MINERALOGY AND MICROSTRUCTURE OF

DINOSAUR EGGSHELLS

by

MARK L. POLLINGER, B.A.

A THESIS

IN

GEOSCIENCE

Submitted to the Graduate Faculty of Texas Tech University in

Partial Fulfillment of the Requirements for

the Degree of

MASTER OF SCIENCE

Approved

Accepted

December, 1997

'^3 ACKNOWLEDGEMENTS

A. / ^

y I wish to thank my major professor. Dr. Sankar

Chatterjee, for helping me to obtain the materials for

this project, his guidance through this project, and,

most importantly, his enthusiasm. His constant

excitement concerning the project kept me going.

I am grateful to the members of my committee. Dr.

Necip Guven not only allowed the use of his x-ray

diffractometer, but he took the time to quality check my

methods to ensure that things were done correctly.

Thanks to Dr. George Asquith for taking the time to

review the manuscript.

Thanks Jack Horner, David Varricchio, and Mark

Norell for contributions of eggshell for this study.

Dr. Calvin Barnes allowed the use of his

petrographic microscope for photographing the thin

sections for the chapter on light microscopy. Mike Gower

of Texas Tech made all the thin sections.

Last but not least, I thank my wife, Brianna

Pollinger, for forcing me to continue working and being

patient with the loss of her husband until this was

completed.

11

TABLE OF CONTENTS

ACKNOWLEDGEMENTS ii

LIST OF TABLES iv

LIST OF FIGURES v

CHAPTER

I. INTRODUCTION 1

II. SCANNING ELECTRON MICROSCOPE ANALYSIS 8

Materials and Methods 8

Avian Eggshell Microstructure 9

Non-Avian Dinosaur Eggshell Microstructure . . 13

Mineralogy 16

Eggshell Measurement by S.E.M 17

Discussion 18

III. X-RAY DIFFRACTION 36

Methods of X-ray Diffraction 36

Avian and Dinosaur Mineralogy 42

IV. LIGHT MICROSCOPY 45

Methods 45

Mineralogy and Microstructure 45

Discussion 51

BIBLIOGRAPHY 61

111

APPENDIX

A. PHYLOGENY OF BIRDS SAMPLED 63

B. X-RAY DIFFRACTION TABLES 65

C. X-RAY DIFFRACTION CHARTS 71

IV

LIST OF TABLES

2 .1 Shell measurements 32

B. 1 X-ray Diffraction Results for Rhea 66

B.2 X-ray Diffraction Results for Troodon 67

B. 3 X-ray Diffraction Results for Maiasaur 68

B. 4 X-ray Standard Values for Quartz 69

B. 5 X-ray Standard Values for Calcite 70

v

LIST OF FIGURES

1.1 Phylogeny of Dinosaurs and Birds Sampled 3

1. 2 Cladogram of the Dinosaurs 5

2.1 Generalized Egg Illustrating Radial View 11

2.2 Photomicrograph of Organic Core of a Turkey Eggshell 21

2.3 Photomicrograph of Interior Surface of a Chicken Eggshell 22

2.4 Photomicrograph of Fibrous Membrane of a Chicken Eggshell 23

2.5 Photomicrograph of a Radial Section through A Rhea Eggshell 24

2.6 Photomicrograph of External Surface of a Rhea Eggshell 25

2.7 Photomicrograph of Exterior of Prairie Falcon Eggshell 26

2.8 Generalized Structure of Avian and Non-avian

Dinosaur Eggshells 27

2 . 9 Photomicrograph of Maiasaura Eggshell 28

2.10 Photomicrograph of Radial Section through a

Maiasaur Eggshell 29

2.11 Photomicrograph of a Sauropod Eggshell 30

2.12 Photomicrograph of a Troodon Eggshell 31

2.13 Shell Thickness versus Shell Circumference 34

2.14 Layer Thickness versus Thickness of Shell 35

4.1 Photograph of Troodon Eggshell Showing Cleavage Planes (lOx) 55

VI

4.2 Photograph of Sauropod Eggshell Viewed Through Crossed Nicols (5z) 56

4.3 Photograph of Sauropod Eggshelx Viewed Through Plain Light (5z) 5"

4.4 Photograph of Titanosaur Eggshell Viewed Through Crossed Nicols (5x) Showing Chalcedony Replacement 58

4.5 Photograph of Troodon Eggshell Viewed Through Crossed Nicols (5x) 59

4.6 Photograph of Emu Eggshell Viewed Through Plain

Light (lOx) 60

A. 1 Phylogeny of Birds Sampled 64

C. 1 X-Ray Diffraction Chart for Rhea 72

C. 2 X-Ray Diffraction Chart for Troodon 73

C. 3 X-Ray Diffraction Chart for Maiasaura ''4

vii

CHAPTER I

INTRODUCTION

The egg plays an important part in the reproduction

of vertebrates. It contains the offspring until the

animal has a chance of survival in the environment

outside of the egg. The basic purpose of the eggshell is

to regulate fluid and gas movement between the inside of

the egg and the outside world.

The earliest vertebrates were aquatic. The entire

process of reproduction for these animals took place in

water. Since the eggs were deposited in water, no need

existed for anything more than a water permeable membrane

to contain the growing embryo. As animals became

terrestrial, the same strategy was used. Amphibians

sought out standing water with which to deposit their

eggs. If the chosen location became dry, the eggs would

be in danger of drying out, killing the embryo. This

tied the amphibians to environments with sufficient

water. This water might be a river, a lake or pond, or

puddles of standing water.

1

The reptilian advancement of the hard eggshell was a

clear advantage. For the first time, the reproductive

process was not tied to sources of water. The reptilian

shell held moisture in, but also allowed for the transfer

of gasses in and out of the shell. The creation of a

solid calcite or aragonite layer, the body of the

eggshell, gave the shell its strength. The shell had to

be strong enough to protect the egg from either the

incubating parent, the overlying sediment, or other eggs

in the nest, yet weak enough to allow the young animal to

hatch out of the egg.

The invention of the ^amniote' eggshell made the

impermeability to fluids possible. At the same time,

pores allowed the embryo to inhale oxygen and exhale

carbon dioxide. Dinosaurs used this basic reptilian

design, while the modern birds took this same format with

added complexity.

Recent phylogenetic analysis suggests that the

members of the class Aves, the birds, are theropod

dinosaurs (Gauthier, 1986; Chatterjee, 1997). Birds are

the closest living relatives of the extinct non-avian

dinosaurs. Because of the close relationship between the

birds and other dinosaurs, any broad comparative study of

dinosaur phylogeny should include the birds. It is for

this reason that this work begins with nineteen eggshell

samples of a wide variety of modern birds. Using the

variation of the modern birds, study proceeds to the non-

avian dinosaurs. We then work our way outward to

dinosaurs that are less and less related to the modern

birds. The basic concept of this investigation is that

the farther removed a dinosaur is from modern birds, the

more different its eggshells will be to eggshells of the

birds. Figure 1.1 shows the phylogenetic relationships

of the members of the dinosaurs as it is now understood

(simplified from Chatterjee, 1997).

Dinosauri

Saurischia

Theropoda

Neornithes

Maiasaura (ornithopod) Titanosaur (sauropod) Oviraptor (non-avian theropod) Troodon (non-avian theropod) Gobipipus Palaeognathae Neognathae

(Galiiformes/Answeriformes) Neognathae(All others)

Figure 1.1 Phylogeny of Dinosaurs Sampled

The Neognathae and Palaeognathae are the two groups

that make up the modern birds. Both groups have living

members. Gobipipus is an extinct bird of modern form.

All other groups listed in the cladogram are extinct non-

avian dinosaurs. The Neognathae represent the bulk of

the modern birds. The Neognathae eggshells come from the

Canada goose, domestic chicken, wild turkey, pied-billed

grebe, California brown pelican, sora rail, Forster's

tern, great blue heron, common pigeon, turkey vulture,

prairie falcon, osprey, red shouldered hawk, great horned

owl, belted kingfisher, and white-necked raven. The

Palaeognathae are the ratites. These are the large

flightless birds such as the Ostrich, Emu, and Rhea.

They are considered primitive to the other flying birds.

Additionally, fragments of eggshell of the early bird

Gobipipus were included. Gobipipus is an extinct bird

from the Cretaceous Barun Goyot Formation of the Gobi

desert in Mongolia.

The first non-avian dinosaur represented is Troodon.

Troodon was a small, intelligent theropod and a member of

a sister group of the Aves. It had a swivel wrist joint,

a characteristic of the maniraptorans. The Troodon

eggshells were collected in the Late Cretaceous Two

Medicine Formation in Montana. Another maniraptoran

theropod is the Oviraptor from the Cretaceous. Oviraptor

has been found in the Gobi Desert of Mongolia. Among the

sauropods, the titanisaurid eggshells from the Upper

Cretaceous Lameta Group of India have been studied.

Finally, the Maiasaura, an ornithopod, is the most

phyiogeneticaily removed dinosaur from modern birds. The

eggshells of the Maiasaura were also collected from the

Two Medicine Formation of Montana. Figure 1.2

illustrates the relationship between the members of the

dinosaurs as it is now believed (from Chatterjee, 1997).

Thyreophora

Ornithischia I

Dinosauria

t Cerapoda

Saurapodomorpha

i i

Saurischia

Theropoda c

• Stegosauria

•Ankyiosauria

. Ceratopsia

•Ornithopoda*

•Prosauropoda

•Sauropoda*

Other Theropods*

Aves*

Figure 1.2 Cladogram of the Dinosaurs

Asterisks represent groups with a sample included

These eggshells were studied using three main tools,

the scanning electron microscope, the x-ray

diffractometer, and the polarizing light microscope. The

scanning electron microscope (SEM) was used to view the

microstructure of the eggshells. Using the SEM, the

shell material can be viewed in three dimensions to see

the relationship between crystals within the shell and

the relationship between layers that make up the shell.

This information can then be used to compare eggshells of

differing species. The x-ray diffractometer was used to

analyze the mineralogical content of the eggshells. X-

ray diffraction sample results were compared to known

samples to identify mineral composition. The polarizing

light microscope was used to view the interaction of the

individual crystals that make up the shells.

Identification of the mineralogy of the shell material

and any surrounding matrix was also attempted.

It is through a comparative process that an attempt

to link the eggshell material of the non-avian dinosaurs

to those of the avian dinosaurs. It is hoped that a

progression of shell morphology can be seen ranging from

the most distantly related species of dinosaur to th(

eggshell modern birds.

7

CHAPTER II

SCANNING ELECTRON MICROSCOPE ANALYSIS

Materials and Methods

For scanning electron microscope (SEM) analysis, a

small chip of shell was removed from each egg. Since

most of the non-avian dinosaur shell was broken material

smaller than a dime, a single small chip was used. One

exception was the sauropod shell. It was attached to a

matrix of rock on its interior surface. In this case,

the shell was broken to a manageable size and as much

matrix was removed as possible without damaging the shell

above. Each avian and non-avian dinosaur eggshell piece

used ranged from about five millimeters to fifteen

millimeters in diameter. The bird shell was broken from

an intact eggshell; therefore, all surfaces were freshly

broken. For the fossil dinosaur eggshell, the sample was

broken to obtain a fresh surface. These samples were

then mounted on aluminum specimen holders by double-sided

carbon tape. For best viewing by the microscope, the

fragments used were mounted so that a freshly broken

surface was visible when looking straight down on the

8

sample holder. Up to four samples were mounted on one

sample holder, each placed so that it would not obstruct

the view of another sample on the same holder. Colloidal

silver paste was then applied to connect the specimens to

the aluminum holder. This silver paste provides an

electrical connection between the shell material and the

sample holder. The paste was then allowed to dry.

The specimens were next placed in a Technics Hummer

V sputter coater. A sputter coater is a machine that is

used to apply a thin (-20 nm) coat of gold palladium to

the egg fragments. This gold coating allows -the entire

surface to be grounded through the colloidal silver, down

the stub, and to the rest of the machine through the

stage- The coating enhances electron emission for

detection by the microscope. After coating, the samples

were ready for use in the SEM. The microscope used in

this study was a Hitachi S-570 scanning electron

microscope.

Avian Eggshell Microstructure

Many workers have looked at the microstructure of

dinosaur eggshell (Hirsh and Quinn 1990, Mikhailov 1991,

Mikhailov et. al. 1994, Hirsh 1994, Zhao 1994). These

workers have found that avian eggshell morphology is

relatively uniform throughout the Class Aves. Growth of

the eggshell begins at a point called the organic core.

From this spot, close to the fibrous membrane lining the

interior surface of the shell, the crystals grow outward.

Mikhailov (1991) calls these crystals ''the zone of radial

plates". In Figure 2.2, the organic core of a Wild

Turkey {Meleagrus gallopavo) is visible. The surface of

the shell is toward the top of the photomicrograph. The

zone of radial plates spreads outward from this central

point. As can be seen in an interior view, the basal

radial crystals are called mammillae (Hirsch and Quinn

1990). This lends its name to the interior layer of the

shell, called the mammillary layer. The degree to which

the mammillae connect to each other varies. The

interiors of some specimens appear almost continuous;

whereas, others have distinct, separate mammillae. Figure

2.3 is an interior view of a modern chicken {Gallus

gallus) eggshell. The fibrous membrane has been

partially removed to expose the mammillae. In Figure

2.4, the connection of a mammilla to the underlying

10

fibrous membrane can be seen. This photomicrograph is

also of a chicken eggshell.

Above the radial units, the crystals begin to grow

upward toward the surface. They radiate outward until

they meet the radial units of the neighboring mammilla,

then continue parallel toward the exterior of the shell.

This has been named the zone of tabular aggregates (ZTA)

(Mikhailov 1991). Together with the zone of radial

crystals, the zone of tabular aggregates makes up the

mammillary layer. Figure 2.5 is of a Rhea {Rhea

americana) eggshell. The top of the photomicrograph is

toward the surface, and the bottom is toward the interior

with the fibrous membrane visible at the bottom. This

edge-on view of an eggshell fragment is referred to as

the radial view. Figure 2.1 illustrates a radial view.

Figure 2.1 Generalized Egg Illustrating

Radial View

11

The radial view allows the shell to be seen from the

inside to the outside of the shell. It is in this way

that we can look at the crystals that make up the shell.

The mammillary layer is visible in the bottom half of the

photomicrograph. The discrete crystals give way to what

is referred to as the zone of squamatic aggregates

(Mikhailov 1991) or squamate zone. This section has also

been referred to as the spongy layer, the palisade layer

(Solomon et. al. 1994), or the prismatic layer (Hirsh and

Quinn 1990) . This squamate zone is identifiable in

Figure 2.5 above the zone of tabular aggregates. Many

vesicles pierce the squamate zone. I have found that

some species appear to have many vesicles, such as the

birds of prey, in comparison to other species, such as

the chicken, which have fewer. The number of vesicles

also varies throughout the squamate zone (Solomon et. al.

1994). Above the squamate zone is a thin layer called

the external zone (Mikhailov 1991) . This zone varies in

compaction and crystaliinity. Some samples have a

readily recognizable separate layer, as can be seen in

Figure 2.6 of a Rhea. The external zone is contacting a

pore and can be seen running from the center right to the

12

bottom center. Above, this zone is contacting pore

material; and below, it meets the squamate zone. The

contact between the two zones is fairly distinct.

Figure 2.7 is of the same area of a Prairie Falcon

(Faico mexicanus) eggshell. The external zone is on top,

and the squamate zone is below. The distinction between

the two is not completely distinct, as in the previous

example. Here, the two zones are differentiated by their

relative compactness. The external zone lacks the number

and degree of vesicles that are contained within the

squamate zone.

Non-Avian Dinosaur Eggshell Microstructure

Non-avian dinosaur eggshell microstructure is

similar to avian microstructure, as should be expected

from their close phylogenetic relationship. There are,

however, some very important differences. The

generalized non-avian dinosaur eggshell does not contain

either the squamate zone or the external zone. The shell

thickness is comparable to that of the birds, but the

mammillary layer takes up the extra thickness. This zone

13

extends to the surface. This generalized form is shown

in Figure 2.8.

More specifically an attempt to further

differentiate the eggshells of non-avian dinosaurs has

led to the creation four basic groups based on pore

geometry and crystal pattern:

Augustispherulitic: "pore canals narrow, more or less

straight, and of fairly constant diameter; shell units

interlock laterally and have tendency to fuse".

(Hirsch and Quinn 1990).

Prolatospherulitic: "pore canals rather irregular and of

varying diameter, changing their course; similar

crystalline structure as in the angusti-type". (Hirsch

and Quinn 1990).

Tubospherulitic: "pore canals similar to the a/igusti-type

with some enlarged openings; shell units not

interlocking and never fused". (Hirsch and Quinn

1990).

Multispherulitic: "narrow, more or less straight,

extremely numerous and closely spaced pore canals;

crystalline structure unknown." (Hirsch and Quinn

1990).

14

Two additional groups added by Hirsch (1994) are

Dendrospherulitic and Obliquiprismatic. Additionally,

the Augusti-type has been divided into spherulitic and

prismatic forms based on the whether or not the crystals

continue parallel or interlock.

Figure 2.9 is a radial cross section through a

Maiasaura eggshell. The crystallites appear to be fused.

Later, we see that in thin section, the crystals can be

seen as distinct. The pore canal in the center is fairly

regular continuing upwards into the shell. Based on this

information, this shell fragment would be best classified

as angustiprismatic. Figure 2.10 is of another fragment

of Maiasaura eggshell. The interlocking crystals are

readily visible. In the middle, a large amount of

recrystallization has occurred.

Zhao (1994) put forth an interesting deviation from

these models. In this case, growth proceeds from the

organic core out to the zone of tabular aggregates, then

begins again through several layers. Shell thickness is

not increased, only divided into several layers. Figure

2.11 is from a sauropod. What appears to be the beginning

of a crystal of the shell is actually positioned halfway

15

from the base and the surface. Furthermore, it is

located above another similar crystal.

Mineralogy

Many zones of recrystallization can be seen. The

most extensive of these can be seen in Figure 2.10. This

appears to simply be calcite to calcite

recrystallization. Figure 2.12 is of the base of a

Troodon shell. Almost all of the lower part of the shell

has been recrystallized, again probably to calcite.

We can correlate our samples with the groups set up

by earlier workers. With an increasing collection of

known samples, we will be able to identify shell type to

its respective dinosaur group. Also, we are now able to

take the samples we have, and with the same technique,

those we obtain and identify those parts we wish to do a

mineralogical study.

Eggshell Measurements by S.E.M.

Using the scale of the photomicrographs of the

scanning electron microscope, measurements of the shell

thickness and the thickness of the individual layers of

16

the shell were taken. These measurements were then

charted to gather information as to the differences or

similarities between the shells of individual species.

The measurements used in the chart are as follows:

SZ/ML is the ratio of thickness between the squamate

zone (SZ) and the mammillary layer (ML). This was found

by dividing the thickness of the squamate zone, as

determined from SEM photomicrograph scale, by the

thickness of the mammillary layer.

Height and width were measured from photographs of

the whole egg using the millimeter ruler used for scale.

For the non-avian dinosaur eggs, height was calculated

from spherocity divided by width. Width was found by two

times the radius.

Spherocity is a measure of the roundness of the

shells and, for the bird eggs, is found by taking the

width divided by the height. For the non-avian

dinosaurs, this value is found by using the average

roundness for all the bird samples.

The radius for the bird eggs is found by taking

dividing the width in half. In the case of the

17

dinosaurs, this was back calculated by dividing the

circumference by n and taking the square root.

The equatorial circumference is found by multiplying

the radius-squared times TI. For the non-avian dinosaurs,

the circumference was found by plotting the circumference

to shell thickness for all the birds on a log-log chart.

Using a straight-line correlation, the fossil dinosaurs

were plotted by thickness and circumference was

determined from the regression line for the avian

dinosaurs.

Thickness of the shells was taken from SEM

photomicrographs using the scale of the bar produced by

the microscope and printed on the photomicrograph. The

units are in micrometers ()Jin) .

Discussion

Several plots were created using the data presented

above. One such plot was a comparison between eggshell

thickness and the circumference of the eggs. The

thickness (im) of each avian eggshell was plotted on the

horizontal axis, and the circumference (cm) was plotted

on the vertical axis. The plot scale was set to

18

logarithmic for both axes. Next, a regression analysis

was performed to acquire a predicted circumference line.

The resulting formula for this line is y = 0.0188x - '' .

This equation suggests that the circumference of the egg

(in centimeters) is equal to the constant 0.0188

multiplied by the shell thickness (in micrometers) raised

to the 1.1421 power. The r-squared value equaled to

.903, allowing us to place a high degree confidence in

the resulting regression equation. From this equation,

other eggshells can be plotted by shell thickness to give

an approximate shell circumference. Care must be used in

a determination of circumference in this manner. Shell

thickness can vary depending on the point of measurement.

This has been provided only as a rough estimate for

determining shell size from eggshell fragments.

The ratio of the squamate zone (SZ) to the

mammillary layer (ML) was plotted against the thickness

of the shell. In examining this resulting graph, a clear

division between the paleognathae and neognathae can be

seen. For the neognathae, as the ratio of the SZ/ML

changes, the shell thickness remains within a range from

90^m to 700|Lim. In the case of the ratites, as the shell

19

thickness increases, the squamate zone increases in

relative thickness to the mammillary layer.

20

c u r e s . z. Core of a

•urke\" ^ .cosne- l

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of a Chicken Eggshell

23

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28

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(UIO) ^ ecus,

34

o o o o I — I

T

CO 0) -P H 4-J

03 •^

1

\

\

r

o o o r—1

(uir

• Ratites

•Galliformes and

Answeriformes

AOther

Neognathes

xGobipipus

hes

1 <i

1

'4 '

-1 1 ( i

ii^

•t

4

D —1

Ji

7

1

^

x -1

1 ,._

O O r-O rH rH

1) ss9u>[0Tm TTsqS

o ^ r-l

LOO

1.000

10.

Layer Thickness

Ratio

Figure 2.14

Layer

Thickness

versus

Thickness

of Sh

ei

- CD

35

CHAPTER III

X-RAY DIFFRACTION ANALYSIS

Methods of X-ray Diffraction

X-ray powder diffraction has proven itself to be a

valuable tool in geochemistry and mineralogy. Its main

use is to identify minerals present within a powdered

sample. This is accomplished by the detection of a beam

of radiation reflected from the sample to be studied.

X-ray radiation produced by an X-ray generator

begins with a high voltage source. In the case of the

machine used for our experiments, an X-ray tube emits

energy that strikes a copper plate. The energy excites

the electrons in the copper, causing x-rays to be emitted

in all directions. This radiation is channeled out of

the generator to the sample to be studied. A detector

receives refracted beams of the x-rays and then transmits

the information it receives to the computer

instrumentation (Moore and Reynolds, 1989) .

The X-ray tube is powered by a ten to fifty kilovolt

energy source. Energy is released across a gap in the

circuit to strike a copper plate, referred to as the

36

'target.' Within this copper plate, electrons move from

a higher orbit to replace those removed from the lower

orbits (Moore and Reynolds, 1989). As the electrons

jump, they release characteristic x-rays for the target

material and the shell positions that were involved. The

x-rays are emitted as waves and have a vector quality

similar to visible light. The wavelength, however, is

much shorter. These x-rays are allowed to escape the

tube tower by a controlled shutter, forcing the waves to

the sample (Moore and Reynolds, 1989).

The diffractometer, also called the goniometer, is

where the x-rays from the source come in contact with the

sample to be studied. The incoming x-rays are filtered

by the Seller slit and the divergence slit (Moore and

Reynolds, 1989). These slits control the beam that will

strike the sample. The divergence slit controls the

width of the beam and the Seller slits make the x-rays

uniform. On the detector side of the diffractometer are

more Seller slits, a receiving slit, and a scatter slit.

The receiving slit controls the amount of rays entering

the detector, and the scatter slit eliminates any

scattering that has occurred.

37

The diffractometer rotates the sample about a

uniform degree set in the computer and at specified time

increments. This is to get the amount of radioactive

counts per time unit. As the detector rotates around the

sample and collects counts of radiation, the sample is

also rotated so that the angle of the incoming waves

diffracts at the same angle as the exiting waves.

The detector is mounted on an arm that rotates

around the sample chamber. Its function is to capture

the incoming diffracted x-rays and provide the computer

system with the number of 'counts' of radiation it is

receiving. The detector is a hollow tube filled with

Argon gas (Moore and Reynolds, 1989). The center of the

tube contains an anode wire connected to a high voltage

source. As the x-rays enter the chamber, the Argon atoms

lose an electron. These electrons, attracted to the

anode wire, create a current that is measured by the

computer system. The amount of current generated gives

an intensity for that angle of diffraction.

The computer system measures the intensity of the

diffracted beam. The intensity is then printed either as

a scrolling pattern or in counts per preset time unit.

38

The instrumentation also controls the speed and angle

increment of rotation of the detector arm and sample.

The waves reaching the sample are uniform in that

they are parallel and in phase with each other. This is

ensured by the slits mentioned previously. As these

parallel waves strike the sample, two waves result from

the contact. The first type is called the primary waves.

These are the original waves that continue in a straight

line into the sample until they are absorbed. These are

unimportant in x-ray diffraction. The other wave type is

the secondary x-ray. These secondary x-rays are what is

read by the detector. The intensity of the sum of these

waves is what is important in x-ray diffraction.

Bragg's Law is the relationship between the incident

wave angle that strikes the sample, the wavelength of the

wave, and the distance between lattice planes of the

sample powder. The wavefronts that reach the sample

being diffracted are all in phase. For the secondary

waves to be of the greatest intensity, they must be in

phase after the diffraction. For instance, if wave 1

strikes the surface, wave 2 must travel a distance that

will allow it to complete one wavelength before becoming

39

parallel to wave 1'. Using geometry, we get the following

equation

HA = H'A = d X sin 0 (3.1)

In equation 3.1, HA and H'A are distances between those

points, d is the distance between lattice planes, and 0

is the angle between the x-ray beam and the lattice

plane.

From equation 3.1, the distance from H to H' is:

HA + H'A = 2d X sin0. (3.2)

Adding the x-ray into the equation gives the following

(Moore and Reynolds, 1989):

2d X sin @ = n X. (3.3)

In the above equation, X is the wavelength of the beam

and n is an integer. Solving equation 3.3 for the

distance between lattice planes results in Bragg's Law;

d = n x { X / 2 X sin 0 ) . (3.4)

40

We find that when n (the distance between H and H') is

equal to a whole number (1,2,...), the waves will be in

phase after the diffraction. However, when n is equal to

a whole number plus one-half (^,1^,...), the resulting

phase will be destructive. Any n between these values

will produce a varying degree of destructiveness

depending on its value.

The intensity of the beam reaching the detector can

be affected by eight factors. The first is called the

structure factor (Fhki) • This is the effect that the

atoms within the powder have on the beam. The intensity

of the original beam (lo) affects the resulting

intensity. The volume (v) of the material being

diffracted alters intensity. Another factor is the

multiplicity factor (m). This is the effect of the

crystal symmetry and number of lattice planes. The

Lorentz-polarization factor (Lp) attempts to correct for

inconsistencies in the change of the sine of theta as

theta changes and the polarization of the diffracted

beam. The atomic scattering factor (fo) is a correction

for secondary waves destructing or amplifying the main x-

41

rays. Phase differences from differing temperatures is

considered by the temperature factor (T). Finally, the

absorption factor (A) takes into account the amount of x-

rays being absorbed by the material. All of these

factors are summed, giving the final intensity equation

for the indices hkl.

2 Ihki=IoXLp (0)xmx I Fhki I xA(0) xT (G) xv ( 3 . 5 )

Avian and Dinosaur Mineralogy

Using the x-ray diffraction principles described

above, avian and dinosaur eggshell was tested for mineral

composition. The shell was first prepared for

diffraction. This was accomplished by grinding the shells

to a fine powder using a mortar and pestle. The powder is

then packed into the sample holder, which is placed into

the diffractometer. The diffractometer output is in the

form of a graph. This graph plots relative intensity in

radiation counts per degree of angle of incidence between

the beam of radiation and the sample. As the sample is

rotated through various degrees, intensity varies. The

resulting chart produces a relatively constant base

42

punctuated by peaks of high intensity. The placement of

the peaks and the relative intensity for each varies

depending on the mineral content. These intensity peaks

are compared to tables of known minerals in order to make

a mineralogical identification.

Upon analysis, the main mineral content of the

samples was found to be calcite. This can be seen by

comparing the data from Tables B.l to B.3 with the x-ray

diffraction standards table for calcite (Table B.4). The

d value of 3.05 for a maximum peak is an x-ray

characteristic of calcite. In some of the dinosaur

samples, quartz was also found to be present. This can

be seen in table A.5 as having a d value of 3.34 for the

maximum peak. The relative intensity of the quartz peaks

was many times lower than that of the calcite peaks.

This lower relative intensity suggests a lower quantity

of quartz in the sample. The origin of the quartz was

originally thought to be replacement. After looking at

the samples with a polarizing light microscope, the

origin of some of the quartz was confimed to be

chalcedony replacement of the original calcite. In other

cases, it was found to be sandstone matrix that was

43

cemented to the shell exterior and filled pore spaces

within the shell. In either case, ohe original shell

material was composed of calcite.

44

CHAPTER IV

LIGHT MICROSCOPY

Methods

The dinosaur and avian eggshells were examined

under a light microscope. The purposes of using the

-ighr rrdcroscope incluoed the examination of the

rr.inera_ogy of the she_ls and their surrounding rr.aorix

and tne observation of the structure of the crystals

that ::;ake up the shell.

Preparation began by piecing off small chips that

were approximately two centim.ezers in size. These

pieces were mounted in epoxy and ground into one thin

section for each specimen by the technician of the

~exas Tech Geology department. The mounting done so

that each sample would oe cut oo expose a radial view

Mineralogy and Microsoructure

Each rhin section was stuaied for mineralogical

content. Calcite (CaCOs) was found to be the primary

mineral present for a^^ shelis. Under poiarized

45

light, the calcite in these sam ples was tan in color

and had.a symmetric extinction as indicated by Ehlers

(1987) . The offsetting extinctions of the crystals

within the shells revealed the interlocking

relationship between these crystals. For the avian

eggshells, r.o other mineral appeared present. The

dinosaur eogshells contained variations of quartz

(Si02) . This quartz inc_uded and surrounded the

original calcite of the eggshell. Some of the quartz

was present as grains. These grains made up the

sandstone r.atrix that surrounding the eggshells as

they were curled. Other quartz is chalcedony, filling

pore spaces and, in places, partially replacing the

original calcite shell.

The "icrostructure types of the bird eggshe_-s

can be divided between the Palaeognathae and

Neognathae. The Palaeognathae eggshells have two

distinct .avers when viewed through crossed nicols.

The interior of the shell has distinct prismatic

crystal structure. This prismiatic structure abruptly

ends, giving a spherulitic exterior. This form varies

between the species.

46

The emu has only one quarter of its eggshell in

prismatic form. The rhea, however, has two thirds of

its eggshell miade up of distinct prismatic form. The

prismatic section of the ostrich makes up about one-

fifth of the shell thickness. The spherulitic section

of the ostrich is very different from that of the emu.

The individual crystals of the ostrich egg retain a

columnar snape all the way to the shell exterior.

This is similar to the Neognathae eggshells. The

difference between the ostrich and the Neognathae is

that the prisms of the ostrich are not as consistent

and uniforiTL. While oriented in the correct direction,

the prismis of the ostrich vary in thickness and

positioning within the shell.

When viewed through crossed nicols, the

Neognathae eggshells retain a prismatic shape from

interior to exterior. Although the boundaries between

the crystals are erratic, individual crystals are well

defined from the surrounding crystals. Viewed through

a light microscope, the shell appears as bands of

light and dark extinction zones. Each band is fairiy

constant in thickness.

4 7

The microstructure of the dinosaur eggshells

varies with species. Each shell can be typed

according to the structural morphotypes described in

Chapter II. The basic morphotype that best fits

Troodon is ornithoid.

The Troodon eggshells are very similar to the

modern bird eggshells when viewed through a light

microscope. This similarity can be seen in the

crystal structure. Both the modern bird shells and

these dinosaur shells have interlocking crystals that

extend in the prismatic layer from the mammillary

layer to the exterior surface of the eggshell. A

sharp crystal boundary exists between adjoining

crystals in the prismatic layer. This can be seen as

neighboring crystals exhibit extinction at separate

degrees of sample rotation. Both avian and these

dinosaur samples also contain a very visible

mamimillary layer.

Figure 4.1 is of Troodon, At a magnification of

lOx, this photograph views the eggshell in plain

light. The letter A in the bottom-right of the

picture is located on the interior side of the shell.

48

The line from A to B is drawn from, the interior of the

shell to the exterior of the shell. This line fol.ows

the c-axis cf the crystals that make up the shell.

Short, thin, dark lines can be seen running at a 45-

degree angle frcrr; the c-axis throughout the shell.

These lines are cleavage planes for the calcite

crystals.

A other di' csaur eo'^'^'riQ^I-S aoDear to be of the

Dincsaurcid type. Both sauropod shells can be best

describee as tubospherulitic. Figures 4.2 and 4.3 are

both cf a sauropod. Figure 4.2 was taken at 5x vvith

crossed niccls. In this view, the replacement cf the

original calcite by chalcedony is clearly visible.

The rep_acement occurs from the exterior and interior

surfaces invrard, using the pores as an access to the

crystals. Fioure 4.3 is the same view under plain

light. In this second view, the replacing chalcedony

^ appears as lightened areas within the shell. Under

plain light, vre see that the replacing quartz takes

the shape of the original calcite.

As the shell grows, excess material is included.

This extra organic ingredient to the shel^ can be seen

as a layering texture within the shell. In Figures

4.2 and 4.3, the organic content appears as lines

running perpendicular to the c-axis of the crystals.

This layering is partially retained by the replacing

chalcedony, suggesting that the replacement was a

gradual process of calcite removal that was

iminediately followed by chalcedony deposition.

Another sauropod can be seen in Figure 4.4. Much

of the original caicite has been replaced. An

original crystal of calcite remains at the center left

of the photograph, as well as partial remains

throughout the top half of the photograph. At the

bottom one fourth of the photograph is the matrix

which the shell was contained after burial. A line of

chalcedony cuts across the shell from the center

right, into the shell at the center, and upward to the

upper left of the photograph. This chalcedony not

only crosses the shell, but also cuts through the

matrix surrounding the shell. This implies that this

reolacement is secondary to the burial of the shell.

The last dinosaur sample is of the Maiasaura.

This shell appears angustiprismatic. The prisms that

50

make up the shell are not uniform in size or

thickness, but they are oriented in an interior-

exterior direction. This shell has the greatest

amount of organic material included within the shell

This included material gives the shell a strong

layered effect when viewed in plain light. The

resulting effect gives the eggshell an appearance

similar to the rinas of a tree.

Discussion

Comparing the dinosaur eggshells, a progression

can be seen in the steps leading to the miodern birds.

The Maiasaura eggshells bear the least resemblance to

the avian eggshells. These eggshells contain only one

layer, the mammillary layer. The growth begins at the

organic core. Crystal growth proceeds outward to the

surface with fairly uniform crystal growth. The

Titanosaur eggshell follows this form. It too is only

composed of the mammillary layer.

When we reach the theropods, a change in the

structure can be seen. The theropod eggshells retain

the mammillary layer as seen in the ornithischian and

51

sauropodomorpha. Through light microscopy, we can see

the addition of the squamate zone. In Figure 4.5, we

see a Troodon eggshell (5x). The mammillary layer and

the squamate zone appear different as viewed in cross

nicols. The mammillary layer can be identified, as it

appears brighter than the squamate zone. The squamate

zone is now visible as a distinct shell layer. The

crystals are irregu_ar and interlocking. As we get

closer to the birds, the crystals become more

palisade.

In the avian eggshells, the crystals are very

distinct in light microscopy. There is a strong

linear relationship to the c-axes. More importantly,

we see the addition of the third layer, the external

zone. This is very evident in the emu eggshell as

viewed in plain light (Figure 4.6). The interior is

to the bottom cf the photograph. The mamimillary layer

is distinct. It appears as tne brown and white

interior layer. Throughout the crystals, layers of

growth are evident. Above this layer, the squamate

zone can be seen. This zone appears homogeneous

laterally. Toward the exterior, the zone becomes less

compact. Sitting immediately above the squamate zone

is the external zone. This zone is easily

distinguished as a compact zone of calcite. The

external zone is only a small percentage of the

overall shell thickness, but it is a very important

identifier to the t\^e of dinosaur which produced the

egg.

Supported by fossil evidence, current thought

holds that the m.cdern birds are theropod dinosaurs.

Phyiogeneticaily, their closest extinct relatives are

other theropod dinosaurs, such as the Oviraptor ani

Troodon. According to this thought, the m.odern birds

can be placed in the saurischia with sauropods. It

would be expected that the eggshell evidence support

the anatomical evidence. We can see a transition from

the non-theropod dinosaur eggshells to the sheiis of

the theropods. There is the addition cf the squam ate

zone and a decrease in the surface ornam.entation. We

can also show a change w ithzn the theropod dinosaurs.

The avian theropods have added an additional layer,

the external zone, v;hich the other theropods lack.

^ ^

^ - / P -y^ /~, ^ 'y- r2. c: <z: ": •

v _ . : ^ - _ - ^ K ^ ' ^ ^ s ^ f ^' ^ r.^ " h s zr c c c li s

-^ - ^ -• r- -- f witr. o » ^ , - y^ ^-~i

. w t ; ^«. k^'.. y .

^r ± ±^ I '. • ' ^ ^ r^. - ^ ^ > V -

; ^ ^ — - - . p - t - p-", '-N- -|-^, o o T , c - i c i ' ^ c -!-^ - i c t o r "

1 -;

D-t

Figure 4.1 Photograph of Troodon Eggshell Showing Cleavage Planes (lOx)

Figure 4.2 Photograph of Sauropod Eggshell Viewed

Through Crossed Nicols (5x)

56

Figure 4.3 ootograph of Sauropod Eggshell Viewed

Through Plain Light (5x)

R'

_ > V- /-N * - r-s "T > " —, r—V r~,

sr.e__ viewe: Tn; fh C; ::n owing

r i g u r e 4 . o

rpv-> ,TJQV^ ^zrosssci N ~ c ^ ' ^ (^x) ewG

Figure 4.6 Photograph of Emu Eggshell Viewed

Through Plain Light (lOx)

60

BIBLIOGRAPHY

Card Number 5-0490 (Quartz). Swarthmore, PA: Joint Committee on Powder Diffraction Standards, n.d.

Card Number 5-586 (Calcite). Swarthmore, PA: Joint Committee on Powder Diffraction Standards, n.d.

Chatterjee, S. The Rise of Birds: 225 Million Years of Evolution. The Johns Hopkins University Press, Baltimore, 1997.

Craycraft, J. ''The origin and early diversification of birds"; Paleobiology 12:383-399, 1986.

Ehlers, E.G. Optical Mineralogy, pp. 107-109. Blackwell Scientific Publications, Palo Alto, 1987.

Gauthier, J. ''Saurischian monophyly and the rise of birds"; pp. 1-55 in K. Pandian (ed.), The Origin of Birds and the Evolution of Flight. California Academy of Sciences, San Francisco, 1986.

Hirsch, K.F. "Upper Jurassic eggshells from the Western Interior of North America"; pp. 137-150 in K. Carpenter, K.F. Hirsch, and J.R. Horner (eds.). Dinosaur Eggs and Babies. Cambridge University Press, Cambridge, 1994.

Hirsch, K. and B. Quinn. "Eggs and eggshell fragments from the Upper Cretaceous Two Medicine Formation of Montana" J. Vert. Paleo. v.10, no. 4, pp. 491-511, 1990.

, K. Sabath, and S. Kurzanov. "Eggs and nests from the Cretaceous of Mongolia"; pp. 87-115 in K. Carpenter, K.F. Hirsch, and J.R. Horner (eds.). Dinosaur Eggs and Babies. Cambridge University Press, Cambridge, 1994.

61

Mikhailov, K.E. "The Microstructure of Avian and Dinosaurian Eggshell: Phylogenetic Implications"; in K. Cambell (ed.). Papers in Avian Paleontology Honoring Pierce Broderick. Contributions in Science. Natural History Museum of Los Angeles County, Los Angeles, Ca. pp. 361-373, 1991.

Moore, D.M. and R.C. Reynolds, Jr. X-Ray Diffraction and the Identification of Clay Minerals. Oxford University Press, New York, 1989.

Solomon, S.E., M.M. Bain, S. Cranstoun, and V. Nascimento. "Hen's egg shell structure and function"; in R.G. Board and R. Fuller (eds.). Microbiology of the Avian Egg. Chapman and Hall, London, pp. 1-24, 1994.

Zhao Zi-Kui. "Dinosaur eggs in China: On the structure and evolution of eggshells"; pp. 184-203 in K. Carpenter, K.F. Hirsch, and J.R. Horner (eds.). Dinosaur Eggs and Babies. Cambridge University Press, Cambridge, 1994.

62

APPENDIX A

PHYLOGENY OF BIRDS SAMPLED

63

Rhea

Ostrich

Emu

Canada Goose

Domestic Chicken

Wild Turkey

Pied-Billed Grebe

Brown Pelican

Sora Rail

Forster's Tern

Blue Heron

Pigeon

Turkey Vulture

Prairie Falcon

Osprey

f •

•

•

•

•

f

•

•

•

•

•

Red-Shouldered Hawk^

Great Horned Owl ^

Belted Kingfisher A

White Necked Raven 0

Figure A.1 Pnylogeny of Birds Sampled

64

APPENDIX B

X-RAY DIFFRACTION TABLES

65

Table B.l X-ray Diffraction results for

Rhea americana

peak

1 2 3 4 5 6 7 8 9

20

23.1 29.45 31.48 36

39.43 43.18 47.15 47.52 48.55

0

11.55 14.725 15.74 18

19.715 21.59 23.575 23.76 24.275

I

290 3840 228 505 740 742 348 1132 950

I obs

7.55 100.00 5.94 13.15 19.27 19.32 9.06 29.48 24.74

Lp

47.001 28.139 24.387 18.218 14.904 12.167 9.976 9.800 9.335

d

3.85 3.03 2.84 2.49 2.29 2.10 1.93 1.91 1.88

Max Intensity 3840

66

peak

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

X-

20

23.05 26.65 27.9 29.41 31.41 35.97 38.38 39.4 43.15 44.55 47.1 47.5 48.47 50.08 26.37 27.38 58.03

Table B. ray Diffraction

0

11.525 13.325 13.95 14.705 15.705 17.985 19.19 19.7

21.575 22.275 23.55 23.75 24.235 25.04 13.185 13.69 29.015

,2 results

Troodon

1

297 170 98

8310 180 510 97 815 785 295 350 1288 1162 80 218 455 138

I obs

0.36 0.20 0.12 10.00 0.22 0.61 0.12 0.98 0.94 0.35 0.42 1.55 1.40 0.10 0.26 0.55 0.17

for

Lp

47.214 34.801 31.577 28.221 24.504 18.251 15.822 14.929 12.186 11.341 10.000 9.810 9.370 8.698 35.587 32.864 6.223

d

3.86 3.34 3.20 3.04 2.85 2.50 2.35 2.29 2.10 2.03 1.93 1.91 1.88 1.82 3.38 3.26 1.59

Max I n t e n s i t y 8310

67

peak

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

X-

20

23.1 26.65 27.95 29.48 30.96 31.45 36.05 36.57 38.4 39.5 43.23 44.6 47.25 47.6 48.6 50.17 50.8 56.6 57.45 58.1

Table B. ray Diffraction

0

11.55 13.325 13.975 14.74 15.48 15.725 18.025 18.285 19.2 19.75 21.615 22.3 23.625 23.8 24.3 25.085 25.4 28.3 28.725 29.05

,3 results

Maiasaura

I

270 215 89

7750 100 182 580 82 179 952 901 210 328 1260 1028 102 102 219 430 120

I obs

3.48 2.77 1.15 100.00 1.29 2.35 7.48 1.06 2.31 12.28 11.63 2.71 4.23 16.26 13.26 1.32 1.32 2.83 5.55 1.55

for

Lp

47.001 34.801 31.457 28.078 25.277 24.437 18.163 17.600 15.804 14.845 12.135 11.312 9.928 9.763 9.313 8.663 8.420 6.584 6.366 6.206

d

3.85 3.34 3.19 3.03 2.89 2.84 2.49 2.46 2.34 2.28 2.09 2.03 1.92 1.91 1.87 1.82 1.80 1.63 1.60 1.59

Max I n t e n s i t y 7750

68

Table B.4 X-Ray Standards for Calcite

d 3.04 2.29 2.10 3.86

I/Il 100 18 18 12

3.86 3.035

2.845 2.495 2.285 2.095 1.927

1.913

1.875 1.626 1.604 1.587

1.525 1.518

1.510 1.473 1.440 1.422

1.356 1.339

12 100 3 14

18 18 5 17 17

4

8 2 5 4

3 2

5 3 1

2

102 104

006 110 113 202 204

108 116 211 212 1010 214 208 119 215 300

0012 217

2010

d A I/Io hkl d A I/Io hkl

1.297 1.284 1.247 1.235 1.1795 1.1538 1.1425 1.1244

1.0613 1.0473 1.0447 1.0352 1.0234 1.0118 0.9895 0.9846 0.9782 0.9767

0.9655

2 1 1 2 3 3 1 <1 1 3 4 2 <1 2 <1 1 1 3 2

218 306 220

1112 21i^ 314 226 2111 2011 404 138

0116,1115 1213

3012 231 322 1011

2111 234

(from JCPDS Card 5-586)

69

Table B.5

X-ray Standard Values for Quartz

d I/Il

3.34 4. .26 1.82 100 35 17

4.26 35

d A

4.26 3.343

2.458 2.282 2.237

2.128 1.980 1.817

1.801 1.672 1.659 1.608 1.541 1.453 1.418 1.382 1.375 1.372

1.288 1.256

I/Io

35

100 12 12

6 9 6 17

<1 7

3 <1

15 3 <1 7 11

9 3 4

hkl

100 101 110 102 111

200 201 112

003 202 103 210 211 113 300 212 203 301 104 302

d A

1.228 1.1997

1.1973 1.1838 1.1802 1.1530 1.1408 1.1144

1.0816 1.0636 1.0477 1.0437

1.0346 1.0149 0.9896 0.9872 0.9781 0.9762 0.9607 0.9285

I/Io

2 5 2 4 4 2 <1 <1 4 1 2 2 2 2 2 2 <1 1 2 <1

hkl

220 213 221 114

310 311 204 303 312 400 105 401 214 223

402,115 313 304 320 321 410

(from JCPDS Card 5-0490)

70

APPENDIX C

X-RAY DIFFRACTION CHARTS

71

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74

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