 grams per
liter Al,(S04)2*18H20 was made up, again with purified
water. It was calculated that 36 ml of this^sulfate
solution would precipitate the 1.5 grams of (Ca(0H)2.
The 36 ml of sulfate solution were added via a buret
to the hydroxide solution at a rate of 2 3 ml per
minute. Too rapid a mixing rate also results m th
precipitation of significant quantities of 9 YPSum
(Kollmann, 1978). This was confiraed here
accidentally when the mixing rate increased due to
a faulty buret.
As predicted in the literature, a whi^ e ' mil^

precipitate formed immediately Wlth ®ach dr°i\ °
sulfate solution. The solution was th^ filtered,
open to the atmosphere, rinsed with purifi ,
and dried at 35°C.
The dried precipitate was analyzed by x-ray diffraction
using a Phillips Norelco diffractometer. Results of the early
experiments showed poorly to well crystallized ettringite in
approximately equal proportions with well crystallized
Minor gypsum was also present.

130
-E x p e r im e n t Two
It was next assumed that the source of the carbonate was
atmospheric carbon dioxide dissolving in the three aqueous
solutions during preparation and mixing. As a consequence,
the next phase of experiments involved preparation and mixing
of all solutions in an atmosphere of nitrogen.
The calcium hydroxide solution was prepared by adding

4.0 grams of Ca(OH)2 to a 1000 ml flask of purified
water. Air was kept from entering the flask by a
constant, low pressure purge with nitrogen. The
solution was allowed to equilibrate and settle for
at least 48 hours prior to filtration. This was done
in an effort to decrease filtering time and,
consequently, the potential for atmospheric
contamination. During the filtering, a positive
nitrogen purge was applied to the top of the
apparatus, again to minimize contact with C02. m e
solution was stored in a polyethylene erlenmeyer
flask flushed with nitrogen prior to sealing with a
rubber stopper lightly coated with petroleum lelly.
The aluminum sulfate solution was prepared as m

Phase One except that the flask was flushed with
nitrogen as the water was added to the salt. Once
again 36 ml of sulfate solution were added to the
calcium hydroxide solution at a rate of ?h
minute. This time both the buret Gontaining the
aluminum sulfate solution and the PolY ® ^ y l e n
reaction vessel were maintained under a constant
nitrogen purge. The reaction vessel was mixed using
a magnetic stirring device during the en
the aluminum sulfate solution was b em g added. The
precipitate was separated by filtration ae
this time under the shelter of a nitrogen purge.
X-ray diffraction of the precipitate revealed the presence
of poorly crystallized ettringite with an estimated 25% calcite
(Appendix 17). It was found that the crystal structure of the

131
ettringite improved greatly if the precipitate was allowed to
age at least 48 hours prior to filtration. Additional aging
did not appear to improve crystalinity. Also, the crystal
structure showed significant improvement when the precipitate
was dried at 25-30°C. When the drying temperature exceeded
approximately 40°C crystal structure was very poor. One
sample, accidentally dried at 82°C, showed only calcite.
Several attempts were then made to remove calcite from
the precipitate using an acid rinse. The first effort used
purified water saturated with C02. It was hoped that the
carbonic acid would be strong enough to dissolve calcite, yet
too weak to have a significant effect on ettringite. After
drying at room temperature, x-ray analysis revealed that
ettringite had been completely replaced by calcite and gypsum.
A second attempt using 0.1 molal HCl resulted in dilution of
the entire precipitate. As a consequence, the acid rinse
approach was abandoned.
Experiment Three
The source of the C02 contamination remaining, in spite
of the careful nitrogen purge, was eventually found to be m
the deionized, doubly distilled water that had been used for
all of the solutions.
Tn 0f experiments the water was boiled for 30

S n S l s an/pIureS, again with a nitrogen(Purge. into
a flask containing 4.0 grams of lime. After cooling
132
and filtration under a constant nitrogen purge the

calcium hydroxide solution was placed under vacuum
and agitated to help remove remaining dissolved
gases. Next the solution was bubbled with nitrogen
to displace as much of the remaining C02 as possible.
The flask was then sealed and stored. The rest of
the procedure was performed as previously described
except that water for the aluminum sulfate solution
was also boiled, subjected to vacuum and bubbled with
nitrogen.
When this precipitate was x-rayed it showed large, well
defined peaks for ettringite indicating both a high percentage
of ettringite and good crystal structure (Appendix 18).
Although calcite was still present, it appeared to be a
relatively minor component. Estimates based on x-ray
diffraction indicated that the purest ettringite synthesized
contained less than 1% calcite by weight. In this semi-
quantitative analysis an internal standard was used by adding
a known weight percentage of calcite to the ettringite and
comparing the effects on the area of the main calcite peak.
The analysis was run with -pure1' ettringite, ettringite plus
2% calcite, and ettringite plus 5% calcite. The weight percent
calcite in the "pure" ettringite was then estimated
graphically, as shown in Figure 27.
It was concluded that the synthetic ettringite from
experiment three was quite good and would be suitable for the
purpose intended. Efforts to obtain a more pure product would
be time consuming and not really justified. The ettringite
synthesis experiments are summarized in Tabl

133
in synthetic ettringite.
P E R C E N T C A L C IT E CALCULATED FROM PEAK AREA
134
Table 9
Summary of Ettrinaite Synthesis Experiments
Saturated
Ca(0H)2 Solution A 1 2( S 0 J 2*18H20 Mixing n2
Experiment f0.024 m( Solution (0.120 mi Water Kate Purge Results
1000 ml 36 ml Double 2-3 Ho Ettringite with

ES-1
distilled; ml/min much calcite;
deionized minor gypsum.
1000 ml 36 ml Double 2-3 Yes Ettringite with

ES-2
distilled; ml/min less calcite than
deionized ES-1. No gypsum
detected.
36 ml Double 2-3 Yes Excellent

ES-3 1000 ml
distilled; ml/min crystalline
deionized; ettringite with
boiled; trace calcite
bubbled with an^ no gypsum
nitrogen after detected
mixing with CaO
and cooling.
Synthesis of Thaumasite
Experiment One
Attempts to synthesize thaumasite began in July 1983
From the procedures described by K o l l n a n n (1978)'

stoichiometric mixtures of Ca(OH)2/ a 3, 4 ^
and Si02 were added to purified w a t e r * ° off s i l i S
aqueous solution. Four different sourcesôf sil
were used in the initial experiments, as shown
Table 10.
135
Table 10
Thaumasite Synthesis
Initial Chemistry of Experiment One Group
Silica Source
Group
TS1-1 #325 mesh Si02 glass spheres

TS1-2 -200 mesh Ca2Si06 (amorphous)
TS1-3 -100 mesh Type I Portland cement
TS1-4 -200 mesh fly ash
Initial Chemistrv1— Grams
H 20 H 20
Sample CaS04-2H20 CaC03 Ca(0H)2 Si02 Initial Final2
TS1-1A 34.4 20.0 14.2 24.0 100 290

34.4 20.0 14.2 24.0 75 75
TS1-1B
. 34.4 20.0 14.2 24.0 50 550
TS1-1C
34.4 20.0 14.2 21.2 125 125
TS1-2A
34.4 20.0 14.2 21.2 150 200
TS1-2B
34.4 20.0 14.2 21.2 175 375
TS1-2C
20.0 14.2 60.0 150 250
TS1-3A 34.4
20.0 14.2 17.0 150 250
TS1-4A 34.0
1Stoicionetric for 1/10 mole of thaumasite

"Included water added after approximately thirty days reaction
time.
The solutions were mixed in 1000 ml erlenmeyer flasks

and placed in a Haake Model NK-22 water bath
maintained at a constant temperature of 30 1 C.
Various initial water contents were tried in an
effort to find the optimum consistency. More water
was added to some of the samples after 30 days m
order to maintain a slurry-like consistency.
After a period of three months each of the samples was
analyzed by x-ray diffraction. The powder method employed is
only capable of detecting crystalline solids present m
quantities greater than 3 to 5%, by volume, of the
sample. Thaumasite was detected only in samples '
TS1-2B, TS1-3A (Appendix 19), and TS1-4A.

136
Portland cement has been commonly been used as the silica
source in previous research (Kollmann, 1978) since the silica
in cement is particularly reactive at high pH. Type I cement
typically contains approximately 20% silica, by weight. Fly
ash is derived from burning of coal in coal-fired power plants.
The resulting ash contains a high percentage of high
temperature, amorphous silica that is unstable at low
temperature and high pH. Typically, fly ash contains 62 to 82
weight percent Si02 + Al203 + Fe203, with silica and aluminum
being the dominant components. Fly ash is frequently used in
concrete as a substitute for up to 30% of the Portland cement.
The fly ash increases the concrete's resistance to
attack (M e h t a , 1986).
Of the three successful experiments, the Portland cement
produced the highest quantity of thaumasite (most complete
reaction) as well as the best orystal structure. In all of

CaS04-H20 were still
these experiments Ca(OH)2, CaC03, and
was amorphous, could
present. The silica, which in all cases
It is difficult to
not be detected by
x-ray diffraction.
, . „ v,., v-r-av diffraction, without
quantify mineral proportion Y
, using this standard
using an internal standard. Even usi g
quantitative determinations are difficult in multi-component
systems. Since one of the components in the thaumasrte
synthesis is amorphous only crude approximations are possible
internal standard was used. Based simply on the

anyway so no
137
area of the main peaks, estimates were obtained for the
percentage of thaumasite present (relative to crystalline
compounds) in the four samples:
Table 11
Estimated Percentage of Thaumasite

In Experiment One Samples
Sample No. % of Thaumasite
TS1-2A <5
TS1-2B <5
TS1-3A 20
TS1-4A 15-20
Following the initial x-ray analysis samples TS1-1A and
TS1-2B were "seeded" with thaumasite from sample 0-2B from
Owens Avenue. The portion of the sample used in the seeding
consisted of a minus 50 mesh plus 60 mesh fraction that had
been elutriated to concentrate the low density mineral,
thaumasite. Sufficient air pressure was applied to the bottom
of the elutriation tube so that particles just reached the top
of the tube before falling back down. The sample was allowed
to mix in this manner for approximately 5 minutes. At that
time the air pressure was slowly increased until a tiny amount
of the soil was blown out of the top the tube. A filter bag
was then placed over the top of the air tube. Another sl'g
increase in air pressure raised a portion of the particles int
the filter bag. Experimentally it was found that separating
approximately 20% of the soil in this manner produced the
highest concentration of thaumasite. Although far from pure,
the product was suitable for seeding purposes. The elutriation

138
technique, however, was shown by this experiment to be
incapable of separating even reasonably pure thaumasite from
the Stewart/Owens Avenue soils.
Experiment Two
Samples TS1-1B, TS1-1C, TS1-2A, and TS1-2C were abandoned
following the initial x-ray analysis.
New samples were prepared using Portland cement

(TS2-3B and TS2-3C) and fly ash (TS2-4B and TS2-4C)
(Table 12). Samples used stoichiometric proportions
of the component minerals with an excess of Portlan
cement or fly ash. All four samples were seeded with
0 5 gram of thaumasite concentrate prepared by
elutriation of sample S-7B from Stewart Avenue.
Table 12
Thaumasite. Synthesis
al Cheini strv of Pxneriment Two Group
Source Initial Thaumasite
H20 Seeding*
Sample CaS04'2H20 CaC03 Ca(0H)2 Si02
initial Ohemistrv--Grams
34.4 20.0 14.2 60 1000 0.5

TS2-3B
10 7.1 30 1000 0.5
TS2-3C 17.2
10 7.1 9 500 0.5
TS2-4B 17.2
10 7.1 9 1000 0.5
TS2-4C 17.2
*Sample S-7B, Stewart Street.
The progress of the reactions of Experiment Two and
remaining groups from Phase One were monitored by x-ray
diffraction for over three years. The results are summarized
in Table 13. Again, quantitative interpretation from x-ray
patterns containing multiple minerals is, at best, approximate
and impossible when amorphous compounds are present.

139
addition, a variety of sample preparation techniques were
employed, further complicating the data. The important point
shown by the results is that changes in the areas of the
primary x-ray peaks, and presumably in the proportions of the
minerals, did occur and that the percentage of thaumasite
increased with time.
Table 13
Estimated Percentages of Thaumasite in R emaining

Samples of Experiment One and Experiment Two**
Sample TS1-3A
Thaumasite Gvosum Calcite Portlandite

Date
20 25 30 25
09/24/83
25 10 15 50
11/06/83
15 15 40
12/03/83 30
10 15 40
01/08/84 35
Sample TS2-3B
15 20 40
01/08/84 20
15 40 5
03/04/84 40
0 5-10 50
40-45 10
* 80 0 10
Sample TS2-3C
40 30 20
11/06/83 10 15
03/04/84 40 5 40
Sample TS2-4A
25 55 0
09/24/83 20
Sample TS2-4C
30 15 40
11/06/86 15
* Relative to crystalline compounds.

** Petroleum jelly slide preparation.
140
Fvpftriment Three
In October 20, 1985, six new experimental specimens were
prepared using silica gel as the source of Si02. Samples were
prepared using the following proportions:
Table 14
Thaumasite Svnthesis-Initial Chemistry of

Experiment Three
Initial Chemistry1 (Grams)
Sample CaC03 Ca(0H)2 i4’1/2H20 Si02 gel H 20
4.00 2.96 5.80 2.40 50

TS3-A
8.00 2.96 5.80 2.40 50
TS3-B
4.00 5.92 5.80 2.40 50
TS3-C
4.00 5.92 11.60 2.40 50
TS3-D
4.00 5.92 5.80 4.80 50
TS3-E
2.96 5.80 2.40 50
TS3-F2 4.00
^ to ic i o m e t r i c proportions for 1/50 mole

20pen to atmosphere
X-ray diffraction analysis of each sample was performed
after 30 days but no thaumasite was detected in any sample.
The reason for this was thought to be the relatively large
particle size (#16 mesh) of the silica gel.
New batches of Samples TS3-A through TS3-G for

Experiment Three were prepared on Novembe ' tg
This time the silica gel and all other
were pulverized to -200 mesh. Component proportions
were as previously shown (Table 14).
X-ray diffraction analysis on January 18, 1987, showed the
following estimated percentages of crystalline compounds.

141
Table 15
Results of Thaumasite Synthesis

ExDeriment Three
Estimated Percentaae of Crystalline Compound
Sample Thaumasite Gypsum Portlandite Calcite
TS3-A 40 35 0 25
TS3-B 30 15 0 55
TS3-C 45 20 0 35
TS3-D 30 50 0 15
TS3-E 15 55 0 30
TS3-F 25 20 0 55
The x-ray pattern for Sample TS3-C is shown in Appendix 20.
Experiment Four— Two Solutions
Since ettringite can be readily precipitated by mixing two
appropriate solutions it was hoped that a similar procedure
might work for thaumasite.
One thousand milliliters of a solution saturated with

Ca(OH)2/ Si02 and Ca(S04) •1/2H20 was prepared by
placing 10 grams of each in a flask with purifie
water. The solution was allowed to equilibrate for
two weeks prior to slow addition of a second solution
of pure water saturated with C02.
The two solutions were stored and mixed at a

temperature of 3.5°C. The C02 solution was added to
the more complex solution with a buret at a rate of
one ml per minute. A white precipitate formed
immediately on contact between the two solutions.
X-ray diffraction analysis showed the precipitate to
consist of an estimated 70% calcite and oO-s gypsum. No
thaumasite was detected and the concept was pursued no further.

142
Experiment Five— Separation/Osmosis
The hypothesis was made that thaumasite might
preferentially nucleate on a single compound. If this was
true, pure thaumasite might be synthesized by separating the
nucleation sites from the remaining compounds by a permeable
membrane.
In an attempt to ascertain which, if any, compound

is the preferred thaumasite nucleus, each was
separated from the remaining components by a filter
membrane. The compound being studied was placed in
the top of a Nalgene 125 ml membrane filter unit with
125 ml of C02 free, purified water. The remaining
compounds were placed in the bottom of the cham er
with 150 ml of purified, C02 free water. The
components were of stoichiometric proportion f /
mole except that the compound isolatedL in the top
compartment was only sufficient for 1/100 mole. This
was to promote as complete a reaction as possible y
keeping the compound under investigation in relative
short supply. The experiment was allowed to stand
at 3.5°C for 6 months.
Samples from each of the two chambers were analyzed by
x-ray diffraction. The results obtained are summarized in
Table 16.
143
Table 16
Results of Thaumasite Synthesis

in Experiment Five
Amorphous
Sample # Thaumasite CaCO. CaSO.'l /2H20 carom. sio,__
TS5-At + +*
TS5-Ab + -
TS5-Bt +* -
TS5-Bb + +
+ - -* -
TS5-Ct +
TS5-Cb + +
_ -*
TS5-Dt
TS5-Db + + +
TS5-Et + — — +*
TS5-Eb + +
= top compartment, b = bottom compartment

* ft
component isolated in top compartment

+ = detected by x-ray diffraction
- = not detected by x-ray diffraction
On the basis of these results it appears that thaumasite
does nucleate preferentially as Ca(OH)2. However, there did
not appear to be any great potential for synthesis of pure
thaumasite. The reactions were incomplete and only a small
amount of thaumasite formed.
Experiment Six— Kinetic Exchange
German research (Kollmann, et. al., 1977, Kollmann, 1978)
has demonstrated that a high pH solution containing calcium,
aluminum, sulfate, silica and carbonate will grow e t t n n g i t e
above a temperature of 15 °C but not thaumasite. Below this
temperature, and particularly in the range oj.
ettringite grows first and then slowly changes to thaumasite

144
through a gradual transition. This suggests that, while
ettringite may be kinetically favored over thaumasite,
thaumasite may be thermodynamically more stable below 15 C.
This hypothesis opens the possibility of converting reasonably
pure ettringite to thaumasite.
In experiment six ettringite was prepared by the best

methods previously developed and described in this
research using vacuum filtration and a nitrogen
purge. The samples were not allowed to dry and were
not aged. It was thought that both aging and drying
could "tighten" the crystal structure and make the
transition more difficult.
The ettringite was placed in the top compartment of

a Nalgene 125 ml membrane filter unit. The bottom
compartment contained the other components necessary
for the conversion. Both compartments were filled
with de-ionized, distilled water. The following
experiments were set up:
Table 17
Initial Chemistry of Thaumasite Synthesis

Experiment Six
initial Chemistry-Gms
Top Chamber Bottom Chamber
Sample Ettringite CaCO. Ca(0H)2 Si02 gel Kaolinite**
5.0 1.8 * 0.5 0.0

TS6-EA
TS6-EB 5.0 1.8 0.5 0.5 0.0
TS6-EC 5.0 1.8 0.5 0.5 0.0
5.0 1.8 0. 5 0. 0 2. 0
TS6-ED
* pH brought to 8.0
** API standard {9
The ettringite from the isolated (top) chambers of Samples
TS6-EA and TS6-EB was x-rayed after 20 days. Although each
sample showed some changes in its x-ray pattern,

145
clear what these changes meant. The samples were allowed to
react for over 30 months before they were checked again. The
later x-ray patterns of Samples TS 6 -EA, TS 6 -TB, and TS 6 -EC were
distinctive for ettringite. In fact, the ettringite seemed
more pure and more crystalline than when the experiment was
started. Sample TS 6 -Ed, however, showed definite double peaks
in the areas of d = 9.7J and d = 5.0J indicating some reaction.
The two peaks that really differentiate thaumasite from
ettringite (d = 4.58J and d = 3.792) were not present and the
approach was deemed unsuccessful. The x-ray pattern for sample
TS 6 -ED is included as Appendix 21.
SUMMARY
Six major experiments were conducted to synthesize
thaumasite pure enough for solubility/thermodynamic
determinations. Although most of the experiments did yield
significant thaumasite, none produced thaumasite sufficiently
isolated from other components that it could be separated and
purified. The effort was abandoned following experiment six.

146
CHAPTER 7
THE THERMODYNAMICS OF ETTRINGITE DISSOCIATION
experimental methodology
The solubility of ettringite was determined at 10 C, 25 C,
and 40°C. For these experiments the purest ettringite
previously synthesized was placed in each of two polyethylene
erlenmeyer flasks. A sample containing gypsum was also
prepared. Since its solubility is well established, gypsum
was used as a check on the experimental techniques. Finally,
a dilute solution containing calcium chloride was prepared.
A calcium chloride solution would turn milky when exposed to
carbon dioxide and serve as a visual indication of C0 2
contamination.
A magnetic stirring rod and doubly d ^ t i l l e ^

deionized water were added to each f_lask. 'r*e_ ^ e r
had been boiled for 30 minutes and placed in a se<al
polyethylene bottle to cool m order to minimize the
amount of dissolved C0 2 present. The composition
solutions are shown in Table 18.
147
Table 18
Composition of Solutions used in Determininq

Ettrinaite Solubility
Sample ET-B ET-C** G CaCl2
Grams of Components
Synthetic
Ettringite* 0.400 0.400 0.400 0.00 0.0
Gypsum 0.0 0.0 0.0 2.00 0.0
Calcium
0.0 0.0 0.0 0.0 8.800
Chloride
800.0 800.0 800.0 800.0 800.0

H 20
* Synthesized in ettringite synthesis Experiment Three.

** Added after measurements at 10° and 40 C.
Air in the flask was displaced with a nitrogen purge prior
to and during the time the water was added. The flasks were
then sealed with a rubber stopper lightly coated with petroleum
jelly. Since the flasks were polyethylene excessive stirring
would have worn a hole through the bottom. The magnetic
stirrers were set with an electronic control that mixed each
flask for a twenty-minute interval every eight hours,
addition the solutions were stirred for ten minutes prior to
any measurements or sampling. Several variations
stirring and settling times prior to conductivity measurement
were tried. No significant variation was noted, as long as the
solutions were stirred briefly for a few minutes prior to the
measurement. Even if the solution was not stirred the

. „ oi irjhtlv lower than when the
conductivity readings were only si g Y
sample was stirred.

148
It was assumed that ettringite would have normal, as

opposed to retrograde, solubility. Since it is
kinetically easier to dissolve a mineral than it is
to precipitate it from a slightly oversaturated
solution, it was decided to proceed from the lowest
to the highest temperature. The temperature of the
solutions was maintained constant using a Haake Model
NK-22 constant temperature bath. Since the unit
itself would not hold more than one flask, an
auxiliary, insulated and covered bath was connected
to the main controller. All sample flasks were
placed in the larger bath, along with the standard
solutions for pH and conductivity.
Unfortunately, the temperature controller in the bath was
malfunctioning such that when set at 10 C, temperatures
fluctuated between 3°C and 20°C. Occasionally the temperature
would rise to 25°C. A phone call to the distributor suggested
a faulty temperature controller. A new controller resulted m
a false sense of improvement. The temperature would seem to
remain nearly constant for a period of several days,
fluctuating only one to two degrees. This resulted m a
considerable waste of time as it continually appeared that "one
more adjustment" should produce the desired stability.
Finally, after a frustrating period of trial and error, the
constant temperature unit was returned to the Desert Research
Institute for repair. Approximately eight weeks later the unit
was returned and operated perfectly from that time on
temperature could be easily set and maintained within ±-0.1°C.
The temperature controller was a d j u r e d to the

desired temperature and the samples a l l o w e d t o
equilibrate. Initial “Samples!
a
cno nduPctivTtye w“ dL a ° s ureTwitnfa Barnstead Model PM
149
70CB conductivity bridge. Measurements of pH were

taken with a Beckman Model 4500 digital pH meter
using a Corning 476051 electrode. The pH meter was
standardized using NBS traceable buffer solutions of
pH 7.00 for the gypsum and calcium chloride solutions
and pH=10.00 and 11.00 for the ettringite solutions.
Conductivity was standardized for the 10 C
measurements with a 140 millimho solution of KCl.
A 280 millimho KCl solution was used for the
experiments at 25"C and 40 C.
Progress toward equilibrium was monitored

periodically by measurement of conductivity.
Measurements of pH were minimized in order to
minimize contamination of the solution from K, Na,
and Cl in the electrode. All measurements of
conductivity and pH were made under a constant
nitrogen purge. Results are summarized below for
the three selected temperatures.
Table 19
Conductivity finKicromhosl and pH of

Ettringite Solubility Experiment at lO'C
ET-10A ET-10B G-10 CaCl^lO

Sample. Conductivity pH
Conductivity pH Conductivity pH Conductivity pH
Date
10.38 825micromhos 6.27 819 7.51
08/22/87 91 10.36 91
269 _____
1,450 — 1,450 . . .
09/02/87 269 —
6.15
407 11.12 1,920 6.13 1,920
01/21/88 404 11.12
— 403 — - 1,980 — 1,760 . . .
02/01/88 406 ___ 1,860 —

413 1,980 6.26
02/06/88 415 —
1,860 6.17
11.20 414 11.20 1,980 6.26
02/07/88* 416
* Samples collected for analysis

150
Table ?0
Conductivity finKicromhosl and cH of

Fttrinaite Solubility Element at 25*C
ET-25A ET-25B G-25 CaCl525

Conductivity pH Conductivity pH Conductivity pH Conductivity pH
Date
481 ___ 476 — 1.94 — 1.93 —

02/15/88 ...
464 — 466 — 2.07 — 1.93
03/01/88 ...
444 — 449 — 2.07 — 1.95
...
429 ... 433 — 2.08 — 1.94
03/15/88
■Raisedtemperature to 60*ConMarch 16, 1988. Droppedto 40'ConMarch 20, 1988 andbackto 25ConHay 10, 1988,
—
431 ... 421 — 2,090 ... 1,890
05/12/88 ...
433 421 — 2,090 — 1,930
05/24/88 5.40
427 10.85 421 10.80 2,070 6.11 1,920
06/05/88 — ... ...
—
418 — 399
... 397 — 2,060 — 1,930
06/26/88 417
10.68 390 10.61 2,070 — 1,910
06/28/88 416 — ... ...
—
07/01/88 415 — - 383
... 374 — 2,050 — 1,920
07/10/88 404 — ...
07/13/88 ... — — 2,070
— —
07/17/88 403 365 — 2,030
... 361 — 2,040 — 1,890
07/24/88 401 — 1,910
07/31/88 398 ... 355 — 2,070
10.90 348 10.71 2,040 6.11 1,900
08/06/88* 390
New Sample - ET-25C
conductivity pH
395 10.93
08/06/88
08/08/88 412
416 10.75
08/09/88 — -----------
08/10/88 415
— — —
08/12/88 415
414 10.60
08/13/88*
* Samples collected analysis

151
Table 21
Conductivity finKicromhos) and dH of

Ettrinaite Solubility
Exoerinentat 40*C
ET-40A ET-40B G-40 CaCl£'

Conductivity Conductivity dH Conductivity B2 Conductivity $
Date $
446 ___ 441 2060 ... 1940

03/22/88
436 ____ 429 2080 — 1900
03/29/88
04/11/88 448 ____ 438 2090 — 1900
453 ____
438 2120 — 1980
04/23/88
449 — 436 2200 — 1920
05/03/88
10.20 438 10.12 2110 — 1920 5.92
05/10/88* 450
* samples collected for analysis
A preliminary ettringite solubility sample at approxi
mately 22"c (room temperature) had been analyzed for component
ions in an effort to establish the anticipated ionic concen
trations. This was necessary to allow the laboratory to
establish appropriate dilution factors and test procedures for
a mineral with an unknown solubility. The sample was prepared
by simply placing 0.3 grams of low grade ettringite (containing
more than 5 % calcite) into a polyethylene container with 1000
ml of doubly distilled, deionized water. The sample was purged
with nitrogen, sealed, shaken frequently, and allowed
equilibrate for approximately four weeks at 22-25°C. Results
of the analysis are presented in Table 22.

152
Table 22
Chemical Analysis of Preliminary Sample for

Fttrincrite Solubility
Description Ca A1 S04 C0 3 OH
Mg/liter 33.0 8.2 41.0 15.9 9.8
All solutions for analysis were collected under a

constant nitrogen purge both in the experiment flask
and the sample container. In order to keep the
liquid to solid ratio nearly constant in the
experiment flasks, the samples were kept very small.
Based on the preliminary analysis (Table 22) a
dilution of 1 0 : 1 was selected as the most appropriate
for the anticipated concentrations and the
requirement for a small sample size. _ .Fifty
milliliters (50 ± 0 . 1 ml) of boiled, doubly distilled,
deionized water were placed into each of five 1 2 5 mi
polyethylene sample bottles _using 3 pipette ®
water had been brought to 20 C(±l), the calibration
temperature for the pipette. Five miHiiite:rs (5.00
+ 0 1 ) of water were then removed from the sampl
container with a 5 milliliter pipette. Two. five ml
( 5 0 0 + .0 1 ) solution samples were collected from each
of the ettringite experiment flasks with the same
pipette . A d d i t i o n of the samples to the Previously
prepared sample bottles resulted m e esi ^
dilution. In one sample from each of the
ettringite flasks the water had previously Totsen
acidified by five drops of nitric acid in ord«-r
keep the aluminum in solution. It was assumed
the dilution would keep the other ion
precipitating, in spite of the temperature change
between the bath and the sample bottle; Th® '
in the bottle was at the, temperature of the
uncontrolled environment, typically 20-25 o.
gypsum sample was prepared for each

Only a single
procedure was identical to that of
temperature. The
ettringite, however, no acidification was necessary.
All solution analyses were performed at the Desert
Research Institute, Water Resources Center laboratory in Reno,

153
Nevada. The ettringite samples were analyzed for calcium,
aluminum, carbonate, and sulfate which were known to be the
only major ions present. The gypsum sample was analyzed for
calcium and sulfate and the calcium chloride solution was not
analyzed at all. Because some contamination would be expected
from the pH electrode, samples were also checked for sodium,
potassium and chloride.
After the solutions had approached equilibrium at 10 C (as
shown by constant conductivity) the temperature of the bath was
raised to 25 +0.1°C. The conductivities were monitored for 30
days. During this period the conductivity dropped steadily
giving the impression that ettringite was precipitating rather
than dissolving. In addition, comparison of analytical results
from the preliminary sample (22°C) and the experiment at 10°C
also suggested that ettringite had retrograde solubility. As
a consequence it was decided to raise the temperature of the
bath to 60°C, let the solutions equilibrate for several weeks
and then lower the temperature to 40 C. In this way the
ettringite, if it indeed was of retrograde solubility, should
precipitate slowly at 60'C and begin to redissolve at the 40 “C.
Again the kinetics of dissolution and nucleation/precipitation
favor this approach.
The solutions were maintained at 40 ‘ ±0. l ‘C for six weeks,
easonable stabilisation of the conductivity measurements was
ctually reached in only 3 weeks. After sampling, the tempera-

154
ture was lowered to 25° ±0.1°C and maintained for 8 weeks.
This time the conductivities for ettringite declined slowly and
then seemingly leveled off. However, in the 9 days between the
final two readings, the conductivity for both ettringite
samples dropped markedly. At that time the 25 C samples were
collected and submitted to the Desert Research Institute, Water
Resources laboratory. Because the samples at 25"c are critical
to the analysis of the ettringite dissociation constant and
because they had shown behavior inconsistent with equilibrium,
a third sample was prepared. The conductivity and pH
measurements for ET-25C were also shown in Table 20.
EVALUATION OR THE ANALYTICAT, DATA FROM THE SOLUBILITY
EXPERIMENTS
The results of the water sample analyses performed during
the ettringite solubility experiments are presented m
Table 23.
Table 23
Analytical Results of Ettringite Solubility Samples
jnalvsis in Mg/Liter
Ca Na K Cl SO, n C03
Samcle No.
4.1 2.5 7.0 70.0 13.0 63.0

ET-lOa 57.8
3.4 2.1 6.0 73.0 13.0 63.0
ET-lOb 58.9
1 2 86.0 17.0 36.4
ET-25a 64.9 1
1 2 87.0 16.0 20.6
ET-26b 62.3 1
1.5 1.7 2 70.0 13.0 57.0
ET-25C 61.6
1.2 5 97.0 18.0 88.5
ET-40a 76.8 3.4
1.8 6 98.0 18.0 85.5
ET-40b 74.5 3.4
2.3 7.0 1230 — <15

G-10 59.4 5.5
<1 <2 1450 — <15
G-25 60.9 <1
1.4 5.0 1480 — <15
G-40 60.5 12.1
155
These data were entered into the WATEQDR computer program
(Bohm and Jacobson, 1981). WATEQDR is an ion-paring chemical
model for determining the distribution of species in waters.
At the present time the program does not consider either
ettringite or thaumasite since their thermodynamic properties
were not known. The program, however, is extremely useful in
calculating the individual ion activities in complex aqueous
solutions. WATEQDR also provides the analytical and calculated
milligram-equivalents per kilogram of the input species. In
entering the data, the total analytical carbonate was split
into carbonate and bicarbonate, as appropriate, on the basis
of solution pH.
The milligram-equivalents per kilogram (epm) of the 10
solutions is summarized in Table 24.

156
Table 24
EPM Balance of Analytical Data
Milligram-Equivalents per Kilogram
Net 1 Net 1
Na K Cl SO, CO, HCO 3 Analytical Error Computed Error

A1 Ca
Sample
'1.458 ' 2 .1 0 0 - .818 9.8 '.646 11.3

ET-lOa 1.446 2.885 .178 .064 M 9 7
.148 .054 -.167 '1.520 ' 2 .1 0 0 -- .797 9.5 .665 1 1 .6
ET-lOb 1.446 2.940
'1.791 ‘1.213 - 2.138 25.9 2.156 32.7
ET-25a 1.891 3.239 .044 .026 '.056
'1.812 '.687 -- 2.403 32.0 1.063 18.0
ET-25b 1.779 3.109 .044 .026 '.056
'1.458 "1.900 -- 1.215 15.1 .244 4.5
ET-25C 1.446 3.074 .065 .044 '.056
1.615 15.5 .407 6 .1
ET-40a 2 .0 0 2 3.833 .148 .031 ".141 " 2 .0 2 0 "1.500 ".738
'2.041 '1.434 '.721 1.55 15.1 .465 7 .2
ET-40b 2 .0 0 2 3.719 .148 .046 ".169
-- '.123 4.017 7.2 3.948 1 0 .1

G-10 29.696 .240 .059 ’ .198 '25.656
__ - '.123 .205 0.3 .098 0 .2
G-25 30.453 .436 .256 '.565 '30.253
-- '.123 ".326 0.5 .427 1 .0
G-40 — 30.253 .527 .036 ".141 "30.879
Unfortunately, there is considerable error in some of the
analyses. The computed balance is off by as much as 33% for
ET-25a and 18% for ET-25b. Fortunately, sample ET-25C was much
better with an error of 4.5%. This is within the 5% error
normally assigned to the analysis of each of the ions (Jim
Heideker, 1988; personal communication).
The reason for the discrepancies in the epm balance is not
readily apparent; however, a comparison of the mole ratios
provides considerable insight. Table 25 compares the
stoichiometric mole ratios of ettringite to those calculated
from the analytical data.

157
Table 25
Stoichiometric and Measured Hole Ratios
Ettringite Samples
Stoichiometric Calculated Ratio:1

Mole
Katio ET-lOa ET-lOb ET-25a ET-25b ET-25C ET-40a ET-40b
Ions
3:1 2.99 3.03 2.57 2.62 3.19 2.87 2.79

Ca: Al
2:1 1.98 1.93 1.81 1.72 2.11 1.89 1.82
Ca:S04
1.5:1 1.51 1.58 1.42 1.53 1.51 1.51 1.53
S04:A1
Gypsum Sample
Stoichiometric Calculated Ratio:!

Hole
Ions 'Rati o G-10 G-25 (HO
Ca:S04 1:1 1:1.16 1:1.007 1:0.98
For samples ET-lOa and ET-lOb the calculated ratios are very
close to the stoichiometric ratios. The calcium to aluminum
ratio show virtually no calcium beyond that necessary for
ettringite. The calcium to sulfate ratio indicates that either
sulfate is slightly high or calcium is slightly low. The
sulfate to aluminum ratio is slightly high which,
combination with the calcium aluminum and calcium:sulfate
ratios, suggests that, in reality, the measured sulfate is
probably a little low. The data for samples ET-lOa and ET-lOb
support the x-ray analysis that indicates very little calcite
contamination in the ettringite. Most of the carbonate
probably came from either the boiled, purified water or from
air entering the flask in spite of the nitrogen purge. Since
the experiment lasted for over a year it is possible that some

158
carbon dioxide entered the polyethylene flasks by diffusion
through flask walls. In any case, the mole ratios and the
computed negative epm imbalance suggest that most of the error
for ET-lOa and ET-lOb is in the measurement of the carbonate.
The calcium to aluminum and calcium to sulfate mole ratios
for samples ET-25a and ET-25b are very low. Since the ratio
of sulfate to aluminum is fairly close, either both sulfate and
aluminum are low, in which case the sulfate to aluminum ratio
is fortuitous, or the measured calcium is too low. Even if the
calcium is raised to the ideal mole ratio, a negative balance
remains. It seems likely that errors in measurement of both
calcium and carbonate have compounded to yield the large, net
negative imbalance. Again, however, the analysis supports the
initial purity of the ettringite.
Sample ET-25C was mixed over a year after Samples ET 25a
and ET-25b using a split of the same synthetic ettringite.
Sample collection and analysis of ET-25c was performed only a
month later than for the original two solutions. In this case,
both the epm balance and the mole ratios are pretty good. The
calcium to aluminum and the calcium to sulfate ratios both show
an excess of calcium beyond that necessary for stoichiometric
ettringite. Once again, the sulfate to aluminum ratio is quite
close and unless this ratio is fortuitous and both sulfate and
aluminum are low, the calcium value would appear high. In
fact, if the calcium figure is correct, it would be more

159
double the amount that would be derived from complete
dissolution of the calcite indicated by the x-ray analysis.
The small negative epm imbalance again seems to involve both
calcium and carbonate. In this case a high reading in calcium
may have fortuitously helped to balance an ever higher
carbonate measurement.
The mole ratios for Samples ET-40a and ET-40b are similar
to those of ET-25a and ET-25b, however the errors are much
smaller. The epm imbalance is, again, negative suggesting the
problems are similar to those discussed for ET-25a and ET-25b.
The epm balance for gypsum samples G-25 and G-40 are
excellent. These good quality data are verified by the mole
ratios shown in Table 25. Sample G-10 has a positive imbalance
of about 10%. The calcium to sulfate ratio is also high,
however, it is not possible to deduce whether calcium is too
high or sulfate too low.
Summary
Although the analytical data for ettnngite are not
outstanding, it was judged suitable for the intended purpose.
The data for samples ET-25C, ET-40a, and ET-40b are actually
quite good. The two samples from 10 C are tolerable,
evaluation of the data is complicated by the presence of
under ideal conditions no carbonate would be

carbonate.
160
present. The x-ray pattern for the ettringite, however, showed
approximately 1% calcite. Furthermore, although water for the
solutions was treated to remove as much of the carbon dioxide
as practical, some carbon dioxide surely remained. Finally,
additional carbon dioxide must have been introduced into the
system during measurement of conductivity and collection of
water samples. This latter contamination was not indicated by
the calcium chloride solution which was apparently too weak to
be effective. Upon completion of the experiment the calcium
chloride solution was opened to the atmosphere and did not turn
cloudy.
The gypsum samples did not show very much carbonate. This
is most likely because carbon dioxide dissolves in aqueous
solutions as carbonic acid. Certainly much more acid can be
dissolved in a strongly basic solution than in one that is
slightly acid. If no carbon dioxide was present in the gypsum
solution, the pH would be 7 at 25”C. The pH values measured
in the solubility experiments for gypsum were around 6,
indicating the presence of some C02.
THE SOI.TTBTT.ITY OF GYPSUM
The solubility of gypsum was measured in this research
primarily as a check on the experimental techniques. All of
the procedures performed on the ettringite samples, incl ' g
the nitrogen purge, were performed on the gypsum samples. In

161
retrospect, a better choice might have been calcium hydroxide.
Calcium hydroxide, while still a simple compound like gypsum,
produces a high pH solution like ettringite. Since reagent
grade Ca(OH ) 2 is available, any carbonate in the solution would
have to have come from the air or water. This would have
provided a little better understanding of the extent of
carbonate contamination.
The individual ion activities for calcium and sulfate were
determined from WATEQDR, as previously described. An example
of the computer printout for 25°C is presented in Appendix 22.
The dissociation reaction for gypsum is:
CaS04*2H20 = Ca2+ + S042' + 2H20.
The dissociation (equilibrium) constant for the reaction is:
Kg = a[Ca2+] a [SO2'].
Using the above relationships and the WATEQDR output, the
equilibrium constant was calculated for temperatures of 10 C,
25°C, and 4 0 °C. The results are presented graphically as
Figure 28. The least squares method was employed to fit a
curve tothe points. Since only three data points were
available, the fit was perfect. The equation describing the
curve, and thus the change of the equilibrium constant with

TEMPERATURE IN
pK GYPSUM
Figure 28 The negative logarithm of ^he dissociation
constant of gypsum as a function of temperatu .
163
temperature (degrees centigrade) is: log K* = -4.6766 +
.005866T - 1.204 x 10 - 4 T2. For comparison the equation used
in WATEQDR is:
log Kt = -4.6535 + .004545T - 1.01 X 10-* T2.
The curves described by both of these equations are shown on
Figure 28 as are the error bars calculated from the data of
this study. In this case the bars are deceptively large due
to the small scale of the p K ^ axis. The error bars are based
on an assumed 5% analytical error in the water analysis. For
samples G-25 and G-40 this is certainly a valid and
conservative assumption. For sample G-10, the error probably
exceeds 5%.
At 25°C the log of the equilibrium constant for gypsum is
calculated to be -4.605 from the data of this study. For
comparison, the value calculated from the equation used in
WATEQDR is -4.603. Published values range from
(Krauskopf, 1979) to -4.61 (Drever, 1981). Above 25 C the
WATEQDR curve and the curve of this study are virtua y
identical. Both give a value of -4.634 at 40 C. Below 25
the curves diverge slightly. WATEQDR yields a value of -4.619
at 10 “C while the K 40 measured by this study is -4.630. This
discrepancy is actually quite small and most likely the result
of the analytical errors indicated by the 10 * epm imbalance
Sample G-10. In conclusion, the equilibrium constant for

gypsum at 25°C and the curve of the change in the equilibrium
constant with temperature, as determined by this study, are in
excellent agreement with published figures.
THE SOLtTBTT.TTY OF E T T R IN G IT E
Individual ion activities were, again, calculated with
WATEQDR. A typical computer printout (25 C) is included in
Appendix 23. The dissociation reaction for ettringite is:
Ca 6 [Al (O H )6]2(S04)3•2 4 H20 =
6 Ca2+ + 2A1 (O H )4” + 3S042' + 40H' + 20 H20.
The dissociation (equilibrium) constant for the reaction is.
Ket = a [ C a 2+] 6 a [ A l (O H )4' ] 2 a [ S 0 2' ] 3 a [ 0 H - ] 4
Using this equation and the ion activities obtained from
WATEQDR, the equilibrium constant was calculated for
temperatures of 10°C, 25°C, and 40°C. These values are
summarized in Table 26.

165
Table 26
Calculated Equilibrium Constants for Ettrinqite
Samples Temperature log K«t
ET-lOa 10°C -48.30

ET-lOb 10°C -48.21
ET-25a 25 °C -47.21
ET-25b 25 °C -47.78
ET-25C 25 °C -48.49
ET-40a 40 °c -47.22
ET-40b 40 °C -47.67
As shown by the equation for the dissociation constant,
equilibrium for this reaction is strongly affected by minor
changes in the individual ion activities. This is particularly
true of calcium and hydroxide which are raised to powers of six
and four, respectively. As a consequence, any errors, in
analytical data are amplified in calculating the equilibrium
constants. For this reason, the data from ET-25a and ET-25b
have not been included in the evaluation of the equilibrium
constant and its change with temperature. The remaining five
data points have been plotted as Figure 29. Using the
squares method on these points results in a best-fit curve
described by the equation:
log ket = 196.429 - 1.6699T + 0.002846T2
This curve is also shown on Figure 29.
The equation gives the log equilibrium constant for
ettringite as -49.49 at 25"C (298.16'K). Since there is only
one acceptable datam point at this temperature, the value

TEMPERATURE
166
167
calculated from the curve is coincident with that calculated
from the ion activities.
The analytical values of the various ions should be within
5 %. Given the epm imbalance of some of the data, errors are
probably a little worse than that, particularly for the
experiments at 10°C. The smallest epm imbalance occurs with
Sample ET-25C. Since 25°C (298.16 K) is the standard state
temperature of chemical thermodynamics, this is most fortunate.
An assumed analytical error of plus or minus 5% results in the
error bars for the calculated equilibrium constants shown on
Figure 29. The error in the calculated equilibrium constants
is probably within one-half a pK unit and, for sample ET-25c,
probably within one-quarter of a pK unit.
If the sole purpose of this research had been to evaluate
the ettringite solubility as precisely as possible, it would
have been necessary to run multiple samples (3 to 5 minimum)
at numerous temperatures between 5 'C and 50"C. Given the other
uncertainties in the geochemical/geohydrologic mechanism of
lim e -in d u c e d heave, th e v a lu e s o b ta in e d w ill be show n to b e
s u ita b le fo r th e ir in te n d e d p u rp o s e in C h a p te r 8.
THE THEnMOnyNAMTC.S OF ETTfTNGXTF. SOTIIBILITY.
The equation of the curve in Figure 29 fits the mean log
KC values to within ± 0 . 2 units and the value at 25'C exactly.

168
In natural logarithms the equation is equivalent to
lnKat = 452.2981 - 3.8450T + 0.006552T2.
From this expression and the relation AGr° = -RTlnk, we may
compute
AGr° = 7.6400T2 - 0.01302T3 - 898.7163T.
Thus at 298.16 °K (25° C) AGr° = 66.14 ±0.26 kcal/mole
Using the relationship
AHr0 = RT2(01nKet/0T) ; AHr° = 0 .02604T3- 7 .6400T2
At 298.16° K this expression yields A H r = 11.0+ 0.3
kcal/mole. The heat capacity of the reaction computed from
ACP° = (aHr°/9T) gives ACP° = 0.07812T2 - 15.28T or, at 298.16 K,
Acp° = 2.4 ± 0.1 kcal/mole. Finally, the expression
- ASr° = AGr°/ T yields Sr° = 15.28T - 0.03906T2 - 898.7163 and 19
cal/deg mole at 298.16 K.
Using the values of Gr°, Hr°, and Sr° obtained above for
the dissociation reaction, the specific values can be
calculated for formation of synthetic ettringite. For example,

, o=
AGr AGporoducts - ._oeactants, or AGF
AGr Ar»et = AG °ro,
a^p *a - AGr°.
duot From standard
tables of thermodynamic data (Krauskopf, 1979), this yields a

169
value of AGF°et = -3641 kcal/mole. Enthalpy and entropy for
ettringite were calculated in a similar manner. The
thermodynamic values obtained are summarized in Table 27.
Table 27
Summary of Thermodynamic Values for Ettringite a_t

25 °C f298.16 °IQ
Parameter Calculated Value
Log Ket -48.49 ± 0.3
AGf° -3641 ± 0 . 3 Kcal/mole
ah; -4128 + Kcal/mole
as; -647 ± 52 Cal/deg mole

170
CHAPTER 8
ANALYSIS AND EVALUATION OF EXPERIMENTAL AND FIELD DATA
t.&RORATORV SIMULATION OF LIME-INDUCED HEAVE
Expansive Pressure
The test to measure the maximum potential pressure from
growth of ettringite/thaumasite in a controlled environment met
with immediate success. The lime and sulfate apparently did
not react with the aluminum and steel in the apparatus m a
manner that inhibited crystal growth. The results of the
experiment have been presented as Figure 24. The maximum
expansive pressure was found to be 7535 pounds per sguare foot
for the soil tested. This pressure is certainly enough to
heave pavements and also foundations and floor slabs of lightly
loaded structures. The measured value is well within the range
commonly measured for expansive clays.
volume Change
The methodology for duplicating the heave mechanism in the
laboratory required the most time consuming and frustrating
experiments of the entire project. The greatest stumbling
block was the unexpected ability of the brass volume change
meter to react with the solutions and inhibit the formation of

171
ettringite. Once this problem was recognized, it was easier
to duplicate the swelling soil in the laboratory.
The experiments provided several important keys to the
understanding of lime-induced heave. It is hoped that the
comprehensive experiments in progress at the University of
California, Berkeley, (Appendix 11), will provide additional
details on some of the reactions.
The results of volume change experiment five were
presented graphically in Figure 25. The diagram shows that the
maximum volume change from kaolinite soils treated witn 6*
hydrated lime (4.5% equivalent quicklime) is, roughly, 50*.
In other words, a one-half-inch thick sample will expand to
approximately three-fourths-inch in height. In these
experiments the reactions were provided with an unlimited
source of sulfate by immersion in a solution either saturated
with calcium sulfate or containing 5500 ppm sulfate from sodium
sulfate. in addition, both silica and aluminum were present
in great excess due to the use of pure kaolinite clay, rather
than natural soil.
The initial volume change rates of samples VC-5A and VC-5B
were nearly identical, even though the sodium sulfate solution
provided more than three times the sulfate per liter than
gypsum solution. Sample VC-5C, which contained calcite,
expanded at a much slower rate than the other two.

172
The similar growth rates for VC-5A and VC-5B indicate that
sulfate is not the rate limiting step in the reaction process.
The fact that the sodium sulfate solution leveled off at a
slightly lower percent volume change than the calcium sulfate
solution, suggests that the reaction ran out of calcium before
it ran out of aluminum. In other words, the pH of the system
may still have been high enough to break down clay minerals.
The stoichiometry of ettringite, Ca6[Al(OH)6]2* (S04)3-26H20,
indicates the need for abundant calcium. The same holds true
for thaumasite, though it is unlikely to have occurred given
the temperature range of the experiment. It is concluded that
clay bearing soils containing either gypsum, or the much less
common sodium sulfate minerals thenardite and mirabilite, can
react with lime to produce heave. Of the two, gypsum probably
results in the higher heave magnitudes due to the additional
supply of calcium. Magnesium sulfate minerals, such as
epsomite, would probably behave in a manner similar to sodium
sulfate.
Sample VC-5C also provides interesting information. The
lower rate of growth is important, especially since expansion
continued beyond the time allotted for the experiment.
Presumably, the ultimate volume change would have approached
that of the other two samples had the test been run for
years. The slower rate may be the result of complex factors
not yet understood. A simplistic explanation, however, is that

173
the reduced rate is the result of the common ion effect. The
presence of calcium carbonate should reduce the solubility of
gypsum. The equilibrium reaction for the dissolution of gypsum
is:
CaS04*2H20 = Ca2+ + SO/" + 2H20
Any increase in the chemical potential of calcium, caused
by dissolution of calcite, should drive the reaction back to
the left. Since calcite was present in the native soil at both
Stewart Avenue and Owens Avenue, the effect on the reaction
rate is of considerable interest. Had calcite not been
present, the heave might have occurred much more quickly. In
fact, the expansion potential might even have been detected in
the laboratory during R-value testing and mix design. The
lime-induced heave reported by the highway departments of Utah
and Texas occurred prior to paving. Although this is entirely
speculation, the rapid response suggests that minimal carbonate
was present in the system.
The sixth phase of the volume change testing used native
soils from areas of major distress along Stewart Avenue. The
results of these experiments have been presented graphically
in Figure 26. In this case, the volume change of the two
samples reached approximately 26% for VC-6A and 21% for VC-6B.
The experiment was terminated after 6 months, however, the
growth curves showed no signs of leveling off. Since sulfate

174
and a high pH were being provided from outside the soil, the
expansion would be limited only by the amount of available clay
(aluminum). Although both soil samples contained abundant
soluble sulfate, neither specimen reacted significantly when
the apparatus was submerged in purified water. After several
weeks the water was replaced with a solution saturated with
gypsum and calcium hydroxide. The response was sluggish but
the two samples soon began to expand at a nearly uniform rate
of approximately 1% per week. The rates were considerably
slower than for the pure kaolinite "soils" but exactly in line
with the 100% volume increase shown on Stewart Avenue over a
period of two years. The slower rate, relative to kaolinite,
suggests that the dissolution of clay is the rate controlling
step in the reactions, even at the maximum pH (12.3) for lime
saturated water. The presence of carbonate, however, also
slows the reaction. The fact that expansion did not occur
until the samples were immersed in a sulfate solution is
important. It suggests that the heave might not have occurred
or would have been very slow if only pure water had been added
to the system at Stewart Avenue. Perhaps the calcium would
have become tied up by normal pozzolanic reactions before
sufficient sulfate could be generated to induce heave.
Subsequent, slower, reactions would have attacked the subbase
through the same mechanism by which sulfate deteriorates
hardened concrete. In hardened concrete ettringite growth
produces crumbling and strength loss but only a very small
volume increase.
175
The movement of ions through the porewater system of soils and
sediments is very slow (Berner, 1971). It may be that a great
deal of time is required for the minerals to ionize in the pure
porewater and then migrate to favorable nucleation sites. It
has been shown by experiment that the nucleation sites are
probably on or around the lime particles where the clay
minerals are releasing aluminum and silicon. Much more rapid
reaction seems to occur when the water entering the soil/lime
system is already rich in sulfate. Under this condition, the
necessity of mobilizing the gypsum ions within the soil is
avoided. Water entering most of the damaged areas of Stewart
Avenue and Owens Avenue appears to have reached the nucleation
sites through capillarity, presumably after moving through a
significant thickness of soil. The sulfate leaching experiment
performed during this research showed that pure water flowing
through a 24 inch (61 cm) long column of typical Stewart Avenue
soil carried over 5500 ppm sulfate. Thus, the use of a sulfate
solution in the Phase 6 experiments is not only the correct
model, but may also be necessary to stimulate reaction.
The addition of lime to the external solution probably was not
necessary for the reaction since little calcium hydroxide would
be present in the capillary water on Stewart Avenue. The lime
was added in the experiment in hopes of speeding up the
reactions so that the expansion could be measured m a

176
reasonable time. Even so, the experiment required over six
months and the benefit of the external lime is not really
known.
FTTRINGTTF, /THAUMASITE GROWTH IN OTHER SOILS
Although lime-induced heave has not been a common problem,
this experiment demonstrated the potential for ettringite/
thaumasite growth in soils other than those of Stewart and
Owens Avenues. Of the fourteen soils tested, eleven were from
areas well outside the Las Vegas valley. As shown by Table 8,
lime-treated soils from the Bonneville Salt Flat, Utah, and
Carson Sink, Pyramid Lake, White Lake, and northwest Reno,
Nevada, showed significant ettringite/thaumasite. Three other
samples, Black Rock Desert, Nevada, Snake River Floodplain,
Idaho, and Yolo Causeway, California, have a somewhat weaker
potential for heave. Additional cases of distress, as
described in Chapter 4, show that the problem is world-wide and
not even be limited to arid environments or soils containing
sulfate minerals.
The mechanical analysis data (Table 7) show that the seven
reactive samples all contained a relatively high percentage
particles in the clay and colloid size range. Those that
not appear to have reacted, generally have relatively low
clay/colloid levels. No chemical analyses were performed on
any of the samples, other than those from Stewart Avenue.

177
Previous research (Kollmann, 1978; Kollmann, et. al., 1981) has
demonstrated that ettringite will form when clay minerals are
mixed in a slurry with lime in the presence of sulfate. It
follows that soils that do not form significant ettringite
either lack sulfate, clay, or sufficient water. Since the
samples of this experiment had abundant water, those that did
not react were deficient either in sulfate or clay. Based on
the hydrometer analyses, all of the samples likely had enough
clay. Therefore, those that did not react probably lacked in
sulfate. Only four of the soils showed sulfate bearing
minerals in the x-ray diffraction analysis of the elutriation
concentrate (Table 8).
The soils of this experiment generally required that the
low density minerals be concentrated in order to positively
identify the ettringite/thaumasite. The amount of ettringite/
thaumasite present was, therefore, quite small. The evaluation
of the Stewart/Owens distress revealed that sulfate and other
ions migrated to the nucleation sites. As a consequence, lime-
induced heave is dependent upon the initial soil chemistry only
to the extent that ettringite/thaumasite nucleation must be
thermodynamically and kinetically favored. The magnitude of
the distress, where it even occurs, is more dependent upon the
ability of the geohydrologic/geochemical system to supply
component ions to the reactions. These factors will be
considered in detail in later sections of this chapter.

178
SYNTHESIS OF THAUMASITE
Synthesis of pure thaumasite has been performed by a
number of workers, as discussed in Chapters 5 and 6.
Unfortunately no one is known to have isolated this pure
thaumasite from the other components involved in the reactions.
Several methods to isolate pure thaumasite were attempted
during this research. These were described in detail in
Chapter 6 but included rinsing of the mineral aggregate, use
of heavy liquids, elutriation, preferential nucleation, and
kinetic exchange. These experiments consumed a considerable
amount of time and, unfortunately, were unsuccessful. Although
several methods were found to increase the concentration of
synthetic thaumasite, none could isolate the mineral to tne
extent that it would be suitable for solubility measurements.
As a consequence, the solubility of thaumasite was not
determined.
SYNTHESIS OF ETTRINGITE
As described in Chapter 6, the synthesis of reasonably
pure ettringite was successful. Gypsum can effectively be kept
from precipitating with the ettringite by mixing the solutions
at a slow enough rate to prevent localized gypsum super
saturation. in contrast, however, calcite presents a much more
challenging task. If all of the carbon dioxide could be
removed from the purified water and all aspects of the

179
synthesis performed in a C02 free environment, it would be
possible to synthesize pure ettringite. Unfortunately, these
conditions are very difficult to achieve.
M A SS—VOTiIIME R E L A T IO N S H IP S
Profiles across severely damaged areas of Stewart Avenue
showed maximum heaves exceeding 12 inches (30.5 cm). This
correlates well with observations in the trenches where the
lime-treated subbase has expanded from an approximate initial
thickness of 12 inches (30.5 cm) to as much as 27 inches
(68.6 cm). Because ettringite/thaumasite is hydrated with an
extraordinary number of attached water molecules, the mineral
takes up a much higher volume than its constituent ions. The
volume change experiments, even using pure kaolinite and
unlimited sulfate, suggest that the maximum heave that could
be expected from 4.5% quicklime would be on the order of 50«.
The trilinear (Figures 18, 19, and 22) and stiff (Figure 20)
diagrams, however, indicate that there has been considerable
influx of ions, beyond those present in the native soil. These
additional ions could account for the observed discrepancy
between the volume change measured in the field and that
measured in the laboratory.
As a check on the mass-volume relationships in the field,
the approximate volume change expected from a given soil
chemistry can be calculated. The mass-volume relationships in

180
the field can be estimated from either the change in density
or from the change in specific gravity. The latter is thought
to be the most reliable since the initial (end of construction)
density would have to be assumed from construction records.
Although this density must still be used in calculating the
total sulfate available per cubic foot of soil, that particular
calculation is not overly sensitive to density. Test pit S-8
was selected for the evaluation because all of the needed data
had been specifically measured in that location and S-8 is
adjacent to a control test pit, S-9. The following assumptions
were made:
1. Thaumasite was the only secondary mineral grown m
the system.
2. Infinite silica was available from dissolution of
clay and infinite calcium and carbonate from
dissolution of calcite. That is, sulfate was the
limiting component.
3. L im e -tre a te d s u b b a s e was o r i g i n a l l y 12 i n c h e s thick,
as per d e s ig n .
4. Sample S-9B represents original subgrade soil
chemistry for S-8.

181
5. All of the sulfate available in the native soil
reacted.
The initial data needed for the calculations were obtained
from a combination of construction field reports, field
measurements taken during the distress analysis, laboratory
testing of the soil properties and chemistry, and the
Encyclopedia of Minerals. These data are summarized in
Table 28.
Table 28
nata for Mass-Vo]ume Calculations
Maximum dry density of native soil 106.9 pcf*

Specific gravity of native soil 2.73 gm/cc
Specific gravity of damaged^subbase 2.37 gm/cc
Specific gravity of ettringite 1.77 gm/cc
Formula weight of ettringite 1254.0 gm/mole
Molar volume of ettringite 708.5 cc/mole
Specific gravity of thaumasite 1.91 gm/cc
Formula weight of thaumasite 1220.0 gm/mole
Molar volume of thaumasite 639.0 cc/mole
Initial dry density of
lime-treated subbase 96.2 pcf*
Final dry density of
damaged lime-treated subbase 59.3 pcf
Final moisture of
damaged lime—treated subbase 59.0%
Initial volume of 1 ft2 of
lime-treated subbase 1.0 ft3
Final volume of 1 ft2 of
lime-treated subbase 2.1 ft3
42.000 mg per kg
Available sulfate (S-9B)
of soil
16.000 mg per kg
Available calcium (S-9B)
of soil
construction (Converse Davis and

* Measured at time of
Associates, 1975).
182
Chemical calculations
a. Assume all 42,000 mg-sulfate reacted to form

thaumasite. ----------
kg-soil
b. One ft3 soil at 96.3 pcf = 4 3 . 8 kg/ft3
c. (43.8 kg/ft3) x (42,000 mg/kg) = 1840 grams of

available sulfate per cubic foot of soil
d. 1840 gm sulfate = 19.2 moles of sulfate per cubic

---------------— foot of soil
96 gm/mole
e. From stoichiometry of thaumasite, 2 moles sulfate

yields 1 mole of thaumasite:
19.2 moles sulfate = 9.6 moles of thaumasite
(9.6 moles) x (1220 gm/mole) = 2 5 . 8 lbs of thaumasite
454 gm/lb
Mechanical Calculations
a. To achieve an average specific gravity of 2.37

(damaged subbase) from weighted average of 2.73 and
l.gi reguires 56% soil and 44% thaumasite.
(.56) X (2.73) + (.44) X (1.91) - 2.37
b. (59.3 pcf) x (.44) = 2 6 . 1 pcf thaumasite
c. (26.1 pcf) x (454 gm/lb)

(1.91 gm/cc) x (28317~cc/ft3) = 0.219 ft3 thaumasite.
d. (.56) x (59.3 lbs) x (454 gm/lb)
(2.73) X (28317 cc/ft3) = 0.194 ft3of soil
1- 59.3 lb
(2.37 gm/cc) x 62.4 pcf) = 0.599 - volume of
voids
So for each cubic foot of damaged subbase there is
approximately:
0.19 ft3 soil

0.22 ft3 thaumasite
0.59 ft3 voids.
jssm
183
g. There are 2.1 ft3 (per square foot) of damaged

subbase that grew from 1 ft3 of treated soil. Thus
the volume of thaumasite required is (2.1) x (0.22
ft3) = 0.44 ft3.
h. Mass of required thaumasite is

(0.44 ft3) X (1.91) X (62.4 pcf) = 54.8 lbs.
i. From step lg, the mass of thaumasite that can be

grown from 42,000 mg-sulfate/kg soil is 25.8 pounds.
j. On the basis of this analysis, the closed system is

deficient by 54.8 lbs - 25.8 lbs = 29.0 lbs of
thaumasite.
k. Thus the available sulfate is only sufficient for

approximately:
25.8 lbs x 100 = 47%
54.8 lbs
of the required thaumasite.
In reality, ettringite very likely grew before thaumasite.
This is well supported by laboratory research of previous
workers (Kollmann, 1978; Kollmann et a l , 1977; Kollmann and
Strubel, 1981). Ettringite requires more sulfate than
thaumasite indicating an even larger deficiency. However,
since the specific gravity of ettringite is lower than that of
thaumasite, the effect would not be as large as might be
anticipated from stoiciometry. Clearly, however, in both cases
the available, closed system, sulfate is less than one half of
that necessary to satisfy the mass-volume requirements.
The laboratory tests using the kaolinite "soil" provided
unlimited sulfate and aluminum to the reactions. In VC-5A the
reaction appears to have been limited by calcium since the

184
expansion ceased before that of VC-5B (Figure 25). Sample
VC-5B was supplied unlimited calcium from the external calcium
sulfate solution. For comparison, the potential volume change
was calculated using the data of test pits S-8 and S-9 but with
calcium as the limiting component. The procedure was exactly
like that used for sulfate. However, in this case there are
two sources of calcium, neither of which is entirely
predictable. The first source is the native minerals, calcite
and gypsum found in the untreated soil. Calcite was probably
not completely dissolved by the 50:1 extraction ratio such that
there is somewhat more available in situ calcium than the
analysis shows. The second calcium source involves soil
treatment with 4.5 weight percent quicklime. Since the
compacted unit weight of the soil varies along the alignment,
the mass of lime added per cubic foot of soil varies. In
addition, the entire construction process of adding and mixing
lime is difficult to control. In spite of these limitations
an estimate is possible:
1. Assume initial unit weight of 96.2 pcf as per

construction records.
2. (96.2 lbs) X (1.045) - 96.2 lbs = 4.335 lbs (1967 gm)

of CaO.
(1967 gm) x 40 (atomic weight of Ca)
56 (formula weight of Ca(OH)2) = 1405
gms of calcium)
4. 96.3 lbs = 43.7 kg treated soil

185
5. (43.7 kg) x (16000 mg/kg)
1000 mg/kg = 699 grams Ca.
6. 699 gm + 1405 gm = 2104 gm available calcium.
7. 2104 gm
40 gm/mole = 52.6 moles Ca
8. from stoiciometry, 6 moles Ca yields 1 mole

thaumasite:
52.6 moles
6 = 8 . 8 moles thaumasite.
9. (8.8 moles) x (1220 gm/mole)

454 gm/lb = 2 3 . 6 lbs thaumasite.
10. From step 2h of previous calculation, 54.8 lbs of

thaumasite are required. The available calcium is
thus only sufficient for approximately
(23.6 lbs) x 100
54.8 lbs = 43% of the required

thaumasite.
Since not all of the calcite dissolved during the

extraction, the actual figure may be closer to 50«.
In most cases the 4.5% quicklime probably supplies
over half the calcium.
The calculated maximum volume change is in good agreement
with the 50% volume change measured in the laboratory for the
kaolinite ''soil.*' The experiments appeared to be first limited
by lack of calcium when sulfate was kept in supply by sodium
sulfate. When both sulfate and calcium are unlimited, the
reaction should continue until aluminum is no longer available.
This could occur either when the pH drops below 10.5 or the
available clay has been exhausted. On Stewart Avenue, east of
Lamb Boulevard, the latter was probably the case. The pH of

186
lime-treated subbase, either damaged or undamaged, was nearly
always above 10.5 on both Stewart and Owens Avenues.
The remaining ions necessary for the measured volume
change would have to be added to the system through the pore
water. In fact, the calculated maximum volume changes probably
greatly exceed that which could have occurred in the field in
a closed system. In most areas, some of which exhibited 100%
expansion, the sulfate content of the native soil was far less
than 42,000 mg/kg. Additionally, x-ray diffraction showed that
much of the sulfate did not react to form ettringite/thaumasite
as it was tied up in gypsum. It is concluded, therefore, that
an influx of sulfate, and presumably, calcium and carbonate was
necessary to generate the observed heave magnitudes. This
conclusion is well supported by the trilinear and stiff
diagrams, as previously discussed.
One very interesting point brought out by the mass volume
analyses is just how little of the heave (volume increase) is
the direct result of the volume of the ettringite/thaumasite
mineral mass. In the reactions, the total volume of the soil
solids per cubic foot decreased from, roughly 56% to 44%.
Presumably, this reflects the change in original soil volume
as soil ions were consumed by ettringite/thaumasite. The
actual volume of thaumasite is only about 0.22 ft out of each
cubic foot of damaged subbase. Consequently, in the expansion
from 1 ft3 to 2.1 ft3, the thaumasite accounts for,

187
approximately, (2.1 x .22) 0.46 ft3 of the 1.1 cubic foot
increase in volume. Correcting for the loss of soil volume due
to reactive consumption, leaves a net volume increase of 24%
due directly to thaumasite. The remaining volume change, which
is 74% of the 1.1 cubic feet of expansion, is the result of
increased voids (loss of density) associated with the mechanics
of dissolving and growing minerals within a highly compacted
soil. The increased voids, decreased original soil volume and
volume of ettringite/thaumasite are depicted graphically in
Figure 30.
At Stewart/Owens, near-end member member thaumasite was
the final reaction product. Only silica* and, perhaps, a small
quantity of aluminum and hydroxide, were consumed from the clay
dissolution. Although calcite and gypsum were, doubtless,
consumed, the x-ray patterns often show calcite and gypsum at
levels that indicate secondary mineralization. Large crystal
aggregates of gypsum and calcite were observed, at Stewart
Avenue, along the upper and lower contacts of the lime treated
subbase. Thus, the secondary growth was verified in the field.
The reactions that account for secondary calcite and gypsum
will be discussed with the geochemical reaction model m a
later section.
188
HEAVED CONDITION
.. 24" UNFILLED VOIDS «

6%
VOIDS/WATER 53%
INITIAL CONDITION
-12"
15% UNFILLED VOIDS
28% VOIDS/WATER ETTRINGITE/

20%
THAUMASITE
57% SOIL SOLIDS SOIL SOLIDS 21%
-0"
Figure 30 Changes in soil volume due to growth of

ettringite/thaumasite.
189
tfigs-FT.UX CALCULATIONS
The evidence seems to require an influx of outside ions
into the lime soil system. Mass-flux calculations were
performed in an effort to see if the necessary ions could reach
the nucleation sites in a reasonable amount of time. At
Stewart Avenue and Owens Avenue, the maximum vertical
expansions were reached within two years of construction. In
addition, Las Vegas has an arid climate with rainfall of less
than five inches per year.
The data used in the mass-flux analysis are summarized in
Table 29.
Table 29
Initial permeability of lime-treated 0.2 gpd/ft2

Final^permeability of damaged lime-treated 3.6 gpd/ft2
subbase1 , 5700 ppm
Sulfate concentration in porewater 3.3
Average hydraulic gradient
"Measured in laboratory _ street middle of LTSB

2Assumed one foot of storm water in flow distance of
1.5 feet below top of pavement and a v e ^ r a g ^ e ^ Qf LTSB; 0 .5
0.75 feet. Flow distance is °ne If ^ LTS B _ The average
foot for undamaged and / ? / ° ° l L t i n g the hydraulic gradient,
of these values was used in estimating
The following calculations were performed:
KI
q = KIA o r f o r A - 1 ft / Q
_L . From Darcy's Law:
r i. w in .
ahig itv for undamaged and damaged
2. Use average permeability
condition.
190
q = ( i . g gpm/ft2) x (3.3) = 6.3 gpd/ft2 = 23.8 liters per

day/ft2
Using the first mass-volume calculations, system is short
29 lbs of thaumasite or:
29 X 454
= 1 0 . 8 moles thaumasite or (2) x (10.8)
-- 21.6 moles sulfate.
1220 gm/mole
(21.6 moles) x (96 gm/mole) x (1000 mg/gm) - 2,073,600 mg
sulfate needed
From sulfate leaching experiment, soil porewater contains
5700 mg/1 sulfate.
2,073,600 mg = 364 liters
5700 mg/liter
8, 364 liters = 15 days
23.8 liters/day
on the basis of the above analysis, it is estimated that
15 days of flooded streets would be required to supply a
sufficient quantity of ions to the nucleation sites. This
appears to be a little high for the Las Vegas climate.
However, much of the water was probably supplied by capillarity

, t +- no not clear exactly how this
from the utility trenches. It
. . than it would likoly
would affect the rate estimate
increase the amount of saturated time necessary to supply the
ions. It is also not Known just how high the water level could
rise in utility trench bacKfill during thunderstorms. Ponding
of water in utility trenches would supply capillary water
after the street flooding had disappeared. Also, water would
pond in trenches from storms far too small to cause street

191
flooding. Overall, the calculations suggest that the required
ions could probably be supplied within the observed time frame.
The common growth of large crystals along the upper and
lower contacts of the lime-treated subbase is physical evidence
of water having entered the system at the horizontal boundaries
(refer to Figure 15). The larger crystal aggregates indicate
that more ions reached the boundaries than were carried by
capillarity into the center of the subbase. This suggests that
water reached the boundaries more often than it reached the
middle of the layer and/or the ion supply was increasingly
depleted as water migrated inward from the subbase boundaries.
CTOCHEMICAT, REACTION MODEL
The geochemical reactions involved in the growth of
ettringite, and its subsequent transition to thaumasite, are
doubtless quite complex in lime-treated soils. The initial
Stewart/Owens soil chemistry, primary and secondary mineralogy,
experiments performed during this research, and the published
solid solution series between ettringite and thaumasite suggest
a series of stepped equilibrium reactions as a general model
of lime-induced heave (Hunter, 1988). These reactions are as
follows:
1. CaO + H20 = Ca (O H )2
(hydration of quicklime)
2. Ca(OH) 2 = Ca2+ + 2 (OH)' .

(ionization of calcium hydroxide, pH rises to 12.3)
192
3. Al4Si4O10(OH) 8 + 4 (O H )' + 10H20 = 4Al(OH)4"+ 4H4Si04

(dissolution of clay mineral, at pH > 10.5)
4. 2H4Si04 = H2Si042~ + 2H+

(dissociation of silicic acid at pH > 11.7)
5. 5Ca2+ + 6H22~Si04 = Ca5(Si601BH2) •4H20 + 60H"

(formation of calcium-silicate-hydrate gel)
6. MxS04-nH20 = XMY+ + S042" + nH20 _

(dissolution of sulfate minerals; x = l , y=2 or x-2, y-1)
7. 6Ca2+ + 2A1 (O H )4" + 4OH" + 3(S04)2" + 26H20 =

Ca6[Al(OH)6]2* (S04)3•26H20
(formation of ettringite)
8. C02 + H20 = H2C03

(formation of carbonic acid)
9. CaC03 + H2C03 = Ca2+ + 2H+ + 2C032"

(dissolution of calcite in carbonic acid)
10. Ca r A l f O H ) , ] , * (S04)3-26 H20 + 2H2Si042" + 2C032 + 4H

S;[sI(OH)I];-(SO:)l-(CO,)V24H,0 + 2Al(OH)'t + SO/' + 40R- +
2H20 , ,
(isostructural substitution as ettringite changes to
thaumasite)
11. Ca2+ + S042" + 2H20 = CaS04•2H20

(formation of secondary gypsum)
12. Ca2+ + C032" = CaC03

(formation of secondary calcite)
Reactions 1 through 5 are "normal reactions resulting m
siliceous cementation of lime-treated soils. Reaction 3 is
shown for kaolinite since it was used successfully m the
laboratory. In fact, any clay mineral could be used in the
model since the sole function of the clay is to provide a
source of silicon and aluminum. In the presence of excessive
sulfate, the rate of the forward reaction in equilibrium pair
number 5 approaches zero. Sulfate from any evaporite (Reaction
6) reacts with aluminum generated by dissolution of any clay

193
mineral to form ettringite (Reaction 7). Based on the
Tennessee Department of Transportation study, sources of
sulfate other than evaporate minerals are possible.
Once ettringite has nucleated, it continues to grow as the
nearly pure end member until the temperature of the system
drops below approximately 15°C. Below 15 C ettringite is
transformed, through a series of intermediate solid solutions,
to thaumasite. The change occurs by isostructural substitution
of silica for aluminum and carbonate for sulfate. Based on the
reaction, there may also be some pH control on thaumasite
formation. Regardless of temperature, the transformation may
not begin until ettringite has consumed sufficient OH to drop
the pH below some threshold level. Secondary gypsum (Reaction
11) likely forms from calcium released by dissolution of
calcite (Reaction 9) and sulfate released from dissolution of
ettringite. Reactions 7 and 10 stop as pH drops below 10.5,
thereby cutting off the supply of aluminum and silicon
(Reaction 3). In the presence of excess calcium, Reaction 12
occurs at that time as carbonate ions are no longer being
consumed by thaumasite.
The temperature control of the ettringite to thaumasite
transition must be, at least, partially a function of the
retrograde solubility of caloite. However, the strong pH
dependence of both carbonate and silica solubility adds
additional complexity to the problem. At high pH, silica is

194
quite soluble. Calcite solubility, however, decreases rapidly
at higher pH. Thaumasite growth, therefore, must be, partially
controlled by a balance between two nearly mutually exclusive
reactions. A diagrammatic representation of the lime-induced
heave mechanism is presented as Figure 31.
One unanswered question is whether or not thaumasite is
even necessary to induce heave. In the laboratory, ettringite
always forms first at any temperature when both aluminum and
silicon are present. The transition to thaumasite may well
have occurred after the heave. At Stewart/Owens, the
transition was complete; no identifiable ettringite was found.
In Kansas (Mitchell, 1986), ettringite was blamed. This may
represent a case where the damage occurred and was studied
prior to the transition or it may be another indication of the
difficulty in distinguishing ettringite from thaumasite by x-
ray diffraction. The Tennessee Department of Transportation
case was not analyzed to determine if the specific distress-
related mineral was ettringite or thaumasite. The position of
the primary x-ray diffraction peak is strongly suggestive of
ettringite but is not conclusive. Since no carbonate minerals
were found in the untreated soils, it is suspected that the
solid solution series would favor ettringite. However, the
extent that carbon dioxide (either dissolved in the porewater
or biogenic) participated on the reactions is not known. Where
C02 can be constantly supplied, laboratory research has shown
that thaumasite can form without the need for carbonate
minerals.
195
196
W ATER FROM RESIDENTIAL
L A W N IRRIGATION, CAR
WASH, POOL DRAINING ETC.
ETTRINGITE + CALCITE+ SILICA“^-THAUMASITE + GYPSUM WHEN TEMP. DROPS BELOW 15 C
CAPILLARY MOVEMENT
NATIVE CLAY PONDED WATER REMAINS

LONG AFTER STORM
Figure 31c Diagram m atic re p re se n ta tio n of the mechanism

of lime induced heave.
198
CHAPTER 9
CONCLUSIONS AND APPLICATIONS
Up to this point the research has been primarily concerned
with developing a detailed understanding of lime-clay-sulfate
reactions and the resultant volume increase. The underlying
goal of the project, however, is to put this knowledge to
practical use in predicting the conditions under which lime-
induced heave is likely to occur. From a thermodynamic
standpoint this is not difficult. The free energy of
ettringite is such that it will be the stable phase whenever
lime (CaO or Ca(OH),), clay, sulfate, and water are present,
in reality, some ettringite can be tolerated in the soil
structure without producing disruptive swelling. On the basis
of this research sulfate levels as high as 5000 mg sulfate per
1000 grams of soil should be acceptable for flexible pavements.
For rigid structures such as concrete slabs or foundations a
more appropriate limit would be in the range of
mg/kg. The real problem is controlling drainage and
capillarity sufficiently to maintain an essentially
system and prevent additional sulfate from reaching
ettringite/thaumasite nucleation centers. This is not
trivial chore, as will be discussed, and may void any economic
advantages of using lime to stabilize sulfate bearing soils.

199
L A B I L I T Y DIAGRAMS
The stability fields, relative to ettringite, of many
minerals and compounds can be derived from the equilibrium and
thermodynamic values obtained during this research. The goal,
however, was to develop diagrams that would be helpful in
evaluating the potential for ettringite/thaumasite growth in
lime-treated soils. For this purpose three ettringite
stability diagrams were selected, as discussed below.
Portland! te fCafOH),!
The stability relations between portlandite (hydrated
lime) and ettringite can be evaluated from the equilibrium
reaction:
Ca6[A1 (OH) 6]2* (S0 4)3*26H20 + 20H' = 3Ca(OH)2 + 3Ca2+ +
3 (S04)2' + 2A1(0H); + 26H20 .
From the expression Gr’ = products - reactants, the
value of g; for ettringite determined in this study, and
published values for the other species (KrausKopf, 1979) G° for
this reaction is 44.49 kcal/mole. The relationship between the
free energy and the equilibrium constant is log K„ = ___

-1.364
From the equilibrium reaction, log Keq
log (a[Ca2+]2 a[Al(OH)4']2 a[S042']3) = -32.64
log a [OH']2
200
J
201
R e a rra n g in g term s re s u lts in
log a[Ca2+]3 a[S02"]3 = -32.64 + 2 log a[0H"] - 2 log a[Al(0H);]
from which the stability diagram of Figure 32 has been
calculated. The stability fields of the two compounds have
been determined with aluminum activities ranging from 10"1 to
10"6. The pOH of lime-saturated soil and the minimum pOH for
dissolution of clay have also been plotted. The diagram is
useful mostly in that it shows the expected increase in the
stability field of ettringite with increase in the activity of
aluminum. An increase in the activity of calcium and/or
sulfate drives the reaction into the stability field of
ettringite. Conversely, an increase in hydroxide activity
drives the reaction toward portlandite. The pOH boundaries of
lime-saturated soil and dissolution of clay greatly limit the
actual stability fields.
Cypsum (CaSCj •2HzOl
The stability relationship between gypsum and ettringite
can be represented by the equilibrium reaction.
3Ca2+ + 2A1 (OH) 4 + 4OH" +

Ca6[Al (O H )6]2' (S04)3*2 6H20
3CaS04•2H20 + 20H20
Using the same procedures as for portlandite, Gr 48.48
log Ket = -35.54. The expression for the equilibrium constant

202
is log Keq = log (a[Ca2+]3 a[Al(0H);]2 a[0H‘]4) = -35.54 which can
be rearranged to _/
log (a[Ca2+]3 a(0H')4) = -35.54 - 2 log a[Al(0H);]
and used to generate the stability diagram shown in Figure 33.
This diagram, while interesting, is only marginally useful
since the activity of aluminum is very difficult to measure.
In addition, the diagram does not consider sulfate which, of
course, is critical to lime-induced heave. Nonetheless, the
figure shows that a very slight increase in the activity of
calcium, a rise in the pH, or an increase in the activity of
aluminum drives the system toward the ettringite stability
field. All three of these changes occur when a clay soil is
mixed with lime.
Bvn-T-inaite a n d t h e S a t u r a t i o n Index
The potential for ettringite precipitation can probably
best be determined from the saturation index. The saturation
index is defined as:
log (ion activity product)

p ( C a r (OH)
203
204
In this case SI -
lo g ( a [ C a ‘* ] ‘ a [ A l ( 0 H ) ; ] ‘ a [ S o ; - ] ‘ a [ 0 H - l ‘ a [ H ;0 ] ” )
-48.5
when the log of the ion activity product is greater than the
log of the equilibrium constant (SI>0) the system is
oversaturated with respect to ettringite and precipitation
could occur. Conversely, when the saturation index is
negative, the system is undersaturated with respect to
ettringite and no precipitation should occur. In reality, even
though the thermodynamics clearly favor this relationship, the
reaction kinetics may not. Often a high activation energy
precludes nucleation, even in solutions grossly oversaturated
with a specific mineral. In the case of ettringite, nucleation
and precipitation probably do occur when the solution is
saturated or only slightly oversaturated. This is evidenced
by the ease with which ettringite can be synthesized from a
variety of components as well as its formation when sulfate
contacts hardened concrete.
Figure 34 is a graphical presentation of the saturation
index relationship for ettringite and its component species.
The limits of pOH for lime-saturated soil and that required for
dissolution of clay minerals are shown, as are the effects of

. • x- “ The calculated locations
two different activities for A1(0H)4 . The cai
for untreated and lime treated soils from both Stewart and
Owens Avenues have also been plotted. These points are based
on the chemical analyses of these soil samples as presented in

p(Car(S04)
205
206
Appendix 5. The individual ion activities were calculated
using WATEQDR and are based on a fairly complete soluble ion
chemistry of the soil.
The diagram shows a distinctive grouping of treated and
untreated soils. This would be expected from the addition of
lime and the consequent rise in calcium activity, aluminum
activity and pH (decrease in pOH) . Once again, the most
difficult variable in the equation is determining the
appropriate range for the activity of aluminum. In general,
it is well known that the activity of dissolved aluminum
increases rapidly above a pH of approximately seven (refer to
Figure 7). Although the presence of sulfate has been shown to
affect aluminum solubility in acid solutions, there does not
seem to be much change for basic solutions (Nordstrom, 1982).
On the basis of Figure 7, the activity of Al(OH)“ can be
assumed to be approximately 10'* for the untreated Stewart/Owens
soils. This has been shown on Figure 34 and is for soils with
a pH in the range of 7 to 8. The estimation of Kl(OH):
activity for lime-treated soils is more difficult. Based again
on Figure 7, the activity could exceed iO- for lime saturated
soil (pH=12.3). However, a more realistic value is probably
in the range of 10-» since this is the value measured in the
determination of ettringite solubility. An activity of 10'3 has
been shown on Figure 34 as a slightly conservative value. In
fact, if the activity actually does reach 10'3 at lime
saturation, 10 3 is not conservative at all.

207
The majority of the samples of untreated soils plot above
the a(Al(0H)„‘) = 10'6 boundary, beyond the stability field for
ettringite. Samples S-4A, S-12B, S-19C, and S-21C, however,
plot in the ettringite stability field. Because the pOH is
higher than the maximum 3.5 required to supply aluminum,
"native" ettringite should not actually be present in this
environment. The data simply indicate unusually high activity
levels for calcium and/or sulfate. In addition, the data
suggest that the real aluminum activity for untreated soils
may be more on the order of 10'7 or 10‘B.
For lime-treated Stewart/Owens soils, the ettringite
stability is defined by the estimated boundary for a[Al(OH)t ]
= 10-3. in this case, all of the lime-treated data points fall
within the appropriate stability field.
FVAT.TTATINr; SUSCEPTIBILITY TP T,TMF,-INDUCED_JiEAVE
Figure 34 has been reproduced at a larger scale without
the data points and presented as Figure 35. The diagram is
interesting as it demonstrates the profound chemical changes
incurred by lime treatment of sulfate bearing soil. For
example, the calculated activities for several Stewart Avenue
soils have been plotted along with the calculated changes due
to addition of 4.5 weight percent CaO. The diagram shows a
pronounced shift well into the ettringite stability field. In

mixing soil with 4.5% CaO.
■NJ
209
fact, unless the native soil has a p[Ca]6 [S04]3 of greater
than, roughly 36, ettringite will always be the stable phase.
Assuming a gypsum source, this corresponds to an extremely low
sulfate level of less than 15 mg/kg of soil at pH = 12.3. The
figure is simply an indication of the very strong potential for
reaction at the high pH. In reality, there must be some
threshold value of sulfate below which reaction kinetics will
inhibit ettringite nucleation. It is not known what that value
might be, however, it is likely to be considerably more than
15 mg/kg. Distress occurred on Stewart Avenue in areas with
initial soil sulfate levels as low as 700 mg/kg, however, the
situation is complicated by porewater chemistry and ion
mobility. A great deal of additional, long-term
experimentation would be necessary to determine the threshold
sulfate value. One difficulty would be in detecting the
earliest, minute quantities of ettringite. Again, due to ion
mobility, the threshold level may not even be important from
a practical standpoint. As has been demonstrated at
Stewart/Owens, a great deal of sulfate can be derived from
outside the system.
in practice, a certain amount of sulfate can be tolerated,
even if it does cause minor heave. This is particularly
for flexible pavements. Figure 36 shows the calculated percent
expansion as a function of the initial sulfate content of the
soil. The diagram uses an assumed density of 100 pcf and
represents the probable maximum volume increase if all of the

PER CEN T VOLUME IN CREASE
Mg/Kg SU LFA TE
Figure 36 Calculated maximum volume inrease induced by complete reaction
of sulfate in lime treated clay soil. Dry density assumed to be 100 pcf.
211
sulfate reacts. Some, perhaps half, of the sulfate, will not
react so the figure is properly conservative in that regard.
The relationships shown are based on laboratory
experiments, assumptions that may not be entirely valid, and
site specific empirical data obtained from soils on
Stewart/Owens Avenue in Las Vegas. In addition, other factors
such as the availability of water and ion mobility have
tremendous bearing on whether or not nucleation of e t t n n g i t e
will even result in distress. On Stewart/Owens even the rock
hard, undamaged, subbase contained minor ettringite. A
with no measurable sulfate could, conceivably, react if sulfate
were brought in from an outside source. This could occur from
surface water, capillary porewater or from biogenic sources,
as may have happened in Tennessee. Other sources of sulfate
from outside the soil system may be possible. The writer, the
University of Nevada, the Desert Research Institute and SEA
INC. make no warranty, expressed or implied, that the use of
Figures 35 and 36, and other data in this research, will not
result in evaluations that are either overly or insufficiently
conservative.
engineering CONSIDERATIONS
The potential for lime-induced heave can be predicted for
the two extremes. If the geochemical environment contains less
than 15 mg sulfate per 1000 gm soil (50:1 extraction ratio)

212
sulfates, no lime-induced distress should occur. At the other
end of scale, where soluble sulfates approach 1% (5000 mg/kg),
clay minerals account for at least 10% of the soil, and the
environment is frequently saturated, significant (> 1/2 inch)
lime—induced heave will occur. The difficulty, then, is
determining heave potential between these extremes and
establishing a safe set of guidelines that can be used by the
practicing geoscientist.
It would be easiest to exclude all soils with measurable
sulfate, and given the state of the art, this might be the
appropriate conservative approach. The risks involved are
high. With Stewart Avenue, lime treatment might have saved
$500,000 in initial construction costs over some of the other
alternatives. Repair of lime-induced distress, along only 2/3
of the roadway, however, cost $2,700,000. In addition,
liability to the engineer for lime-induced heave has increased
with awareness of the problem. Unfortunately, excluding all
sulfate soils from lime stabilization is overly conservative
and may incur excessive construction costs.
A limited amount of swelling produced by low sulfate
levels can readily be tolerated, provided the R-value does not
decrease significantly. At Stewart Avenue, however, lime-
induced heave occurred in areas where native soils may have
an initial sulfate content as low as 700 mg/kg but were
adjacent to a major water source. In addition, sulfate levels

as high as 20,500 mg/kg were recorded in native soils from
undamaged areas where subbase had to be removed with a
jackhammer. The majority of these areas were east of Lamb
Boulevard where clay content was generally low. Sulfate levels
as high as 43,500 mg/kg were recorded in undamaged subbase.
In these cases, sulfate was tied up in gypsum rather than
thaumasite. The particular value of 43,500 mg/kg was found in
the same trench as, and only a few feet away from, an area of
severe heave. The heave followed a linear trend adjacent to
a water main.
In conclusion, the results of this study indicate that
lime treatment of sulfate-bearing clay soils is risky, even at
relatively low sulfate concentrations. It does appear that
approximately 10% by weight, or more, clay-sized particles are
needed for adverse reactions. While both sulfate and clay
minerals are required, their threshold concentrations are
complicated by ion mobility in soil pore water. Excessive
water may mobilize and concentrate necessary ions in areas
where distress might otherwise not occur. Since diffusion
through saturated fine-grained soils is extremely slow, lime-
induced heave occurs preferentially in areas where water flows
more freely. This includes, but is certainly not limited to,
utility trench backfill and construction joints.
If utility trenches use impermeable synthetic liners and
are sloped to drain and construction joints are adequately

sealed, it should be possible to successfully use lime
stabilization in soils with high concentrations of both sulfate
and clay minerals. Excellent surface drainage would also be
mandatory to prevent ponding of water. The ultimate technical
solution would include an impermeable membrane or capillary
break beneath the lime stabilized soil. This should be quite
effective; however, removing and replacing the soil in order
to install the barrier would offset lime's major cost advantage
which is in-place stabilization.
Since cement-sulfate-clay reactions are similar to those
of lime-sulfate clay, similar risks are present for soil
cement. Heave in soil cements has also been documented where
sulfate is present (Lukas 1975).

215
REFERENCES
American Public Health Association, American Water Works

Association and Wastewater Pollution Control Federation,
1980, Standard Methods for Examination of Water ana
Wastewater, 15th Edition, 1193 p.
Barnes, H. L. , 1980, editor, Geochemistry of hydrothermal ore
deposits: New York, John Wiley and Sons.
Bell, J. w . , 1982, Subsidence in the Las Vegas Valley: Nevada
Bureau and Mines Geol., Bull. 95, p. 13“1^;
Bensted, J. , and Varma, Prakash, 1973, Studies of Ettringite
and Its Derivatives, Part IV: The low-sulphate form
calcium sulphoaluminate (monosulphate): Cement Technology,
l\
Berner, R. A., 1971, Principles of Chemical Sedimentology.
Bohm!r~ r d anS J°acobson! L 1981, WATEQDR an updated
C a U ? c r n I a VaDepartm ent of Transportation 1976

stabilization study: A selected lltera\ur® rJ}T£rt
Materials and Research Department, Research Repor
C a l i f o r n i a ^ e ^ r t m e n t of Transportation, 1 9 7 4 , Highway Research

Report-Lime Soil Stabilization Study, P h a s e I I , Laboratory
Investigation of California Soils for ^ m e Reactivity.
Transportation Laboratory Research Report CA-DOT TL 2812
California6 d i v i s i o n of H i g h w a y s “ ? select^
Department, 1967, Lime-soil stabilization,
literature review, 94 P; 1974, subgrade Soil
coS g a £ r
Street to Nellis Boulevard, Las Vegas, Nevada. v
Consultant Report 40 p. 1Q7r proiect No.
converse, Davis, and Associates June 13 ^ V a / e ^ting,
N-75-808-D, Final Report on Lime Tr « unpublished
Stewart Avenue Improvements, Las Vegas,
consultant inspection Report 7 p. cement exposed to
sulfates: Highway R e s . ^ r d , descriptive
Mineralogy": John Wiley and Sons, New^York, l” 1 . 1 ‘3 ^
Dapulveration M n d S E ' & r & o T « ^ l i « stabilization:

Highway Res. Rec., 92, p. 103 126.
216
Dinger, J. S., 1977, Relation between surficial geology and

near-surface groundwater guality, Las Vegas Valley, Nevada:
Unpublished PhD dissertation, Department of Geology,
University of Nevada, at Reno.
Drever, James I., 1982, The geochemistry of natural waters:
Prentice-Hall, Inc., Englewood Cliffs, N. J., 388 pp.
Eades, J. L. , and Grim, R. E. , 1966, A quick test to determine
lime requirement for lime stabilization: Highway Res. Rec . ,
139, p. 62-72. ^ ^ ^ , , ,.
Eades, J. L. , and Grim, R. E. , 1960, Reactions of hydrated lime
with pure clay minerals in clay stabilization: Highway
Research Board, Bulletin No. 262, p. 51-63.
Edge, R. A., and Taylor, H. F. W., 1971, Crystal structure of
thaumasite: Acta crystalography, Bulletin 27, 594-601.
Font-Altaba, M. , 1960, A thermal study of thaumasite:
Mineralogical Magazine, 32, 567-572.
Fournier, R. 0., and Marshall, W. L %, 1983, Calculation o
amorphous silica solubilities at 25 to 300 C and apparen
cation hydration numbers in aqueous salt solutions using t
concept of effective density of water: Geochemical
Cosmochimica Acta, V. 47, No. 3, p. 579-586.
Gaffron, Winston, 1988, Tennessee Department of Transportation,
Mochvilie Tennessee: Personal Communication.
Garrels R.' m ., and Christ, C. L . , 1965, Solutions, Minerals
and Equilibrium: San Francisco, Freeman, Cooper and Company.
Gouda, G. R., Roy., D. M . , and Sarkar, A., 1975, Thaumasite in
deteriorated soil cements: Cement Concr. Res., 5 / 519-522.
Graf, Edward, 1986, Pressure Grout Inc., San Francisc ,
California: Personal Communication. Mr,rraw_H n i
Grim, R. E., 1968, Clay mineralogy: New York, McGraw Hill,
Habib P 'p and Aversence, D., 1987, Gonflement d'un sol

H a oonienant des sulfates et traits S la chaux et au ciment:
Revue Francaise de Geotechnique, 42, 61 64. Nevada-
Heidker, James, 1988, Desert Research Institute, Reno, Nevada.
H i £ T 2 . ,
C° a " d ^ n , D. *., I960, Lime fixation in clayey
Hol?isS: BHlgr y \endear?awcett:tlnN.2 6 D., ôratory

investigation of the use of mixtures of lime and pulverized
fuel ash for soil stabilization: Roads Road Constr.,
44(517), 3-6.
Lime-induced heave in sulfate-bearing clay
Hunter, Dal, 1988,
Geotechnical Engineering, ASCE, 114(2),
soils: Journal of
150-167. 1960, Ettringite from Franklin,
Hurlbut, C. S. and Baum, J. L. Mineralogist, v. 45, No. 11 and
New Jersey: The American
12, P. 1137-1143.
217
Kelley, Conard M. , 1977, A long-range durability study of lime

stabilized bases at military posts in the southwest:
National Lime Association Bull. 328, Washington, D. C. , 29
Kirov, G. N., and Poulieff, C. N., 1968, On the infra-red

spectrum and thermal decomposition products of thaumasite.
Mineralogical Magazine, No. 36, p. 1003-1011.
Kollmann H. , 1978, Minerlogische untersuchungen uber
ausbluhungs und treiberscheinungen and baustoffen durch
sulfate: Giessener Geologische Schriften, Giessen, Germany,
Kollmann’, H. , Strubel, G. , and Trost, F. (1976). _"Synthesen

von Ettringit und Thaumasit." Fortschritte der Mineralogie,
Beihefte, 54(1), p. 50—51. „„ Mlnpral-
Kollmann, H. , Strubel, G. , and Trost, F. , 1977, Mineral
synthetische untersuchungen zu treibursachen durch Ca
sulf at und Ca-Si-carbonat-sulf at hydrat." Tonmdu s t r i e
Zeitung, 101(3), Germany, 63-70. m q 77 ' i
K° S i o n s ^ h a , = ^ r
gips-putzen durch ettringie und thaumasit. Zement K
Kollmann"^0 #H ^ ,* and"2Strubel, G. 1981,

Mischkristalle von Brenk (Eifel): Chemical Erde, 40,
Giessen, Germany, 110-120. r^nnhpmistrv*
Krauskopf, Konrad B, 1979, introduction to Geochemistry.
McGraw-Hill, Inc., New York, N. Y. , 617 pp.
TaHd C C Moh. Z. C., and Lambe, T. W., 1960, Receive sox
u M e Mesiirch i t the Massachusetts Institute of Technology.
Highway Res. Board Bull. 262, 64-84.
^ o v ^ t - o f ^ ? 1^ S i S T u l i c;M p o U ;
L e h m S n ? Y JR !S ^ r i n g m “^laache?
GebietîH^Jeifes1J^hbtich de? Mineralogie und Geologie, 6, 273-
275. -o u Rffl,rvpr Ben. and Roberts, R.
Longwell, C . p o s i t s of Clark County,
NiMadaf 'Nevada Bureau of Mines and Geology, Bulletin 62,
Lukas,^W., 1975, Betonserstorung SO,.angriff unter bildung

von thaumasit und woodfordit: Cement Concr.
^ * — •-i -1.!-mo ypc: T"Ch clt IOWcl St3.t0
Mateos, Manuul, 196 ' ° soil Mechanics and Foundations
DivisionÂSCE ^Proceedings ,Syol • ?1. *>• * . ^ u _ fly
M°ashe and ^ t h e f U m e ^ a c l f v e ^ a t e r i a l s : Highway Research
Board, Bulletin 231, p. 60-66.
218
McDowell, Chester, 1966, Evaluation of soil-lime stabilization

mixtures: Highway Research Record, 139. ,
McDowell, Chester, 1972, Flexible pavement design guide.
National Lime Association, Bulletin, 327.
Mehra, S. R. , Chadda, L. R . , and Kapur, R. N. , 1955, Role of
detrimental salts in soil stabilization with and without
cement I. The effect of sodium sulfate: Indian Concr. J . ,
Mehta,3p. K., 1986, Effect of fly ash composition on sulfate

M resistance of cement: American Concrete Institute Journal,
Mi“ i r ^ “ ^ 8D4r9^ r b|ci1luS = Thonindustrie-
M i H U r k NCi . “ ^ E “ « . M . , 1979. P l u v i a l l a . e s ana

e stim a te d p lu v ia l c lim a te s o f Nevada: N evada Bureau M in e s
Mitcheii?UJ^ K w iP
6
8
9
l
' ractical p r o b l e m s l r o m surprising soil
behavior: J. Geotech. Engrg. Div., A 3 CB, 112( 3 ), 259 289.
Mitchell, James K., 1988, Department of Clvl1.
University of California, Berkeley, California: Personal
„ o ™ ! CEa ^ ° a nn a T a y l o r , H . E . W 1970 C ry sta l stru ctu re of

ettringite: A c ta Crystalography, B u l le t i n 2 6 , 3^ . ^
n ? S i l J f r o r c r t at r e S,' SilifV: Geological society of

America, Bulletin 69, 1620-1621.
A., 1960, Ettringite
Murdoch, J. , and Chalmers, California: American
("Woodfordite") from Crestmore,
Mineralogist, 45, 1275-1278. mineral:
Nordenskiold, A. E., 1878, Thaumasite, ein neues m m .
Compt. rend. 87 p.. 3 1 4 . ffect of sulfate on aluminum
Nordstrom, D. K. , 1982, m e e n c ___ofahilitv Relations
concentrations in natural waters: B o n e Stahl ^
in the System Al203 " s03 “ H ^° ar
P e c r G e ? a l 1 r ai9 A7 t % e x i s ( D
42pa6S e n t o f T ra n s p o rta tio n , A u s tin ,
Ra“ , Lo?en:n i 9 8 3 M ” ;hCSep“ tment of Transportation, Salt

Lake City, Utah: Personal 197A Encyclopedia
R °ofMinerals; V a n ^ o s t r a n d Reinhol^Co. f New York, p.^197-198;
Ruff^ C . G. , and Clara, Ho. . 1966- '

Time--t-P-ature^trength-
reaction product relationships m 11 42-6 0 .
mixtures: Highway Research eco ' r city of Las Vegas,
SEA, Inc. , 1983, e T o fliis B W o Las Vegas,
Stewart Avenue 28th Street e
Nevada: Unpublished consultant repor .
219
SEA Inc., 1988, Evaluation of continuing pavement distress,

Owens Ave., Las Vegas, Nevada: Unpublished consultant
S h e r w o o d P . T. , 1958, Effect of sulfates on cement-stabilized

clav: Highway Res. Board Bull, 198, 45-54.
Sherwood, P. T. , 1962, Effect of sulfates on cement and lime
treated soils: Highway Res. Board Bull. 353, 98"107* .
Taylor, H. F. W. , 1964, The chemistry of cements: Academic
pvpqc New York, Vol. 1, 460 p.
T a y l o r / W. H. , and Arman, Ara, 1960, Lime stabilization using
precondition soils: Highway Research Board, Bulletin 262,
Thompson, M. R., 1966, Lime reactivity of Illinois soils:

J. Soil Mech. Found. Div., ASCE, 92(5), 67 92. survey
United States Department of Agriculture 1972, lltl
laboratory methods and procedures for collecting soil
samples: Soil Survey Investigation Report No 1, 31
- ? o S : = -
related substances in the presence^ of sulphates, cemenr ana
Concrete Research, Vol. 5, p. 225 232' ,t . Arkj_v for
Welin, E., 1956, Crystal structure of thaumasite.
Mineralogi och Geologi, Sverige^ 2 1 • California's
Zube, E., Gates, , and Hatano, FL, ^ ' construction:
experience with lime trearme
California Highways and Public Works.
Sample Number S-2A S-2B S-2C S-3A
Sieve Size Percent By Weight Passing
1-1/2 Inch 100 100 100

1 Inch 100 100 94 96 90 100
96
3/4 Inch 97 83 87 91 81 100 100
1/2 Inch 89 64 77 80 100 74 97 93 92
3/8 Inch 78 56 100 66 75 99 68 91 86 89
No. 4 62 46 98 54 63 98 58 81 72 85
No. 8 52 44 47 74 • 57
No. 10 35 97 54 98 81
No. 16 45 36 36 67 48
No. 20 - - - - - - “ “
No. 30 41 - - 28 - - 25 59 45 -
No. 40 _ 25 96 - 46 97 - - - 74
No. 50 36 _ - 22 - - 17 50 43 -
No. 60 _ 22 94 - ’ 42 97 - - - 70
No. 100 32 19 72 21 40 95 13 42 41 61
No. 200 19 12 52 17 29 91 6 38 38 46
Hydrometer Percent Fines of Total Sampl e

Silt T.U74-.005mm) _ 11 20 - 22 44 35 15 ~
Cl ay (.005-.001mm) - 1 20 - 5 32 1 21
Colloids (<.001mm) - 1 12 2 15 ” 2 2
■
Liquid Limit . _ 42 _ 33 36 - 59 57 30
Plastic Index NP NP 19 NP 4 14 NP 20 43 9
Moisture Content (%) 8 25 25 8 35 17 20 37 21 7
FIELD DENSITY TESTS
Depth (feet) 0.46 1.25 2.00 5.75 1.08 2.50 0.50 1.00 2.50 0.0
In-Place Dry D e nsit y-( pcf) 125.1 89.9 100.2 122.3 78.1 99.5 112.3 96.7 110.8 98.4
Maximum Dry D e nsit y-( pcf) 141.4 120.0* 125.9 129.5 120.0* 118.1 129.0 119.0* 114.9 123.1
Relative Compaction (%) 88.5 74.9 79.6 94.4 65.1 84.2 86.8 81.3 96.4 79.9
11.3 9.4 13.0* 14.6 9.0 12.5* 16.8 9.0

Optimum Moisture (%) 6.0 13.0*
& Assoc
Lime Treated Subgrade Testing, Stewart Avenue", 7 - 1 - 7 5 :, Converse Davis
nhtainpd from "Final Reoort on
220
Appendix 1 a
MECHANICAL ANALYSIS
S-6B S-6C S-7A S-7B S-7B1 S-7C S-8A
Sample Number S-4B S-4C S-4D
Percent By Weight Passing
Sieve Size
92 100 100 100 100
1-1/2 Inch 69 94 97 96
1 Inch
_
87 -
_ 85 100 69 92 93 95
3/4 Inch 63 83 89 89
1/2 Inch 100 100 80 99
74 99 59 78 87 100 82
3/8 Inch 99 97
57 90 49 75 84 98 67
No. 4 100 97 89 54
_ 42 82 39 -
No. 8 71 80 95
No. 10 99 95 82 - - -
42
34 76 29 -
No. 16' _ _ - 69 77 94
No. 20 21 32
No. 30 29 71 -
72 _ - - 65 75 93
No. 40 97 82 25
_ 25 67 15 -
No. 50 61 73 93
No. 60 95 73 68 - . - -
22
57 57 22 65 13 SB 72 92
No. 100 85 9 46 67 86 18
No. 200 59 32 39 18 59
Hydrometer Percent Fines of Total Sample

_ 17 23 - 42 31
Silt (,074-.005ram) 10 15
Clay (. 005- .001mm) 19 _ 1 30 - 3
1 6 1 40
Co lloi ds (<.001mm) 3 -
33 51 24 - 80 52
Liquid Limit 32 24 27 NP
17 3 NP 22 NP
Plastic Index
Mo istu re Content (%)
17
13
6
7
14
15 36 9 54 21 30 7
FIELD DENSITY TESTS

3.00 0.43 1.1 1.00 2.67 0.50
Depth (feet) 2.00 2.50 4.17 1.00
73.8 102.2 129.3 61.1 90.5 87.9 131.1
In-Place Dry D e n s i t y - ( p c f ) 87.1 85.8 102.2
106.0* 122.9 141.0 106. 106.0* 106.9 141.0
Maximum Dry D e n s i t y - (p c f ) 119.0* 123.1 123.1
83.2 90-95 57. 85.4 82.2 90-95
Relative Co mpac tio n (%) 73.2 69.7 83.0 69.6
18.5* 12.2 6.0 18. 18.5* 18.5 6.0
Optimum Mo istu re (%) 12.5* 10.8 10.8
Assoc.
Lime Treated Subgrade Testing, Stewart Avenue", 7-
*Data o b tain ed from "Final Report on
Appendix 1 b
MECHANICAL ANALYSIS
S-8B S-8C S-8D S-9A S-9B S-9C S-9D S-10A S-10B S-10C
Sample Number
_ 100 100 -
1-1/2 Inch _ _ 96 97 -
1 Inch _ _ 95
100 100 94 -
3/4 Inch _ 88 92 100
1/2 Inch 92 99
_ _ 98 84 88 99
3/8 Inch 86
78 100 100 100 100 - 96 71 84 98
No. 4 _ _ - 56 “
No. 8 74 99 - -
99 99 98 100 95 - 81 96
No. 10 43 -
No. 16 71 98 - - - -
98 _ - - - “ - -
No. 20 _ - - 32 - -
No. 30 68 97
96 97 82 94 82 - 73 94
No. 40 _ _ - - 24 " “
No. 50 65 96
94 93 71 92 71 - 68 90
No. 60 49 18 62 90
No. 100 64 91 92 88 55 84
87 84 66 55 71 30 13 53 49
No. 200 54

Silt (TU74-. 005mra) 50 74 _ 19 51 - - 48 14
Clay (.005-.001mm) 2 8 _ _ 29 17 - 1 7
7 3 " 4 28
Colloids (<.001mm) 2 5 - -
56 31 ■ 30 52 39 24 - 82 38
Liquid Limit 70 18
20 33 18 13 31 23 10 NP 25
Plastic Index 5 57 15
Moi sture Content (%) 59 32 23 11 10 17 15
FIELD DENSITY TESTS

4.50 0.00 1.50 2.50 4.00 0.46 1.33 3.33
Depth (feet) 1.25 3.00
87.4 95.5 93.7 74.7 73.0 69.3 126.5 61.5 88.2
In-Place Dry De ns i t y - ( p c f ) 59.3
106.9 108.8 105.0* 118.5 112.9 141.0 108.0* 108.0
Maximum Dry Densit.y-(pcf) 105.0* 106.9
89.3 86.1 71.1 61.6 61.4 88-92 56.9 81.7
Relative Compaction (%) 56.5 81.8
19.2* 10.0 12.9 0 18.5* 18.5
Optimum Moisture (%) 19.2* 18.5 18.5 13.8
, Converse Davis & Assoc.
Lime Treated Subqrade Testing, Stewart Avenue ", 7-1-75
obtained from "Final ReDort on
ME C H A N I C A L AN ALYS IS
S-11B S-11C _
S-11D S-12A S-12B S-12C S-12D S-13A
Sample Number S-10D S-11A
"Percent By Weight Passing
Sieve Size
100 100
1-1/2 Inch _ 100 - - -
_ - 92 88
1 Inch 92 100 -
73
- 100 86
3/4 Inch 100 85 99 64
96 - 98 83
1/2 Inch 99 75 80 59
98 68 93 100 100 95
3/8 Inch 99 92 76 47
No. 4 98 56 85 99
_ - 89 39
No. 8 44 - -
73
78 99 99 100 100
No. 10 94 -
30
34 86
No. 16 _ - - - " ~ “
No. 20 83 22
No. 30 26 68
70 97 96 97 97
No. 40 83 16
18 80
No. 50 92 94 64
No. 60 76
63 11
64
57
96
92
95
91 73 85 87 63 10
No. 100 75 59 69 67 34 5
No. 200 43 4 47 77
Percent Fines of Total Sample
Hydrometer - -- W 59 -
Silt (.074-.005mm) 44 33 -
2 39 - - 9 5 -
Clay (. 005- .001mm) 5 3 -
Colloids (<.001mm) - - 1 5 -
47 37 41 37 58 42 57
Liquid Limit 29 36 22 30 NP
14 NP 14 22 19 18
Plastic Index 19 7 12 14 13 3
Moisture Content (%) 14 21 39 29
FIELD DENSITY TESTS
4.33 0.00 1.17 2.33 3 0.12
4.00 2.50 18.0 3.00
Depth (feet)
82.5 103.4 92.1 62.8 77 135.8
In-Place Dry Densit,y-(pcf) 89.7 107.4 65.3 73.9
108.0 108.0 108.0 108.0 - 141.0
Maximum Dry D e n s i t y - ( p c f ) 125.6 130.0 108.0* 108.0
76.4 92-96 85.3 58.1 - 95-97
Relative Compaction (%) 71.4 80-85 60.5 68.4
18.5-* 17.6 ■ 17.6 14.3 14.3 14.3 6.0

Optimum Moisture (%) 11.7 9.0
& Assoc.
Lime Tr eated Subgrade Testing, Stewart Avenue", 7-1-75, Converse Davis
I *nata obtained from "Final Report on
MECHANICAL ANALYSIS
S-14A S-14B S-14C S- 15A S-15B S-15C S-16A S-16B
Sample Number S-13B S-13C
Sieve Size
100 . 92 - - 100
1-1/2 Inch 85 81 100
1 Inch 89 100 -
87 94 100 80 100 74 95
3/4 Inch 100 88
100 83 83 97 75 95 68
1/2 Inch 98 63 83
94 99 76 74 95 71 90 -
3/8 Inch 59 81 50 68
No. 4 83 99 63 54 83
No. 8 51 _ _ 47 - 38
38 77 68 100 58
No. 10 71 98 -
40 - - 34 “ 28
No. 16
No. 20 _ 23 - - 21
No. 30 31 50
55 97 22 70 - 49 98
No. 40 _ _ 15 - 16
No. 50 24 49
50 96 18 69 - 44 96
No. 60 66 10 38 92 12 43
No. 100 45 88 18 15
37 70 14 11 54 5 29 72 8 35
No. 200
8 25 20 42 30
Si U""{T074-. 005mm) 23 58 3
7 2 6 - 8 26 -
Clay (. 005- .001mm) 8 - 4 2
6 5 1 23 1
Colloids (<.001mm)
46 52 27
Liquid Limit 30 NP NP 5 NP NP
Plastic Index NP 24 NP NP 18
22 30 7 55 21 6
Moisture Content (%) 41 25 7
FIELD DENSITY TESTS
2.00 • 0 .48 1.00 1.50 0.46 1.00
Depth (feet) 1.50 3.00 0,.46 1.17
88.4 123 .8 54. 4 73. 6 131.5 86.3
In-Place Dry D e n s i t y - ( p c f ) 61. 4 64.5 118 .5 76.7
107.0* 103.4 130 .0 107.,0* 98. 6 141.0 107.0*
Maximum Dry D e n s i t y - ( p c f ) 106.,0* 101.3 130 .0
71.7 85.5 90- 95 50..8 74.,6 90-95 80.6
Relative Compaction (%) 57..9 63.7 90- 95
19.8 11.0 19..4* 21..5 7.0 19.4*
20.518,.5*11.0 19.4*
Optimum Moisture (%) & Assoc.
Treated Subgrade Testing. Stewart Avenue". 7-1-75, Converse Davis
*Data obtained from "Final Report on Lime
224
A p p en d ix 1e
225
i
MECHANICAL ANALYSIS
S-21B S-21C S-22A S-22C S-22D S-23A S-23B
Sample Number S-19C S-19D S- 21A
Sieve Size
100 _ - 100 -
1-1/2 Inch 100 92 97
1 Inch 100 100 100 100
94 87 89 87 100
3/4 Inch 78 90 96 75 88
73 81 89 77 68 81
1/2 Inch 68 60 76 - 67 83
3/8 Inch 69 79 83 72
50 45 68 100 55
No. 4 62 71 69 46
58 54 39 48
No. 8 99 100 62
No. 10 64 45
35 35 38
No. 16 54 42
No. 20 32 24 31
No. 30 49 32 46
35 98 97
No. 40 52 24
43 23 28 16
No. 50 97 93 42
45 30 38
No. 60 26 21 10 96 91 18
No. 100 37 35 16 31
23 12 4 86 86 12
No. 200 28 21 9
Percent Fi nes of Total Sampl e
Hydrometer 10 46 ay
Silt (.074-.005mm) 24 15
5 1 33 - 1
Clay (. 005-.001mm)
Colloids (<.001mm)
1
3
- ; 3 1 _ 7 - 1
35 29 73
Liquid Limit 52 14
17 NP NP 16 10 NP
Plastic Index NP NP NP 4 39
5 14 3 10 22 10
Moisture Content [%) 7 5
FIELD DE NSIT Y TESTS
3.00 0.50 2.00 3.50 0.21 1.00
2.50 3.50 0.50 1.08
Depth (feet)
121.1 128.2 84.2 84.4 132.2 65.0
In-Place Dry Densit,y-(pcf) 109.9 106.5 121.2 94.4
127.5 141.0 117.3 117.3 141.0 115.0*
Maximum Dry Densit.y-(pcf) 125.2 125.2 130.0 1 0 7.0**
95.0 90-95 71.8 72.0 90-95 56.5
Relative Compaction (%) 87.8 85.1 90-95 88.2
7.0 14.4 14.4 6.0 15.0*
8.0 8.0 9.0 19.4* 11.1
Optimum Moisture (%)
rse Davis & Assoc.
Lime Treated Subgrade Testing, Stewart Avenue", 7-1-75 , Conve
*Data obtained from "Final eport on
A ppendix 1g
MECHANICAL ANALYSIS
Sample Number S-23C S-24A S-24C S- 25A S-25B S-25C S-26A S-26B S-26C S-27A
Sieve Size ---- ---- Percent B.y Weight Passing
- - - - 100
1-1/2 Inch 100 94
1 Inch 82 _ 100 - - 100 100
_ 99 100 - 95 98 88
3/4 Inch 75
_ 93 98 - 78 90 80
1/2 Inch 72 75
3/8 Inch 100 69 - 85 97 68 81
100 71 84 - 51 64 60
No. 4 98 56 46
t No. 8 45 - 57 - 39
97 _ 99 - 59 " 53 100
No. 10 30 34
No. 16 35 - 44 -
No. 20 “ _ - 23
26 32 22
No. 30 _ - 100 39 98
No. 40 96 83 26
_ 23 - - 17 16
No. 50 19
95 73 - • 20 99 " 36 96
No. 60 16 99 12 33 93 11
No. 100 95 12 64 16
6 58 9 11 94 8 27 78 6
No. 200 93
Hydrometer
82 _ 54 - --------8 ------58------ - 24 73
Si It (.074-.005mm)
Clay (.005-.001mm) 7 _ 2 - 1 2 “ 2 1
Colloids (<.001mm) 4 - 2 - 2 4 _ 1 4
. 30 39 _ - 25 - 48
Liquid Limit
19 NP NP 8 NP NP 26 NP
Plastic Index
Moisture Content (%)
11
16
NP
6 20 6 14 16 6 39 18 6
FIELD DENSITY TESTS

0.50
Depth (feet) 2.67 0.50 2.00 0.54 1.50 2.50 0.48 1.00 2.17
90.4 126.4 109.3 92.6 96.7 62.7 96.7 131.1

In-Place Dry D e nsit y-( pcf) 106.6 119.1
130.0 113.0* 114.4 125.9 105.0* 117.2 141.0
Maximum Dry D e nsit y-( pcf) 118.0 125.9 115.2
78.5 95-98 96.7 80.9 76.8 59.7 82.5 90-95
Relative Compaction (%) 90.3 94.6
• 16.4* 16.6 9.3 19.2* 14.3 7.0
14.4 9.3 14.0 9.0
, Converse Davis & Assoc.
iimp Treated Subgrade Testing. Stewart Avenue", 7-1-75
♦nata nht.ain.ed_.from "Ftaal ReDort on
227
Appendix 1h
---------------------------------------------------------------------- .a
M E C H A N I C A L ANALYSIS
;-28B S-28C S-29A S-29C S-30A S-30B S-30C

Sample Number S-27B S-27C S-28A
-- Percent iTv Weight Passing
Sieve Size
- -
1-1/2 Inch
1 Inch 100 100
3/4 Inch 97 - 91
1/2 Inch 87 - 84 100
3/8 Inch 61 _ 69 99
No. 4 _ 55 -
No. 8 47 100 - 99 55 100

38. 10 38 100
- - 41 -
No. 16
No. 20 30 _
No. 30 32 99
No. 40 21 96 25 98
_
-
21
97
-
No. 50 21 94 - 94
No. 60 18 82 14 88
No. 100 10 61 6 76
No.' 200
Percent Fines of Total Samp!e
Hydrometer 56 69 a /H
10 60 “ 4
ram
— Silt "(7074-.005mm) 3 2 6
1 5 5 2
Clay (.005-.001mm) 1 3 _ 4 - 1 3
Colloids (<.001mm) 1 1
32 23
53 34 3
Liquid Limit 12 NP 13 NP NP
NP 27 NP NP 20 12
Plastic Index 37 26 6 18 5
Moisture content (%) 32 29 9
FIELD DENSITY TESTS
0.25 3.00 0.50 - 2.00
0.92 2.00 0.40 0.67 2.25
Depth (feet)
130.1 80.2 125.8 - 84.8
89.7 83.3 118.9 71.9 83.3
In-Place Dry D e n s i t y - ( p c f )
141.0 114.0 126.2 - 118.5
105.0 111.5 130.0 108.0 116.0
Maximum Dry D e n s i t y - ( p c f )
90-95 70.4 99.7 - 77.1
85.4 74.7 90-95 66.6 71.8
Relative Compaction (%)
7.0 15.3 9.8 - 10.4
13.6 11.0 18.5 ■ 13.7
Optimum Moisture (%) 19.2
Treated Subgrade Testing. Stewart Avenue", 7-1-75, Converse Davis & Assoc.
*nata ohtaijied from "Final Report on Lime
to
to
Appendix 1i co
MECHANICAL ANALYSIS
Sample Number S-31A S-31B S-33A S-33C S-34A S-34B S-34C S-B2 S-B3
1-1/2 Inch 65
1 Inch _ _ 100 100 62 - - -
3/4 Inch 100 _ 81 87 50
1/2 Inch 89 _ 73 67 38
3/8 Inch 81 _ 67 54 34
No. 4 64 _ 53 34 24
No. 8 48 _ 40 21 19
No. 10 _ _ 100 - - 100 100 100
No. 16 34 - 29 14 15
No. 20
No. 30 23 _ 19 9 13
No. 40 _ _ 99 - - 98 97 94
No. 50 15 _ 13 6 11
No. 60 _ _ 98 - - 96 95 86
No. 100 10 _ 8 97 4 7 93 90 79
No. 200 5 - 4 80 2 1 89 88 77

Si It (.074-.005mm) _ _ 68 - 57 58 69
Clay (.005-.001mm) _ _ 7 - - 23 19 5
Colloids (<.001mm) - - 5 9 11 -
Liquid Limit 34 26 _ _ 32 _ _
Plastic Index NP 9 NP 5 NP NP 10 - -
Moisture Content (%) 6 21 5 14 5 5 30 23 16
FIELD DENSITY TESTS
Depth (feet) 0.50 1.08 0.50 2.50 0.50 1.50 3.00
In-Place Dry De nsit y-( pcf) 119.3 114.5 122.2 86.9 126.6 117.8 79.2
Maximum Dry De nsit y-( pcf) 130.0 120.0** 130.0 117.8 130.0 - 116.2
Relative Compaction (%) 90-95 90-95 90-95 73.8 95-98 - 68.2
Optimum Moisture (%) 11.0 13.0 11.0 12.6 •11.0 - 13.8

, 7-1-75, Converse Davis & Assoc.
*Data obtained from "Final teport on Lime Tredted Subgrade Testing, Stewart Avenue
MECHANICAL ANALYSIS
0-2BU 0-2C 0-3B 0-3C
0-1B 0-1C 0-2B
Sample Number
Sieve Size_
1-1/2 Inch 100 100
92 100
1 Inch 94 100 82
3/4 Inch 82 61
76 76 87
1/2 Inch 67 79 100 55 '
3/8 Inch 69 98 45
61 60 58
No. 4 43 96 32 100
54 100 38 97
No. 10 24 29 95 32
No. 40 44 99 30 95
97 21 93
No. 60 42 91 27 92
35 94 13 12
No. 100 5 82 22 85
26 88 8
No. 200
Hydrometer
6 75 20
Silt (.074-.005mm) 20 42 1
42 1 - 3
Clay (.005-.001mm) 4 4 1
Colloids ( .001mm) 2 4 1 41
35 19
Liquid Limit 42 NP 26
23 NP NP 20
Plastic Index NP 17 28
28 23 5 10
Moisture Content
2.33 2.92 0.85 2.25

0.85 1.67 0.85
Depth (feet)
104.8 84.5 81.8 93,3
123.8 82.7 89.7
In-Place Dry De nsity-(pcf)
122.6 116.5 123.0* 112.0
135.0* 112.1 123.0*
Maximum Dry De nsity-(pcf)
85.5 72.9 62-67 83.3
90-95 73.8 70-75
Relative Compaction (%)
11.4 12.7 13.0* 15.0
8.1* 15.2 13.0*
Stewart Avenue", 7-1-75, Converse Davis & Assoc.
*Data obtained from "Final Report of Lime Treated Subgrade Testing,
MECHANICAL ANALYSIS
0-4BU 0-4C 0-5B 0-5C

Sample Number
Percent By Height Passing
Sieve Size
1-1/2 Inch 100 100
90 100 100 100 100
1 Inch 89 84
82 80 89 98 94
3/4 Inch 76 68 77
1/2 Inch 69 70 72
66 61 66 57 66
3/8 Inch 57 49 100
41 59 47 51 42
No. 4 37 140 29 37 99
No. 10 28 54 95
45 30 31 20 22
No. 40 10 17 92
9 43 26 28 17
No. 60 23 22 11 11 90
No. 100 8 40 87
34 19 14 10 6
No. 200 7
Hydrometer Percent Fines of Total Salts

9 - 4 77
Silt (.074-.005mm) 5 27 7
5 - 4 1
Clay (.005-.001mm) 1 1 3
Colloids ( .001mm) 1 2 1
41 - 56
-
Liquid Limit NP NP 34
Plastic Index NP 24 NP
21 20 3 26 27
Moisture Content 4 20
FIELD DENSITY TESTS
0.95 1.60 0.50 0.80 2.5

Depth (feet) 0.75 1.85
95.6 109.3 123.8 92.7 89.7
In-Place Dry Densit y-( pcf) 112.1 80.1
123.0* 119.0 143.7 123.0 117.3
Maximum Dry Density-(pcf) 123.0* 109.6
75-80 91.8 86.2 65-70 76.6
Relative Compaction (%) 87-92* 73.1
13.0* 12.5 4.9 13.0* 13.2
ODtimum Moisture (%) 13.0 15.2
& Assoc
Testing, Stewart Avenue", 7-1-75, Converse Davis
*Data obtained from "Final Report of Lime Treated Subgrade
Group
Major Divisions Symbol* Typical Names Laboratory Classification Criteria
0 60 _ ( D jo l’
W ell-graded gravels, gravel-sand » C , -------- g reater th a n 4 ; Q *
lu re s , lit t le or no fines 0 ,0 0 ,0 X 060
P o o rly graded gravels, gravel-sand n N o t m e e tin g a ll g ra d a tio n re q u ire m e n ts fo r G W

lu re s , l it t l e o r n o fines
A tte rb e rg lim its b e lo w " A " A b o v e “ A " lin e w ith P .l.

S ilty gravels, gravel-sand-silt m ix tu lin e o r P .l. less th a n 4 b e tw e e n 4 and 7 are border-
C la y e y gravels, gravel-sand-clay i A tte rb e rg lim its b e lo w " A ” d u a l s ym b o ls

lin e w ith P .l. gre a te r th a n 7
lures
0 60 , _ _ ( O jo l 1
W elt-graded sands, g ra v e lly sands, little Q j -------- g reater th a n 6 ;
o r n o fines 0 10 0 , 0 X 0 60
P o o rly graded sands, g ra v e lly sands, N o t m e e tin g a ll g ra d a tio n re q u ire m e n ts fo r SW
SI lit t le o r n o fines
A tte rb e rg l i m i t l above " A " L im its p lo t t in g in h atched

S ilt y sands, sand-silt m ix tu re s lin e o r P .l. less th a n 4 zone w ith P .l. b e tw e e n 4
A tte rb e rg lim its above " A ” re q u irin g use o f dual s y m

C la y e y sands, sand-clay m ix tu re s
lin e w ith P .l. g reater th a n 7 bols ,
In o rg a n ic silts and ve ry fin e sands,

ro c k flo u r , s ilty o r c la y e y fin e sands,
o r c la y e y silts w ith S light p la s tic ity
Plasticity Chart
In o rg a n ic clays o f lo w to m e d iu m
p la s tic ity , g ra ve lly c la ys, sandy clays,
s illy c la ys, lean clays
O rg a n ic s ilts a nd o rg a n ic s ilty clays o f

lo w p la s tic ity
1
In o rg a n ic silts, m ica ceous o r d ia to m a -

ceous fin e sandy o r s ilty soils, elastic
silts
In o rg a n ic clays o f h ig h p la s tic ity , <at

clays _____________ _
-) - O rg a n ic clays o f m e d iu m
p la s tic ity , o rg a n ic silts
to high
1
Pt Peat a nd o th e r h ig h ly o rg a n ic soils
Hi
, C M .„ d SM „ „ up . into tubdivitiont o. d ,nd u . . . .o , -o .d . ...............id , oniy. Sttbdivi.ion i, o .,.d on "• «« « " h’ "
L .L . is 28 o r less end th e P .l. is 6 o r less, the s u ffix u used w h e n L .L . is greater th a n 28 c o m b in a tio n s o f g ro u p s y m b o ls . F o r e x a m p le :
i^ B o rd e rlin , c la s s ific a tio n s , used fo r soils possessing c h a r.c ta ris t.e s o f tw o g ro u p s, are des.gnatad b y c o m b .n a t.o
GW -GC, < ra il-g ra ded gravel-sand m ix tu r e w ith c la y b in d e r.
Appendix 2 Uni fi ed S o i l s C l a s s i f i c a t i o n S y s t e m .
( S o u r c e : H u n t , 1 9 8 3 , p.
P 353.)
EXPANSIVE PRESSURE (PSF) VOLUME CHANGE (%)
233
Appendix 4 T rial dilution ratios
To+a I
S o lu b le S o lu tio n
Mn2+ Na+ K+ S0„2- CO,2- HC0-.” c r S I0 9 S a lts* pH
a i 3+ Ca2+ Mq2+
Mq/1000 am S o i l * * (ml 11l e q u l v a l e n t s / 1 I t e r )
900 275 9,600 0 2,0 00 600 1,000 17,575 •

S—13 <50 4,000 125 (10.15) 7; 5
( 0 .7 8 ) (0.15) (4.00) (0) ( 0 .6 8 ) ( 0 .3 4 )
Lime Treated « o .in ( 3 .9 9 ) (0.21) -
1,500 900 1,100 0 3,170 650 1,150 8,5 55 7 .4

S-1C <50 310 125 (3.75)
(0.12) (1.00) ( 0 .4 6 ) (0.46) (0) (1.07) ( 0 .3 7 )
N at iv e (< 0 .1 1 ) ( 0 .3 1 ) -
850 300 20,000 0 1,800 350 31 ,4 10

S-2B 8,000 no - (18.3) 7 .5
( 0 .1 8 ) (0.87) ( 0 .1 5 ) (8.33) (0 ) ( 0 .7 2 ) (0 .2 0 )
Lime Treated - (7 .9 8 )
1,000 900 800 0 3,0 00 400 6 ,5 0 0

S-2C 320 80 - (3.54) 7 .2
(0.32) (0.13) (0.87) ( 0 .4 6 ) (0.33) (0) (1.20) ( 0 .2 3 ) -
Nat 1ve -
1,400 420 6,750 1,300 0 1,200 1,350 15,245

S-3B <50 2,800 20 <1 9.7
(1.22) ( 0 .2 2 ) ( 2 .8 1 ) ( ( . )7) 0 ( 0 .6 8 ) (8.63)
Lime Treated « o .in ( 2 .7 9 ) ( 0 .0 3 ) « 0.1 )
1,800 850 24,500 0 2,865 1,150 1,350 41, 6 15

S-3C <50 9,000 100 <1 (22.94) 7 .7
( 0 .1 6 ) ( < 0 .1 ) (1.57) ( 0 .4 3 ) (1 0 . 2 0 ) (0) (0.94) ( 0 .6 5 )
N a t iv e (0.11) (8 .9 8 )
850 1,250 34,255

S-3D <50 8,000 210 <1 1,350 600 20,500 0 2,7 45
(19.73)
7.4
( 0 .3 5 ) «0.1 ) ( 1 .1 7 ) (0.31) ( 8 .5 4 ) (0) ( 0 .9 0 ) ( 0 .4 8 )
N at iv e ( 0 .1 1 ) ( 7 .9 8 )
60,000 500 192,000 0 2,100 7,850 - 299,990

S-4A 37,500 40 - (1 7 5 . 6 2 ) 8.1
( 0 .6 6 ) (52.2) ( 0 .2 6 ) (7 2 .9 5 ) (0) ( 0 .6 9 ) ( 4 .4 3 )
N at iv e - (3 7. 4 3)
1,750 35,000 0 2,1 00 2,150 1,450 55,675

S-4B 50 11,500 275 - 2,900 •7.7
( 2 .5 2 ) ( 0 .8 9 ) (1 4. 5 6) (0) (0.84) ( 1 .2 1 ) (31.96)
N at iv e ( < 0 . 11) (1 1. 4 8) ( 0 .4 5 )
5,500 21,000 0 2,650 800 - 39,750

S-4C - 8,500 10 1,300 (22.52) 7 .7
( 0 .0 2 ) ( 1 .1 3 ) ( 2 .8 1 ) (8.74) (0) ( 0 .8 9 ) ( 0 .4 5 )
N a t iv e ( 8 .4 8 ) -
• E x c l u d e s A l 3 + , Mn2 + , S I 0 2
• • L i m e T r e a t e d and N a t i v e S o l i s e x t r a c t e d a t 50 : 1 d i l u t i o n ra tio . Base Sample e x t r a c t e d 5:1 d i l u t i o n ra tio
A p p en d ix 5a
Tota I
S o lu b le S o lu tio n
A 13+ Ca2+ Mq2+ Mn2+ Na+ K+ S0a2" C 0,2" hco -t cr S107 S a lts* pH
Mq/1000 qm S o i l * * (ml 11l e q u l v a l e n t s / l I t e r )
850 250 6,500 0 1,850 450 12,510

S-63 2,5 00 110 - (7.25) 7.7
( 0 .1 8 ) (0.74) (0.13) ( 2 .7 1 ) (0) ( 0 .7 4 ) (0.25) -
Lime Treated - ( 2 .5 0 )
200 325 700 500 650 300 3,195

S-6C - 440 80 - (1.96) 8 .9
(0.17) (0.29) (0.33) (0)33 ) (0.26) (0.17) -
N a t lv e ( 0 .4 4 ) ( 0 .1 3 )
70 280 0 372 70 135 1,302

S-7A <50 100 105 - 170 7 .8
(0.36) ( 1 .1 7 ) (0) ( 1 .2 2 ) (0.39) (5.79)
Base (0 .1 1 ) ( 1 .0 0 ) (0 .1 7 ) (1.48)
400 24,500 0 3,230 550 1,600 40,355

S-7B1 <50 10,500 75 1,100 7.8
(0.20) ( 9 .9 9 ) (0) ( 1 .0 6 ) (0.31) (23.12)
Lime Treated ( 0 .1 1 ) (1 0 . 4 8 ) ( 0 .1 2 ) - (0.96)
800 2,750 0 3,720 700 1,400 10,020

S-7C <50 600 50 1,400 8 .0
(0.41) ( 1 .1 5 ) (0) ( 1 .2 2 ) (0.39) ( 5 .0 7 )
N a t iv e ( 0 .1 1 ) ( 0 .6 0 ) ( 0 .0 8 ) - ( 1 .2 2 )
750 11,500 0 1,650 1,000 - 20,600

S-8B 3,800 200 1,700 7 .8
(0.38) ( 4 .7 9 ) (0) ( 0 .6 6 ) (0.56) (11,99)
Lime Treated - ( 3 .7 9 ) ( 0 .3 3 ) - ( 1 .4 8 )
1,050 6,000 0 1,150 450 “ 11,280

S-8C - 1,150 180 - 1,300 8.1
(0.54) ( 2 .5 0 ) (0) ( 0 .4 6 ) (0.25) ( 6 .9 3 )
N a t iv e ( 1 .1 5 ) ( 0 .3 0 ) (1.13)
1,150 58,500 0 550 700 “ 84,500

S-9A - 21,000 950 - 1,650 7.0
(0.59) (2 4. 3 5) (0) (0 .1 8 ) (0.39) (4 9 .4 7 )
(2 0 .9 6 ) ( 1 .6 5 ) ( 1 .4 4 )
N a t iv e
650 42,000 0 600 250 60,850

S-9B 16,000 700 650 7.3
- (1 7. 4 9) (0) ( 0 .2 0 ) (0.14) - (3 5 .8 5 )
(1 5. 9 7) ( 1 .1 5 ) - ( 0 .5 7 ) (0.33)
N at iv e
950 6,500 0 1,300 550 - 11,355

S-9C 1,200 205 - 1,150 ( 6 .4 7 ) 7.9
- (0.48) ( 2 .7 1 ) (0) ( 0 .4 3 ) (0.31)
N a t iv e ( 1 .2 0 ) ( 0 .3 4 ) ( 1 .0 0 )
• E x c l u d e s M 3\ Mn2 + , S I 0 2
'• L i m e T r e a t e d and N a t i v e S o l i s e x t r a c t e d a t 50:1 d ilu tio n ra tio . Base Samp le e x t r a c t e d 5:1 d i l u t i o n ra tio ,
Total
S o lu b le S o lu tion
pH
N>
cr S107 S a lts * •
1
K+ HCOV
soa2- .
0
Na +
0
Mq2+ Mn2+
1
Ca2+
Mn/1000 am S o i l * * (ml 1 1l e q u 1v a le n ts /lIte r)
700 1,150 39,415
9,500 4 50 - 1,300 650 24, 500 0 2,315
(22.82)
8.2
S-10B <50 (0.33) (9.99) (0) ( 0 .7 6 ) (0.39)
( 9 .4 8 ) ( 0 .7 4 ) ( 1 .1 3 )
Lime Treated « 0.1 1)
3,700 650 1,500 11,950

<50 900 375 1,400 375 3,0 50 0
(0.37) (5.85) 8.0
S-10C (1.22) (0.19) (1.27) (0) ( 1 .2 8 )
N a t iv e (< 0 .1 1 ) ( 0 .9 0 ) ( 0 .6 2 ) -
800 1,450 60,400

2,2 00 1,350 40, 500 0 8 .3
S-11B 14,000 100 - ( 0 .3 2 ) (0.82) - (34.73)
: (1.91 ) (0.69) (16.86) (0)
Lime Tre ate d (1 3. 9 7) ( 0 .1 6 )
700 450 51,075

1,000 1 ,050 34, 500 0 (29.91) 7.3
S-11C 13,000 375 (14.37) (0) ( 0 .2 8 ) (0.26)
_ (1 2. 9 7) ( 0 .6 2 ) - (0.87) (0.54)
N a t iv e
2,4 00 1,000 37, 500 0 1,700 850 — 55,950

7.5
S-12A 11,500 1,000 - (15.62) (0) (0 .68 ) ( 0 .4 8 ) (31.01)
N a t iv e
_ (1 1. 4 8) ( 0 .1 6 ) ( 2 .0 8 ) (0.51)
1,850 500 51,750

1,250 750 24, 500 0 7.2
S-12B - 12,000 900 ( 0 .6 1 ) ( 0 .2 8 ) (30.19)
- (1.09) (0.38) (14.37) (0)
N a t iv e (1 1. 9 8) ( 1 .4 8 )
2,400 4 50 17,600
1,200 700 9,5 00 0 7 .5
S-12C - 2,600 750 (0) (0.7 9) ( 0 .2 5 ) - (11.01)
- (1.04) (0.36) (3.96)
N a t iv e ( 2 .5 9 ) ( 1 .2 3 )
650 500 — 4,2 75

400 225 1,750 0 (2.64) 8 .3
S-12F - 440 310 (0) ( 0 .2 1 ) ( 0 .2 8 )
( 0 .5 1 ) - (0.35) ( 0 .1 2 ) (0.73)
N a t iv e ( 0 .4 4 )
1,900 3,5 00 74,945

4,500 850 46,000 0 8.3
18,000 195 - ( 0 .7 6 ) ( 1 .9 7 ) - (44.51)
S-13B - (3.92) (0.43) (19.15) (0)
Lime Treated (17. 96) ( 0 .3 2 )
3,475 1,200 1,550 31,375

2,8 00 800 17,000 0 (1 8 . 1 4 ) 7.8
S-13C - 5,500 550 (0) ( 1 .1 4 ) ( 0 .6 8 )
( 0 .9 0 ) - ( 2 .4 4 ) (0.41) (7.08)
N a t iv e ( 5 .4 9 )
• E x c l u d e s A l 3 + , Mn2 + , S I 0 2
Base Sample e x t r a c t e d 5:1 d i l u t i o n r a t i o
••Lim e Treated and N a t i v e S o i l s e x t r a c t e d a t 50 : 1 d i l u t i o n ra tio
Tota 1
Soluble S o lu tion
a i 3+ Ca2+ Mg2+ Mn2+ Na+ K+ SOi.2- CO,2- HC0^“ C l- S !0 ? S a lts* pH
Mq/1000 gm S o i l * * (ml 11I e q u l v a l e n t s / 1 I t e r )
9,500 40 1 ,0 0 0 475 23, 000 500 610 750 1,650 35,875

S-14B - _ (21.19) 8.7
( 9 .4 8 ) ( 0 .0 7 ) (0.87) (0.24) (9.58) ( 0 .3 3 ) ( 0 .2 0 ) ( 0 .4 2 )
Lime Tre ate d
195 2,4 50 900 43, 000 0 2,680 1,150 1,600 65,875

15,500 8 .3
( 0 .3 2 ) “ (2.13) (0.46) (17.91) (0) ( 0 .8 8 ) ( 0 .6 5 ) (37.82)
Lime Treated - (1 5. 4 7)
12,500 900 2,400 900 40, 500 0 855 1 ,1 0 0 1,550 59,155

(1 2. 4 8) ( 1 .4 8 ) (2.09) (0.46) (16.87) (0) ( 0 .2 8 ) ( 0 .6 2 ) (34.28)
N a t lv e -
120 2,150 700 48, 000 0 2,150 1,000 - 72,620

S-1 5B 18,500 8.1
( 0 .2 0 ) (1.80) ( 0 .3 6 ) (19.99) (0) ( 0 .8 5 ) ( 0 .5 6 ) (42.29)
Lime Treated - (1 8. 4 6) “
445 600 475 49,000 0 700 200 - 68,920

17,500 (39.74) 7 .0
N a t iv e (1 7. 4 6) ( 0 .7 3 ) “ (0.52) ( 0 .2 4 ) (2 0 . 4 0 ) (0) ( 0 .0 8 ) ( 0 .1 1 )
-
425 700 500 4,0 50 0 1,200 350 - 7,825

600 8.3
(0 .7 0 ) (0.61) (0.26) (1.69) (0) ( 0 .4 8 ) ( 0 .4 8 ) ( 4 .5 4 )
N a t iv e - ( 0 .6 0 ) “
20 3,900 1,150 24,000 1,600 0 1,400 1,700 39,070

S-168 7,000 (2 2 . 8 3 )
(6.9 9) ( 0 .0 3 ) ( 3 .3 9 ) ( 0 .5 9 ) ( 9 .9 7 ) ( 1 .0 7 ) 0 ( 0 .7 9 )
Lime Treated -
1,050 4,100 1,600 18,500 0 2,745 1,000 1,450 32,795

S-16C 3,800 (1 9 .0 7 ) 7.5
(3'. 79) ( 1 .7 3 ) - ( 3 .5 7 ) ( 6 .8 2 ) ( 7 .7 0 ) (0) (0 .90 ) ( 0 .5 6 )
N a t iv e -
1,950 450 6,500 0 2,745 750 1,450 14,170

S-1 60 1,050 700 ( 8 .1 7 ) 7. 5
(1.0 5) ( 1 .1 5 ) - ( 1 .7 0 ) ( 0 .2 4 ) (2.71) (0) (0 .90 ) (0 .4 2 )
N a t iv e -
900 175 15,500 0 1,700 450 24,925

S-17B - 6,000 200 - (1 4. 5 7) 7.9
( 5 .9 9 ) (0 .33 ) ( 0 .7 8 ) (0 .0 9 ) ( 6 .4 5 ) (0) (0 .68 ) ( 0 .2 5 ) -
Lime Treated
♦ Ex c lu d e s A l ^ + , Mn2+, SIO2
**Ll me Treated and N a t iv e S o i l s e x t r a c t e d a t 50:1 d i l u t i o n r a t i o . Base Sample e x t r a c t e d 5:1 d i l u t i o n r a t i o .
Total
S oluble S olu tion
HCO-s- C l" SIO? S a lts * pH
Mq2+ Mn2+ Na+ K+ SO*2- C0x2*
a i 3+ Ca2+
Ma/1000 am S o l i * * (ml 11l e q u l v a l e n t s / l I t e r )
5,500 0 1,600 600 - 11,480

230 200 2 ,5 0 0 800 (6.58) 8 .5
S-17C - ( 0 .4 1 ) ( 2 .2 9 ) (0) ( 0 .6 4 ) (0.34)
( 0 .2 3 ) ( 0 .4 5 ) - (2.22)
N ative
0 330 70 150 1,081

10.5 <1 160 90 320 7.7
S-18A <50 100 (0) (1.32) (0.39) (6.07)
( 0 .1 7 ) (< 0 .0 1 ) (1.39) (0 .4 6 ) (1.33)
Base (< 0 .1 1 ) ( 1 .0 0 )
17,500 1,200 0 500 1,750 27,603

7,500 3 <1 700 200 (16.63) 9.5
S-18B <50 (7.29) ( 0 .8 0 ) 0 (0.28)
( <0 .1 1 ) ( 7 .4 9 ) ( 0 .0 5 ) (< 0 .0 1 ) (0.61) ( 0 .1 0 )
Lime Tre a te d
5,000 0 3,4 00 1,000 1,550 14,050

600 300 <1 2 ,9 0 0 850 (8.04) 8.3
S-18C <50 ( 2 .0 8 ) (0) ( 1 .3 6 ) ( 0 .5 6 )
( 0 .6 0 ) ( 0 .4 9 ) « 0.01) (2.52) ( 0 .4 3 )
N a t iv e ( < 0 . 11)
1,300 0 1,150 " 43,610

10 1,000 650 28,000 10.4
S-19B 11,500 ( 0 .6 5 ) (3 5 . 8 6 )
Lime Tre a te d _ (1 1. 4 8) (0 .0 2 ) - (0.87) ( 0 .3 3 ) (11.66) ( 0 .8 7 ) 0
5,000 0 75 55 7,2 05
1,850 35 150 85 (4 1 . 8 1 ) 7.3
S-19C ( 0 .3 1 ) -
B a c k f l 11 _ (1 8. 4 6) ( 0 .5 8 ) - (0.91) ( 0 .4 3 ) (2 0 . 8 2 ) (0) ( 0 .3 0 )
25,000 700 350 800 1,650 38,100

9,500 300 950 500 (2 2 . 5 3 ) 9 .0
S-213 <50 (1 0 . 4 1 ) ( 0 .4 7 ) (0 .1 4 ) ( 0 .4 5 )
( 9 .4 8 ) (0 .4 9 ) - (0.83) ( 0 .2 6 )
Lime Tre a te d (<0 .11 )
0 2,200 1,100 1,350 101,750

1,000 - 2 ,1 0 0 1,350 69,000 7 .5
S-21CN <50 25,000 (0) ( 0 .8 8 ) ( 0 .6 2 ) (59.30)
( 1 .6 0 ) (1.83) ( 0 .6 9 ) (28.73)
N a t iv e « 0.1 1) (2 4 . 9 5 )
1,000 50 350 23,560

10 - 650 900 16,000 9.4
S-22B - 4,600 ( 0 .6 7 ) ( 0 .0 2 ) ( 0 .2 0 ) - (13.15)
(0 .0 2 ) (0.57) ( 0 .4 6 ) ( 6 .6 2 )
Lime Tre a te d ( 4 .5 9 )
0 1,300 300 4,650

95 350 650 1,500 8.2
S-22C - 455 - ( 0 .5 2 ) ( 0 .1 7 ) - (2.55)
(0.30) ( 0 .3 3 ) ( 0 .6 2 ) (0)
N a t iv e ( 0 .4 5 ) ( 0 .1 6 )
• E x c l u d e s A l 3 + , Mn2 + , S I 0 2
Base Sample e x t r a c t e d 5:1 d i l u t i o n r a t i o .
• • L i m e T r e a t e d and N a t i v e S o l i s extra cted a t 50 :1 d i l u t i o n ra tio .
Appendix 5 e
Tota 1
Soluble S o lu tion
S0a2 - HCOt;" c r S !0? S a lts* pH
A, 3+ Mg2+ Mn2+ Na+ K+ CO, 2 -
Ca2+
Mq/1000 qm S o l ) * * (ml I I l e q u l v a l e n t s / l I t e r )
2,750 0 210 160 4,021

160 16 - 550 175 7 .7
S-24A ( 1 .0 4 ) (0) (0.84) ( 0 .9 0 ) - (1 6 .7 0 )
- ( 7 .9 8 ) ( 0 .2 6 ) (4.79) ( 0 .8 9 )
Base
31,000 400 750 2,200 1,550 51,015

6,500 15 7 ,5 0 0 2,650 8.7
S-24B <50 (12. 91) ( 0 .2 7 ) ( 0 .3 0 ) ( 1 .2 4 ) (29.11)
( 6 .4 9 ) ( 0 .0 2 ) - (6.53) ( 1 .3 5 )
Lime Tre a te d {<0.11>
0 800 950 22,990

3,200 240 - 2 ,5 5 0 1,250 14,000 •7.9
S-24C - ( 5 .8 3 ) (0) ( 0 .1 2 ) ( 0 .5 4 ) - (1 3 . 0 1 )
( 3 .1 9 ) ( 0 .3 9 ) (2.22) ( 0 .7 2 )
N a t iv e
2,100 0 2,650 21,805

2,850 5 3 ,4 5 0 750 10,000 10.0
S-25B - ( 1 .4 0 ) 0 ( 1 .5 0 ) - (1 3 . 2 9 )
(2.8 4) ( 0 .0 1 ) - (3.00) ( 0 .3 8 ) (4.1 6)
Lime Tre ate d
0 2,1 50 2,350 - 25,310

3,200 410 2 ,9 5 0 1,250 13,000 7 .8
S-25C - (0) ( 0 .8 6 ) (1 .3 3 ) (1 4 . 6 7 )
( 0 .6 7 ) - ( 2 .5 7 ) ( 0 .6 4 ) ( 5 .4 1 )
N a t iv e (3 .19 )
200 600 600 850 21,480

4,400 30 1,100 700 13,000 8.8
S-26B <50 ( 5 .4 1 ) ( 0 .1 3 ) ( 0 .2 4 ) ( 0 .3 4 ) (1 1 . 8 8 )
( 4 .3 9 ) ( 0 .0 5 ) - ( 0 .9 6 ) ( 0 .3 6 )
Lime Tre ate d {<0 .11)
0 2,850 700 1,450 21,290

2,750 240 1,800 1,500 10,000 7 .9
S-26C <50 (0) ( 1 .1 4 ) ( 0 .3 9 ) (1 1 .1 6 )
( 2 .7 4 ) ( 0 .3 9 ) - (1.57) (0 .7 7 ) ( 4 .1 6 )
N a t iv e ( < 0 . 11)
0 1,150 500 1,600 39,675

25 1,400 1,100 26,500 8.2
S-27B <50 9,000 ( 0 .4 6 ) ( 0 .2 8 ) (2 2. 5 7)
( 0 .0 4 ) - ( 1 .2 2 ) ( 0 .5 6 ) (11.03) (0)
Lime Treated ( < 0 . 1 1) ( 8 .9 8 )
0 2,4 00 800 1,450 33,590

290 1,100 1,500 20,500 7.7
S-27C <50 7,000 - (0) ( 0 .9 6 ) ( 0 .4 5 ) (1 9 .1 5 )
( 0 .4 8 ) ( 0 .9 6 ) ( 0 .7 7 ) ( 8 .5 4 )
N a t iv e ( < 0 . 11) (6.9 9)
950 600 15,210 7.4

260 950 1,350 9,000 0
S-27D - 2,100 (0) ( 0 .3 8 ) ( 0 .1 7 ) - ( 8 .3 5 )
( 0 .4 3 ) ( 0 .8 3 ) (0 .3 8 ) (3.7 5)
N a t iv e (2.1 0) -
• E x c l u d e s A l 3 + , Mn2 + , S I 0 2
50:1 d i l u t i o n r a t i o . Base Sample e x t r a c t e d 5:1 d i l u t i o n r a t i o .
••Lim e Treated and N a t i v e S o l i s e x t r a c t e d a t
240
Tota 1
S oluble S o lu tion
(N
CO,2 - HC0n“ C l" S107 S a lts * pH
in
Mq2+
O
K+
1
A|3+ Ca2+ Mn2+ Na+
Mq/1000 am S o i l * * (ml I 1l e q u l v a l e n t s / 1 I t e r )
700 9 ,2 0 0
o o
S-288 - 1,350 10 1,000 1,250 3,800 1,100 10.0
Lime Treated ( 1 .3 5 ) ( 0 .0 2 ) ( 0 .8 7 ) (0.64) ( 1 .5 8 ) ( 0 .7 3 ) ( 0 .3 9 ) -
200 _ 33, 550

S-28C 1,000 8,000 500 1,500 23,500 0 650
( 0 .1 6 ) ( 7 .9 8 ) - ( 0 .4 4 ) (6.77) ( 9 .7 9 ) (0) ( 0 .2 6 ) ( 0 .1 1 ) (19.51)
N a t iv e -
S-29B 2,200 20 . 2,600 550 8,500 200 1,950 550 - 16,570

( 2 .2 0 ) ( 0 .0 3 ) - ( 2 .2 6 ) ( 0 .2 8 ) ( 3 .5 4 ) ( 0 .1 3 ) ( 0 .7 9 ) ( 0 .3 1 ) (9 .5 4 )
Lime Treated -
70 9 135 19 145 0 330 50 _ 758

( 0 .7 0 ) (0 .1 5 ) - ( 1 .1 7 ) ( 0 .1 7 ) ( 0 .6 0 ) (0) ( 1 .0 8 ) ( 0 .2 8 ) (4.15)
Base -
<50 3,750 25 <1 1,800 600 11,000 200 1,800 750 1,500 19,925
S-30B
(3.74 ( 0 .0 4 ) (<0 .01 ) ( 1 .5 7 ) (0.31) ( 4 .5 8 ) ( 0 .1 3 ) ( 1 .5 7 ) ( 0 .4 2 ) (11.51)
Lime Treated (<0.11>
1,150 175 <1 1,350 900 3,200 0 3,400 1,650 1,400 13,225
<50 (6.69) 8 .0
N a t lv e «o.n> ( 1 .1 5 ) ( 0 .2 9 ) (<0 .01 ) ( 1 .1 7 ) ( 0 .4 6 ) ( 1 .3 3 ) (0) ( 1 .3 6 ) ( 0 .9 3 )
2,000 10 2,150 600 7,000 1,200 250 1,350 - 14,560

S-33B ( 8 .7 7 )
Lime Treated ( 2 .0 0 ) ( 0 .0 2 ) - (1 .8 7 ) (0.31) ( 2 .9 1 ) (0.8 0) ( 0 .1 0 ) ( 0 .7 6 )
"
240 5,500 1,450 12,000 0 2,750 1,700 1,300 24,590

S-33C <50 950 8.1
(4 .7 9 ) ( 0 .7 4 ) ( 5 .0 0 ) (0) ( 1 .1 0 ) ( 0 .9 6 ) (13.93)
N a t lv e «o.m ( 0 .9 5 ) ( 0 .3 9 ) ”
125 350 375 1,100 0 2,150 400 - 5,400

900 •8.2
( 0 .9 0 ) ( 0 .2 1 ) ( 0 .3 0 ) (0.19) ( 0 .4 6 ) (0) ( 0 .8 6 ) ( 0 .2 3 ) (3.15)
N a t iv e - **
•Ex clud es A ) I +, Mn2+, S102
••L im e Treated and N at iv e S o i l s e x t r a c t e d a t 50:1 d i l u t i o n r a t i o . Base Sample e x t r a c t e d 5:1 d i l u t i o n r a t i o .
A p p en d ix 5g
Tota I
Sample Number Ca2+ Mq2+ Na+ So lub le S o lu t I o n
K+ SO.2' CO,2" HC0t “ C l"
Mq/1000 qm S o i l * (ml 111eq u 1v a 1e n t s / l 1t e r )
0-1BU 3,400 75 1,050 800 9,000 1,200 0 700 16,225
Lime Treated ( 3 .3 9 ) (0.1 2) ( 0 .9 1 ) (0.4 1) ( 3 .7 5 ) ( 0 .8 0 ) (0) (0 .39 ) (9.7 7) 9.7
(undamaqed)
0-1B 11,500 475 1,250 1,350 32,000 1,200 100 200 48,075
N ati ve (11.47) ( 0 .7 8 ) ( 1 .0 9 ) ( 0 .6 9 ) (13. 32) ( 0 .8 0 ) ( 0 .0 4 ) ( 0 .1 1 ) (27. 50) 9 .3
0-1C 310 205 2,000 1,350 4,300 800 1,400 600 10,965
Nat ive ( 0 .3 1 ) ( 0 .3 4 ) (1.7 4) ( 0 .6 9 ) ( 1 .7 9 ) ( 0 .5 3 ) ( 0 .5 6 ) (0.3 4) ( 6 .3 0 ) 9.3
0-2B 4,250 25 ’ 650 600 11,500 600 400 250 18,275
Lime Treated ( 4 .2 4 ) ( 0 .0 4 ) ( 0 .5 7 ) ( 0 .3 1 ) (4.7 9) ( .4 0 ) ( 0 .1 6 ) (0.1 4) 9.5
0-2C 15,000 750 1,000 750 45,000
Nat 1ve 0 700 350 63,550
(14.97) ( 1 .2 3 ) ( 0 .8 7 ) (0.3 8) (18.74 (0) * ( 0 .2 8 ) (0.2 0) (36. 67) 7.4
0-3B 8,000 50 600 425
Lime Treated 19,500 400 400 750 30,125
(7.9 8) (0.0 8) ( 0 .5 2 ) ( 0 .2 2 ) ( 8 .1 2 ) ( 0 .2 7 ) 9.1
(0 .1 6 ) (0.4 2) (17.77)
0-3C 3,700 550 1,000 800 13,000 0 800 250 20,100
N ati ve (3.6 9) ( 0 .9 0 ) (0 .87 ) (0.4 1) (5.4 1) (0) ( 0 .3 2 ) (0.14) (11.74) 7.9
0-4BU 5,500 75 4 50 350 13,500
Lime Treated 1,000 0 850 21,725
(5 .49 ) (0 .12 ) (0.39) (0.18) ( 5 .6 2 ) (0.6 7) 9.9
. (undamaqed) (0) (0.4 8) (12.95)
0-43 7,000 55 700 4 50 17,000

Lime Treated 1,000 300 600 26,795
(6.99) ( 0 .0 9 ) ( 0 .6 1 ) (0.2 3) ( 7 .0 8 ) ( 0 .1 2 ) ( 0 .1 2 ) (0.34) 9.3
0-4C 10,000 750 3,100 1,200 37,000
Nat ive • 0 650 750 53,450
(9.98) (1.2 3) (2.7 0) (0.61) (15.41) (0) 7.9
( 0 .2 6 ) (0.42) (30.61)
0-6BU 270 5 950 650 6,500
Lime Treated 1,500 0 300 12,605
(2.6 9) ( 0 .0 1 ) (0.8 3) (0.33) ( 2 .7 1 ) ( 1 .0 0 ) 10.2
(undamaqed) (0) (0.1 7) (7 .74 )
0-6B 3,550 10 250 325 8,500 0 1,450 250 14,335

Lime Treated (3.54) (0.0 2) (0 .22 ) (0.1 7) ( 3 .5 4 ) (0) 7.7
( 0 .5 8 ) (0 .11 ) (8.2 1)
0-6C 7,500 55 2,150 1,600 26,500 0 750 200 38,705
Nat 1ve (7.49) ( 0 .9 0 ) 7.8
(1.8 7) (0.8 2) (11.03) (0) ( 0 .2 8 ) (0.1 1) (22.50)
•Lime Treated and N ati ve S o il s e x tr a c te d a t 50:1 d i l u t i o n r a t i o . Base Sample e x t r a c t e d 5:1 d i l u t i o n r a t i o .
Appendix 5h
242
Appendix 7a
X -R A Y DIFFRACTIO N SCAN
Sample: S-14B - Damaged Lime Treated Subbase; Mineral Aggregate
P olyhalite, Gypsum
Gypsum
Thaumasite
Thaumasite
Thaumasite
X -R A Y D IFFRA CTIO N SCAN
Sample: S-19B - Damaged Lime Treated Subbase; Single Crystal
X -R A Y D IFFR A CTIO N SCAN
Sample: S-30B - Undamaged Lime Treated Subbase; Mineral Aggregate
Appendix 7 d
X - R A Y D IF F R A C T IO N S C A N
Sample: 0-1B - Damaged Lime Treated Subbase; Mineral Agg re g at e
Appendix 7e
&K 4 M : SS5. ^ 1 « M 19811
Energy dispersal/scanning electron the lack

Th auma sit e, Ettringite and a mixed c r y s t a l s t r u b e l , 1981);
of a l u m i n u m in p u r e T h a u m a s i t e ( f > o m t o l l m a n
249
250
Ca
Sample : S-8B
Damaged Lime T re a te d Subbase
M in e r a l A ggregate
Appendix 9a Typical energy dispersal patterns from the

scanning electron microsope for Stewart Ave.
251
Sample: 0-1B
Damaged Lime Treated Subbase
M in e ra l Aggregate
Appendix 9b Typical energy dispersal patterns from the

scanning electron microsope for Owens Ave.
252
253
R8jfy?
Mr. Dal Hunter
March 8, 1988
Page 2
If you see any ways in which this program might be strengthened to

highlight the key factors (without running the number of test> out of
sight!), we would certainly appreciate it. Are there any main factors
that have been overlooked?
I look forward to hearing from you and also learning more about
your own research on this fascinating, but difficult problem.
Sincerely yours,
James K. Mitchell
Professor of
Civil Engineering
JKM/nh
A p p e n d i x 11b D e s c r i p t i o n ot l i m e / h e a v e e x p e r i m e n t s
in p r o g r e s s at U.C. Berkeley.
255
2 5 - 1 2 8 --------------------------------
3.41 9.56 [Ca3Si(Ol06-12H20](S0O(C03)
d 9.56 5.51
20 100 Calcium Carbonate Silicate Thaumasite

100 40
i/ i Sulfate Hydrate
dA 1/1 hlcl d A r/i hkl
Rad. CoKajX 1.7890 Filter Dia. 114.8mm 100 100 2.357 4 312
Cutoff I/I j Microphotometer 1/1 cor. 2 101 2.282 <1 204
Ref. Knill, Mineral. Mag., 32^416 (1960) 40 110 2.191 6 320
5 111 2.155 13b 402,223-t-
5 200 2.106 5 313
S.G. P63/m (176)
Sys. Hexagonal
co 10.40 A C 6 102 2.086 2 410
a<) 11.03 b0 Z 2 E)x [1.83] 201 2.045 4 411
4
a P y 3 322
16 112 2.019
Ref. Ibid. 210 1.934 3 412
1
6 202 1.911 10 500
Sign -
(a 1.470 n to/3 1.504 £y
Color Colorless 20 211 1.809 3 331
2V D 1.91 rap 16 300 1.778 3 421
Ref. Ibid. <1 301 1.733 3 332,006
<1 113 1.692 2 511
Specimen from Ballyalton, noruiei.. 2 220 1.626 4 414
Validated by calculated pattern 24-28. 14 302 1.592 4 600
To replace 13-156. 4 310 1.570 <1 430
<1 004 1.551 1 431
10 311 1.538 1 513
213 1.467 1 226,107
>.499 } 10
Appendix 1 2 X - r a y diffraction p e a k s for thaumasite.
to
<ji
U\
/'
m n tm m ....... ...........................M l.............II
Ca6Al2(SOH)3Ca0i2*25H2O
Calcium Aluminum Sulfate
Hydroxide Hydrate
Rad. CuK0l x 1.5405 Fillet Ni Dia. 2.616

Cui off 1/1, Diffractometer l/ l c o r. 2.564
Ref. Nat. Bur. Standards Circ. 539, £ 3-4 (1959) 2.524
2.487
S.G. Pbj/mmc (194) 2.434
5. Hexagonal
co 21.44 A c: 1.9092 2.422
11.23 b0
P y z : Dxl.754 2.401
2.347
Ilcf. Ibid.
2.230
2.209
n oj fi lY Sign 2.185
2V D ra p Color Colorless 2.154
Ref. Ibid. 2.130
2.124
Sample prepared at NBS. Spcct. anal, showed 0.1-1.0\ 2.081
Si, Sr; 0.01-0.lb Ag, Cr, Cu, Mr., No, Pb; 0.001-0.01% 2.062
B, On, Cs, Fc, Mn, Ni, Sn, 2n, Zr. 2.033
Pattern made at 25*C. 2.027
1.979
1.975
9 - H1 A
9.73 5.61 3.E 9.73 C a 6A l 2 (S 0 l| ) 3 ( 0 H ) l 2 * 2 5 ll20
★
100 Calcium Aluminum Sulfate
1/1 100 80 50
H y d r o x id e tty a rn
fEttrincitc)
d A 1/11 hkl d A 1/11
Filter L ) ia .
Had. A 1.946
Cut o f i/i i l/l c o r.
1.905
Ref. 1.875
1.853
S.G 1.845
Sys. C
co
A 1.829
ao bo Dx
y Z 1.812
n P 1.809
Ref.
1.786
1.768
Sign
n oj /3 y
D rap Color
2V
Ref.
See preceding card
Appendix 1 3 X - r a y diffraction p e a k s for ettringite.

259
261
262
diffraction pattern for sample
265
267
Appendix 22a WATEQDR ion activity calculations tor gypsum, samp---------- .
Z. ZZZZZZe-- ZZ Z.zZZZZZe*ZZ
0. 3283 ® 4 e -8 5
0.0000006+0® Z. 000000e-00
0 . lS4395e-05 0. 000000e-r00 z.ZZZZZZs+aZ
Z. 1 0 6775e-®5 0.000000e+00 a.zazzaze+zz
0.0000006+00 0 . i 5 *S 3 0 e — 09
0.6 l 96 l 4 e -0 6
0.000®00e+0®
0.35932£e-®6 0.0000806+0® „>j0 .0000006 +0® TSTÊlEhSH^TUT^-
__^
0. 2083 6 7 e -0 6 hi
' 0 . ic;wJ6i9a-v5tr 0.0800006-00 0.000000e+0®
'0.'000000e-^0®i> jX•0i 3 a A 3 5 £ e - l 0
'0.696£S6e+07 0. 0.000006-*-®® a~*'^ '
0. 4©'*436b -07 -2rT7nzr?000e-<-02r
earnest
eomarj
•;:c,’ 'temperature 0.000000B+00
0. 1000006-^03
0. i00000e-*-03
0. 1000006 •*■03
tTS^zT
OH
CaOH
■K c v 5 u lT
Na£S 0 4
N aH C 03
‘ A&<KS 04
3 95 -
:k c i -..
6 3 HSOA
sample G -2 5
Appendix 22b WATEQDR ion activity calculations for gypsum
1water
r.x - W ' *; ■ :»'•; O - ' Y . #
W *■*-•-!•. ‘ -i* t •\V*v »it
ip .-.ro -.•••;-•V ■
t
• •n’
: ; - f? IP Ip p fp P
E--' •• •■•
,
_______• " '
- -------------------------- -
; " P : ll£
ir.it ;a. so* vil
P 3 I 1 1
- — — - — ---------------------- — y
V ^ n ^ t u r . I -8 ^ c.B r . ^ - C , f1
3. :
Ana Lytica. e3ncatfc =_ a fe^.3 Cr.alytical e rnian a a
-4. fc>u.s y
— “ — - ■ p -
« ♦* r e o o x - maui. «**
•. • ,• .-■ • .. . ..
'6 ■, oxy cert * 0.000 mg/ - __ T
l g § 1| J P ... 1 S § P § § § If f l I B H i l i
I
*** total co--cer.t rations cJ irout ssecies
a r * ’ " ’l 1 ” ” .. V i.-, a y --* - •., - Y .j
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F cornou ino t i e C i s t r i p u t i on of so ec les.

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M IN N

The Geochemistry of Lime-Induced Heave in

Sulfate Bearing Clay Soils

A dissertation submitted in partial fulfillment of

the requirements of the degree of Doctor of Philosophy,

Robert Dalton Hunter

Where do I start? Bob and Robbie Hunter taught me to do

will notice that it took guite awhile. My parents gave me the

gift of tenacity, among other things. Dr. Roger Jacobson of

the Desert Research Institute provided outstanding technical

and moral support throughout this lengthy ordeal. His efforts

and patience are greatly appreciated. SEA, Consulting

Engineers, Inc., has been very supportive of this project and

is gratefully acknowledged. Adrienne Frederick of Adrienne's

Office, a long-time friend, typed this beast, including the

dreaded "big nasty awful table" and numerous chemical

equations. Thanks Adrienne— you probably saved my marriage.

Finally I want to thank my family: Candace, my wife, for

her support and patience; and my children, William and Susan,

Clay soil is commonly stabilized in-place by mixing with

anhydrous (CaO) or hydrated (Ca(OH)a) lime. The resulting

chemical disequilibrium causes various cementing and exchange

reactions between the lime and clay. On Stewart Avenue, Las

Vegas, Nevada, unusual reactions between lime, clay, and

sulfate minerals caused severe swelling in lime-treated

subbase. Reconstruction costs approached $3,000,000. Lime-

induced heave has also occurred in California, Utah, Kansas,

Texas, Tennessee, and Paris, France. On Stewart Avenue, heave

resulted from growth of thaumasite, a complex multi-hydrated

calcium silicate-carbonate-sulfate mineral. Thaumasite forms

a solid solution series with ettringite, a multi-hydrated

calcium aluminum sulfate mineral. At temperatures above 15 C,

ettringite probably forms first and later converts to

thaumasite. At least 50% of the sulfate migrated to the

nucleation centers, mostly in capillary water derived from

ponding in utility trenches. Mass flux estimations indicate

sites within the observed time frame of two years.

Solubility determinations were made on ettringite

synthesized during this research. Study results, which

considered ion pairs, are reasonably represented by the

equation log Ket = 196.429 - 1.6699T + 0.002846T2, and

corresponds to —48.49 at 25 "C. The logarithmic expression

leads to AG° = -66.14 ± 0.27 kcal/mol, AH” = -11.0 ± 0.3

kcal/mol, ACP° = 2.4 ± 0.1 kcal/mol, and ASr° = -196 ± 52 cal/deg

mol for the dissociation of ettringite at 25°C. Using this

data, ettringite was found to be the stable phase at high pH

and sulfate concentrations above 15 mg per kg of soil. On

Stewart Avenue approximately 25% of the heave was due to added

and increased soil voids. Complete reaction of 10,000 mg

sulfate/kg soil should induce a one-inch (2.5 cm) heave from £ , ~ # /

a 12-inch (30.5 cm) thick lime-treated soil. Because of ion

mobility, lime treatment of soils containing measurable sulfate

is risky. Swelling can probably be held to tolerable levels

by careful control of drainage and capillarity. Costs of

preventing chemical heave in soils containing sulfate minerals

may exceed the potential savings from lime or cement

LIST OF FIGURES viii

LIST OF APPENDICES xiii

2 THEORY AND PRACTICE IN LIME STABILIZATION OF CLAY

3 LIME-INDUCED HEAVE OF SULFATE BEARING CLAY SOILS:

4 OTHER CASES OF LIME-INDUCED HEAVE AND RELATED

TABLE OF CONTENTS (Continued)

5 THE MINERALOGY OF THAUMASITE AND ETTRINGITE 93

6 METHODOLOGY FOR EXPANSIVE POTENTIAL AND MINERAL