Citation
Multielement analysis in whole blood using a capacitively coupled microwave plasma atomic emission spectrometer

Material Information

Title:
Multielement analysis in whole blood using a capacitively coupled microwave plasma atomic emission spectrometer
Creator:
Besteman, Arthur David, 1971-
Publication Date:
Language:
English
Physical Description:
ix, 166 leaves : ill. ; 29 cm.

Subjects

Subjects / Keywords:
Atomization ( jstor )
Blood ( jstor )
Electrodes ( jstor )
Lead ( jstor )
Lithium ( jstor )
Microwaves ( jstor )
Plasmas ( jstor )
Signals ( jstor )
Tungsten ( jstor )
Zinc ( jstor )
Atomic emission spectroscopy ( lcsh )
Blood -- Analysis ( lcsh )
Chemistry thesis, Ph.D ( lcsh )
Dissertations, Academic -- Chemistry -- UF ( lcsh )
Trace elements -- Analysis ( lcsh )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph.D.)--University of Florida, 1997.
Bibliography:
Includes bibliographical references (leaves 154-165).
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Arthur David Besteman.

Record Information

Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Resource Identifier:
028623269 ( ALEPH )
39476611 ( OCLC )

Downloads

This item has the following downloads:


Full Text













MULTIELEMENT ANALYSIS IN WHOLE BLOOD
USING A CAPACITIVELY COUPLED MICROWAVE
PLASMA ATOMIC EMISSION SPECTROMETER















By

ARTHUR DAVID BESTEMAN





















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

UNIVERSITY OF FLORIDA

1997
































I would like to dedicate this dissertation to my

parents, Arthur and Audrey Besteman. Their love and support

has meant so much to me. I am very blessed to have them as

my parents.
















ACKNOWLEDGMENTS


I would like to thank Dr. Jim Winefordner for allowing

me to be a member of his group and for teaching me so much

about analytical chemistry. Working for him has truly been

a pleasure. I would also like to thank Dr. Ben Smith for

the great deal of help that he gave me in my research.

The whole Winefordner group has contributed to this

research, whether it be help with the project or help in

making working here a better experience. I would especially

like to thank Bryan Castle for all his help with the

computers and Dr. Kobus Visser for his help in making

modifications to my project. I must also thank Jeanne

Karably for her help with everything.

Over the course of this research project I was

fortunate enough to have three undergraduate assistants,

Don-Yuan Liu, Nancy Lau, and Gail Bryan. They all

contributed a great deal to this project and I appreciate

all their hard work.

I am grateful to the Chemistry Department Machine Shop

for their work in constructing the electrodes. I am also


iii









grateful to the University of Florida Infirmary for drawing

my blood without causing too much pain.

I must thank the Centers for Disease Control and

Prevention for the initial funding of this work. I also

thank Texaco Company and the University of Florida Division

of Sponsored Research for providing my support for the past

three years.

There are also several people I must thank for their

contributions before I entered graduate school. My high

school chemistry teacher, Mr. Roger Bratt, helped cultivate

my interest and appreciation for chemistry. During my

undergraduate education I worked for three summers with Drs.

Mark and Karen Muyskens. Through this experience I learned

much about doing research and how to work independently. I

am very grateful for all that they taught me.

Finally, I must thank my family and friends for all the

support they have given me while I have been so far from

home. I could not have done it without them.




















TABLE OF CONTENTS


ACKNOWLEDGMENTS ....... iii

ABSTRACT .. viii

CHAPTERS

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

2 BACKGROUND .. ... 4


Atomic Emission Spectrometry .
Excitation Sources .
Choice of Emission Lines .
Microwave Plasmas in Atomic Emission .
Capacitively Coupled Microwave Plasma
Microwave Induced Plasma .
Microwave Plasma Torch .
Comparison to the Inductively Coupled
Conclusion .


4
7
. 4
. 7
. 8
. 10
. 12
. 13
. 15
Plasma 16
. 16


3 CLINICAL ELEMENTAL ANALYSIS IN BLOOD .. .19


Introduction .
Medical Significance .
Trace Elements .
Lead .
Manganese .
Lithium .
Zinc .
Magnesium .
Major Elements .
Sodium .
Potassium .
Methods of Analysis .
Lead .
Screening methods .
Clinical methods .
Primary and Trace Elements .
Atomic absorption spectrometry
Atomic emission spectrometry .
Spectrophotometry .

v


. 19
. 20
. 20
. 21
. 24
. 24
. 25
. 26
. 27
. 27
. 27
. 28
. 28
. 28
. 32
. 38
. 39
. 40
. 41










Inductively coupled plasma mass
spectrometry 42
X-ray fluorescence 44
Electrochemical techniques .. .44
Conclusion .. 47

4 EXPERIMENTAL SETUP AND MATERIALS .. .48

Setup .. .48
Microwave Plasma Electronics .. .48
Waveguide .. .50
Torch ... .. .50
Plasma Gases ... .52
Electrode ... .53
Lens Setup ... .54
Detector .. .56
Photodiode array .. .57
Charge coupled device 57
Computer Software ... .60
Materials 61
Aqueous Standards 61
Blood Standards ... .61

5 SAMPLE INTRODUCTION .... 65

Introduction 65
Methods of Sample Introduction into a CMP ... .65
Nebulization .. .66
Thermal Vaporization ... .68
Cup electrode .. .68
Filament electrode .. .72
Hydride Generation .. 74
Development of Electrode for Blood Analysis 75
Cup Holder Electrode ... .75
Platform Electrode ... .79
Suspension Method ... .87
Spiral Filament Electrode ... .89
Conclusion ... .. .93

6 ANALYSIS OF LEAD IN BLOOD .. 94

Introduction .. 94
Optimization of Parameters .. .94
Helium Flow Rate 94
Drying and Ashing Conditions 95
Cleaning ... 98
Sample Size .99
Sources of Noise 100
Analysis ... 100
Aqueous Standards .. 100
Bovine Blood Standards 101
NIST Standards .. 107

vi










Human Blood Standard 107
Blood and Aqueous Standards .. .109
Conclusion .... 114

7 MULTIELEMENT ANALYSIS IN BLOOD 115

Introduction ... 115
Trace Elements ... 117
Zinc .... 117
Lithium ... 118
Magnesium .. 125
Manganese .. 130
Primary Elements ... 130
Sodium ... 130
Potassium ... 134
Comparison to Literature Values .. .138
Conclusion 140

8 CONCLUSIONS AND FUTURE WORK ... 141

Conclusion 141
CMP-AES as a Lead in Blood Screening Method 141
CMP-AES as a Multielement Clinical Technique 141
Future Work 142
Analysis of Other Health Related Elements 143
Using Aqueous Standards for Blood Analysis .145
Commercially Made Filaments .. .146
Simultaneous Multielement Analysis ... .148
Other Biological Fluids .. .149
Plasma ... 149
Serum 150
Urine and spinal fluid .. 150
Miniaturize System .. 151
Acousto-optic tunable filter 151
Miniature detector 152
Atomization Method for Other Techniques 153

LIST OF REFERENCES ... 154

BIOGRAPHICAL SKETCH ....... .166
















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

MULTIELEMENT ANALYSIS IN WHOLE BLOOD
USING A CAPACITIVELY COUPLED MICROWAVE PLASMA
ATOMIC EMISSION SPECTROMETER

By

Arthur David Besteman

December 1997


Chairperson: James D. Winefordner
Major Department: Chemistry

A capacitively coupled microwave plasma atomic emission

spectrometer (CMP-AES) has been evaluated as a clinical

method for the direct analysis of several of the primary and

trace elements in whole blood. A tungsten filament spiral

electrode was used with the CMP, and whole blood samples

were deposited on the electrode and subsequently dried,

ashed, and atomized. The emission was measured with a

spectrometer and either a photo diode array or a charge

coupled device detector. A sample size of only 2 4L was

required and the time for each sample run was under 4

minutes. This method has a wide dynamic range, allowing the

determination of both the primary elements in blood and the

elements present in trace quantities.


viii









Much of the initial work focused on measuring the

levels of lead in blood. A detection limit of 30 ppb for

lead in whole blood was obtained and good accuracy was

obtained in the analysis of whole blood standards from the

National Institute of Standards and Technology.

The research then focused on applying the CMP-AES to

other elements in blood. The elements studied were

potassium, sodium, lithium, magnesium, manganese, and zinc.

Good linearity was obtained for these elements and the

concentration levels obtained for these elements were

consistent with literature values.

The primary advantages of this method are that no

sample pretreatment or dilution is required, it is easy to

run, has a low instrument cost, and is capable of doing

multielement analysis.
















CHAPTER 1
INTRODUCTION





The research project involved developing a capacitively

coupled microwave plasma atomic emission spectrometer (CMP-

AES) as a clinical method for multi-element analysis in

whole blood. Microwave supported plasmas are an excellent

source for atomic emission spectrometry. They produce a

high degree of excitation of atomic and polyatomic species,

have a relatively low cost, and are simple to operate.

CMP's have shown the ability to accomplish direct elemental

analysis in complex matrices [1-3]. Direct analysis is

desirable because it eliminates the use of hazardous

chemicals and the dilution of the sample in trying to

minimize matrix effects [1]. Direct analysis also

eliminates any contamination of the sample or interference

with the plasma that could be introduced by the solvent.

A sample introduction method has been developed that

enables the CMP-AES system to directly determine the

concentration of several elements in whole blood without any

sample dilution or pretreatment. A tungsten electrode is












used which has a spiral loop at the top. The samples of

blood are placed on this loop and dried by inductively

heating the electrode using microwave power. A flow of

helium gas is introduced through a quartz torch that

supports the electrode, and a low power plasma is formed at

the top of the electrode to ash the blood sample. The power

of the plasma is then increased for atomization and

excitation of the sample. The resulting emission is

measured using a spectrometer and either a photodiode array

or a charge coupled device detector. The peak area of the

atomic emission line of the analyte is then compared to an

analytical curve of standards to determine the concentration

of the analyte in the blood.

Initially this research focused on developing a

screening method for lead in whole blood. The design of the

filament was optimized, as well as the conditions for

drying, ashing, and atomizing the sample. All optimizations

were done using lead as the analyte. The method worked well

with whole blood, and gave excellent linearity and good

precision. The accuracy was tested by analyzing blood lead

Standard Reference Materials (SRM's). Good agreement was

obtained with SRM's with concentrations greater than 100

ppb.

The CMP-AES method was then used for the analysis of

several of the medically significant primary and trace











elements in blood. The following elements were chosen for

analysis: sodium, potassium, magnesium, manganese, lithium,

and zinc. For each element an atomic emission line was

chosen that was free from interference and that produced a

linear analytical curve over the concentration range of

interest. The operating conditions had to be modified to

some extent for several of the elements. Analysis was

performed on human blood standards for each element

sequentially by the method of standard additions. The CMP-

AES gave good linearity and precision for these elements.

The determined blood levels for most of the elements studied

were consistent with those found in literature.

In this dissertation, the development of the CMP-AES

for use as a method for elemental analysis in whole blood

will be discussed. A brief overview of atomic emission and

the microwave plasma as an analytical method will be given.

The clinical importance and the methods currently used to

analyze the elements studied will also be presented. The

main portion of the dissertation will discuss the

experimental setup used, the development of the sample

introduction system, and the results of the analysis of the

selected elements in whole blood. The last chapter of the

dissertation will discuss the conclusions made from the

research and the possibilities for future work.
















CHAPTER 2
BACKGROUND


Atomic Emission Spectrometry


Atomic emission spectrometry is a useful method for

elemental analysis. It is very specific, has a wide dynamic

range, and has the capability of measuring many elements

simultaneously. Typically, its disadvantages include poor

sensitivities and serious matrix effects [4].

Atomic emission is the process of an atom being brought

to an excited state. The relaxation of the atom from the

excited state results in the emission of radiation. The

outer shell (valence) electrons are the components of the

atom that are excited. The electrons can be excited to a

number of different levels. The photons emitted from the

electrons as they relax from the different energy levels

have characteristic frequencies (v) giving rise to many

wavelengths for each element. The energy levels of each

element are different which results in a distinct emission

spectrum for each element. The energy (E) associated with

each emitted photon is determined by the product of Planck's

constant (h = 6.63 x 103" Js) and the frequency,












E = hv = hc/X

where c = the speed of light (3.00 x 108 m/s in a vacuum).

Figure 2.1 gives a simple example of the energies associated

with various transitions. The dotted lines represent the

excitation of electrons to two different energy levels, and

the solid lines indicate the various modes of relaxation

with their corresponding energies.

Not all transitions have the same probability of

occurrence. In general, the strongest emission is observed

from transitions which terminate at the ground electronic

level. This is called a resonance transition. If the

condition of thermal equilibrium is maintained, then the

number density (atoms per cm3) of analyte atoms in a given

excited state (nj) can be related to the total number

density of analyte atoms (nt) by the Boltzmann

distribution:


Sneg -E l/kT
Z(T)



The temperature (T) is the absolute temperature (K). E, is

the excitation energy (J) relative to the ground state, and

gi is the statistical weight of state i. Z represents the

electronic partition function:

Z(T) = Y 0 ge-Ei/kT
_j 0 i

















Level 2


Level 1


Ground State


<- E21=hv21=hc&1


<- E2=hv2=hc/X2


<- E =hv1=hc/k


Figure 2-1. Energy diagram for excitation and emission [5].


-











The radiant power of emission (<,) between two states (from

state i to state j) is given by the product of the

population density of the excited atoms (n,), the transition

probability (A j, s ') that an excited atom will undergo the

transition from j to i, the energy of the emitted photon

(hvji), and the volume element observed (V in cm3):

,E = nhv A 1V

This value, as well as the number density of excited atoms,

is proportional to the analyte concentration in the sample.

This relationship is good only for low concentrations. By

measuring the intensity of emission from standards of

various concentrations of the analyte, the exact

relationship between analyte concentration and 0, can be

determined.



Excitation Sources

Many types of excitation sources are used for atomic

emission. Generally the excitation source is also the

atomization source. In atomic emission, the sample must

first be atomized. This is the process of forming free

atoms. When the free atoms are formed, they can then be

collisionally excited to produce the atomic emission lines.

For many years, flames were the most commonly used

atomic emission source because they are simple,

reproducible, and inexpensive. The flames used in atomic










8

emission are formed by the combustion of an oxidant gas and

a fuel gas. There are several disadvantages to using a

flame as an atomic emission source. The energy of the flame

is difficult to control, and it does not generate enough

energy to atomize all the elements or to populate high

excited states of some transitions.

The introduction of plasma sources for atomic emission

spectrometry has significantly improved the detection

limits, accuracy and precision for atomic emission

spectroscopy. A plasma is a partially ionized gas sustained

through an electrical discharge or through a microwave or

radiofrequency field [5-6]. Plasmas are advantageous

because they have a higher temperature and a less reactive

environment than flames. Plasmas also produce a higher

degree of excitation generating more atomic emission lines

for use in analysis. Inductively coupled plasmas (ICP) are

currently the most widely used. Microwave plasmas are also

effective atomic emission sources. Two types of microwave

plasmas are the microwave induced plasma (MIP) and the

capacitively coupled microwave plasma (CMP).



Choice of Emission Lines

The atomic emission lines are spectrally separated by

using an optical dispersion device, typically a grating or a

prism. The emission lines must be chosen carefully for











optimum signal-to-noise (S/N). The most intense line for

the element of interest is not always the best line for

analysis. The spectral line chosen must be free from

spectral interference. Interferences may come from the

emission of the inert gas used, impurities in the gas, other

concomitants in the sample, or the plasma support materials.

For analysis in complex matrices, concomitants in the sample

can be a significant problem. The resolution of the

spectrometer plays an important role in determining how well

the spectral line can be distinguished from nearby spectral

lines.

Another factor in choosing an emission line is self-

absorption. As discussed previously, the emission intensity

is proportional to the number density of the excited atoms.

At high concentrations, the number density of atoms in the

various energy levels can be very high. The atoms present

in the lower energy levels can absorb the energy emitted

from the relaxing excited states. At high number densities

in the lower energy levels, a significant fraction of the

emitted energy can be absorbed instead of being detected as

emission signal. This is a significant problem if a

resonance line is used because the majority of the atoms are

present in the ground state. When self absorption begins to

occur, the slope of a log-log plot of emission intensity vs









10

concentration will deviate from the desired value of one and

approach a limiting value of one half [5]. In conventional

flames, the linear concentration range is often no more than

two orders of magnitude because of self absorption [7].

When analyzing samples of such a high concentration that

self absorption occurs, there are two basic strategies. The

first is to dilute the sample to a concentration where self

absorption does not occur. The second is to choose a weaker

spectral line that gives a linear response over the

concentration range of interest.



Microwave Plasmas in Atomic Emission Spectrometrv


Microwaves are radio waves in the frequency range of

1.0 GHz and upward [8]. Microwaves have been very useful

for applications in radar and communications because of

their high frequency and short wavelength. The high

frequency of microwaves provides wide bandwidth capability.

The wavelength is long enough to penetrate materials, but

short enough to allow microwave energy to be concentrated in

a small area. This feature has been taken advantage of in

microwave ovens [9].

Two methods for transmitting microwave energy from one

point to another are the coaxial cable, and the waveguide.

The coaxial cable consists of two cylindrical conductors









11

separated by a continuous solid dielectric. The microwaves

travel through the dielectric [10]. Coaxial cables are

capable of a large bandwidth and are small in size, but have

the disadvantages of high attenuation and cannot handle high

powers. The waveguide can be either a circular or

rectangular hollow pipe. It is capable of handling high

powers with low loss, but is large in size and only has a

narrow bandwidth.

The first microwave discharge was observed in the

1940's by electrical engineers and physicists working on

radar equipment [11]. It was viewed as a nuisance instead

of a potential technological advancement. In 1951, Cobine

and Wilbur described some of the features of a microwave

plasma [12]. They described the plasma using helium, argon,

air, oxygen, and nitrogen as the support gases.

In 1958, Broida and Chapman used a microwave-induced plasma

(MIP) to analyze nitrogen isotopes [13]. Kessler and

Gebhardt used a capacitively coupled microwave plasma (CMP)

to analyze limestone in 1967 [14]. Mavrodineanu and Hughes

used a microwave plasma torch in 1967 to view the emission

spectra of several elements by introducing solutions into

the crater of a graphite discharge tip [15]. Fallgatter et

al., examined an argon microwave plasma as an excitation

source for atomic emission spectrometry in 1971 [16]. The












development of microwave plasmas has grown over the years

because of their high excitation efficiency for both

metallic and non-metallic elements, their low background

emission, and their low cost [17]. In recent years,

microwave plasmas have been applied to many different

analytical applications including analysis of solids,

biological fluids, and oil [1-3]. Several authors have

written extensive reviews of the use of microwave plasmas in

spectrochemical analysis [17-22].



Capacitively Coupled Microwave Plasma (CMP)

For a CMP, a magnetron (microwave power tube) generates

the microwaves which are conducted through a coaxial wave

guide. Within the waveguide, a standing wave is produced

which builds up microwave energy that is transferred to the

tip of a central single electrode. By oscillating in the

microwave field, the electrons gain enough kinetic energy to

collisionally ionize the support gas. This produces a

flame-like plasma at the tip of the electrode. The plasma

that is produced is capable of atomizing and exciting the

analyte in a sample. The signal is measured by focusing the

emission on the entrance slit of a spectrometer. The

multielement emission is usually measured with a photodiode

array (PDA) or a charge coupled device (CCD).










13

Several parameters must be optimized in order to obtain

satisfactory results with a CMP. These parameters include

the microwave power, the plasma gas flow rate, and the

position of the electrode with respect to the detector.

Optimum microwave powers differ depending on the type of

samples and the method of sample introduction. Helium is

used most often as the support gas with flow rates ranging

from 3 to 10 L/min [23].

Spencer et al. studied various parameters for a high flow

rate (>6 L/min) CMP [24]. The temperature measurements were

made with the following plasma conditions: 10 L/min helium,

150 cm3/min hydrogen and 700 W of applied power. The

following results were obtained for the analysis of aqueous

solutions: excitation temperature = 3430 K; and electron

number density = 4.4 x 1014 cm3. They determined that the

values of Tec and n. are not statistically different for the

introduction of aqueous and organic solutions into the

plasma.



Microwave Induced Plasma (MIP)

Microwave induced plasmas (MIP) are created by using an

external resonant cavity or some other structure to couple

microwave energy to a stream of gas in a quartz tube. MIP's

are sustained at low powers (25 to 200 W) with argon or









14

helium as the support gas [18]. A microwave power supply is

attached to an antenna or circuit loop by a coaxial cable.

The energy goes through the antenna or loop and is

introduced into the resonant cavity generating a standing

wave. A quartz tube is placed in the cavity in such a way

that its axis is parallel to the line of electric field

oscillation. MIP's that use an electrothermal type of

atomizer have resulted in the best detection limits [18].

Microwave induced plasmas are more widely used than

capacitively coupled microwave plasmas because MIP's require

lower power and can be operated at atmospheric pressure. In

addition, CMP's involve the use of an electrode which can

cause spectroscopic contamination and memory effects if it

erodes [23]. However, CMP's do have several advantages over

MIP's. MIP's can only be operated at low powers while CMP's

are stable over a wide range of power levels (50-2000 W).

At higher powers, there are fewer matrix effects and more

intense signals. Also, a wide range of gases can be used to

sustain CMP's and CMP's are more tolerant to the

introduction of foreign materials than MIP's [25]. Sample

introduction problems have hindered the development of

commercial MIP instruments [5]. Memory effects are also a

problem in MIP atomic emission spectroscopy [18]. The

memory effects are probably a result of etching of the

quartz tube by the plasma providing a region where analyte









15

atoms can collect. An MIP is most useful as an excitation

source when it is combined with a separate sample atomizer.



Microwave Plasma Torch

Jin et al. developed a new type of microwave plasma

called the microwave plasma torch (MPT) [26-32]. A MPT

contains three concentric tubes, with the outer tube made of

brass and the inner tubes made of copper. The outer tube

serves as the microwave cavity which couples the microwave

energy to the torch forming a plasma at the top of the

torch. The carrier gas containing the sample aerosol enters

the inner tube and the plasma gas (helium or argon) flows

through the middle tube. This microwave plasma is very

stable and has a high tolerance to the introduction of

foreign materials [30]. The linear dynamic range for the

MPT was generally more than three orders of magnitude and

the detection limits for 15 rare earth elements were in the

part-per-billion (ppb) range [32]. This is a significant

advancement over the MIP because the MPT can withstand the

introduction of wet aerosols. Solutions are nebulized by an

ultrasonic nebulizer and the resulting aerosol is introduced

through a desolvation-dessicator system. The MPT does

however suffer from matrix effects and air entrainment in

the torch.












Comparison to the Inductively Coupled Plasma (ICP)

The inductively coupled plasma (ICP) is widely used in

industry and research. The ICP has a somewhat higher

temperature than the microwave plasma and produces a high

degree of excitation. The ICP consists of several

components. A gas, typically argon, flows through a torch

made out of three concentric quartz tubes. The top of the

torch is immersed in a high energy induction coil which

carries radiofrequency power (at 27 or 40 MHz) in the range

of one to three kilowatts. This causes the oscillation of

the argon atoms, and the high energy collisions that result

produce a plasma at the top of the torch with a temperature

more than 6000 K [6,33]. The sample is generally introduced

by nebulization [34]. A fine mist of sample is generated by

pumping the sample through a pneumatic nebulizer and spray

chamber.



Conclusion


Atomic emission spectrometry is a very selective

analytical method that can be used for many types of

samples. Plasma sources have further increased the

usefulness of atomic emission spectrometry. Table 2-1 shows

a comparison of the plasma sources discussed. Although the

ICP and the MIP are currently in wider use than the CMP, the










17

CMP is better able to analyze complex matrices. This

feature of the CMP can be used for direct elemental analysis

in blood.












Table 2-1. Comparison of inductively coupled plasma (ICP),
capacitively coupled microwave plasma (CMP),
microwave induced plasma (ICP) and microwave
plasma torch (MPT) for atomic emission
spectrometry [21].




ICP CMP MIP MPT



Argon Argon
Gas Argon Helium or or
Helium Helium




Power (W) 500-1500 70-1000 10-150 40-500




Gas
temperature 2000-6000 2000-3500 500-2000 1000-6000
(K)



Relative
standard 0.5-2% 2-10% 0.5-2% 1-5%
deviation



Linear
dynamic ~105 ~104 ~103 -104
range



Limit of
detection 0.1-100 0.1-1000 0.1-100 0.1-100
(ppb)















CHAPTER 3
CLINICAL ELEMENTAL ANALYSIS IN BLOOD


Introduction


The human body requires a delicate balance of the

levels of various elements. Too much or too little of a

particular element can have devastating physiological

effects. Some typical ailments are a result of an imbalance

of elements in the body. High levels of sodium and low

levels of potassium, magnesium, and calcium all lead to

hypertension (high blood pressure) [35]. Hypertension is

the most common disease in industrialized societies and

contributes to the development of cardiovascular disease,

stroke, and renal failure [35]. The reduction of the levels

of certain elements caused by medical treatment with some

drugs can also cause serious problems [36].

Elements are transported by the blood and taken up in

varying amounts by organs and tissues [4]. The significance

of the levels of various elements in health makes it

important to have readily available techniques to monitor

these elements. The biological importance of each element












studied during the course of this research and the methods

used to measure them will be discussed.



Medical Significance


Trace Elements

An element is classified as a trace element if the

concentration is below 250 ppm [37]. Trace elements can be

classified into two groups, essential and nonessential. An

element is considered essential if lack of that element

causes problems. Essential trace elements include

manganese, copper, zinc, tin, and nickel. Nonessential

elements are those that are present in biological organisms

but have not been determined to play an important role [4].

The role of trace elements in the body has received

much attention by the scientific community. Although they

are present in low concentrations, they can play essential

roles in biological functions, and can also be detrimental

to biological activity if present in too great an amount

[14]. Trace elements are very important in the structure of

enzymes and are needed in the production of proteins. Trace

elements are also essential for the normal growth and

development of the human skeleton [36].

The metabolism of certain trace elements is involved in

various diseases. Therefore, the measurement of the









21

concentration of trace elements in biological fluids can be

used as a test for certain diseases. Poor health can also

be caused by environmental exposure to some elements. The

proper levels of trace elements are especially important

during pregnancy to insure a healthy child [36], and in the

elderly for their immune response [38]. Trace element

losses must be monitored closely in patients receiving

radiation therapy or chemotherapy. These patients may

require additional supplements of certain elements to

compensate for losses due to significant weight loss from

their illness or treatment [39].

Lead

Lead (Pb) poisoning is the leading environmental threat

to children in the United States [40-41]. The primary

sources of lead exposure are lead based paints and lead-

contaminated dust and soils. The Department of Housing and

Urban Development estimates that 4 million homes containing

young children have lead-based paint hazards [42]. Children

can also be exposed to lead though air, water, and food.

Lead poisoning affects virtually every system in the

body. It is especially harmful to the developing brain and

nervous system of unborn and young children [40, 43]. Lead

causes health problems because the body is unable to

distinguish between lead and calcium. When a person

consumes lead it is assimilated into the blood stream the











same way calcium is. Young children and pregnant women

absorb calcium more efficiently to meet their added

requirement so they are particularly at risk. Typically,

adults absorb 10 to 15 percent of the lead that reaches

their digestive tract. Pregnant women and young children

can absorb as much as 50% of the lead [44].

In blood, 94% of the lead is bound to the hemoglobin.

Within the past five years, it has been found that lead

concentrations as low as 100 ppb in the blood can be

detrimental to the health and intellectual development of a

child [40, 45]. Figure 3-1 shows the health effects of

various levels in the blood [40]. Acute lead poisoning can

result in anorexia, dyspepsia and constipation followed by

abdominal pain [46]. The detrimental effect of lead

poisoning on young children has led the Centers for Disease

Control and Prevention (CDC) to lower the acceptable level

of lead concentrations in the blood of children to 100 ppb,

compared to a level of 250 ppb considered acceptable from

1985 to 1991. The symptoms of lead poisoning are often

invisible at first, preventing the diagnosis and treatment

of most cases. The number of lead poisoning cases can be

greatly reduced if a large scale screening program is

implemented. This would require an inexpensive, easy-to-use

method to detect trace amounts of lead in blood.










Concentration
of lead in blood
(ppb)


Health effect in
humans


(Children)


1000 Brain and kidney damage (adults)


Brain and kidney damage (children)


Increased blood pressure
(middle-aged men)
200
Decreased IQ and growth in
young children

Pre-term birth, reduced birth weight,
and decreased mental ability in
infants from mother's exposure during
100 pregnancy



Figure 3-1. Health effects of lead poisoning [40].












Manaanese

Manganese (Mn) is a important as a constituent of

metalloenzymes and as an enzyme activator [37, 47].

Research with animals has shown that Mn deficiency can lead

to impaired growth, skeletal abnormalities, disturbed

reproductive function, and problems with lipid and

carbohydrate metabolism. A deficiency of manganese leads to

a decreased level of blood clotting proteins and has also

been observed in several diseases including epilepsy [47-

48].

Toxic levels of manganese can be the result of chronic

inhalation of airborne particulates containing high

concentrations of Mn from mines, steel mills, or some

chemical industries. Patients with liver disease are also

at risk from Mn toxicity because their liver may not

adequately clear the Mn absorbed from a normal diet. The

main signs of Mn toxicity include depressed growth and

appetite, impaired iron metabolism, and altered brain

function. Severe psychiatric abnormalities including

hyperirritability, violent acts, and hallucinations can be

caused by Mn toxicity [37].

Lithium

Lithium (Li) is used in the treatment of manic

depressive psychosis [49]. Lithium is administered in the

form of lithium carbonate or another lithium salt with as











much as 1800 mg taken daily [50]. Blood normally only

contains lithium at a level of low ppb, but for therapeutic

lithium levels, a range of 0.5-1.5 mM is maintained in the

blood [51]. This is close to the toxic level, and a level

of 5 mM can be lethal. This necessitates the monitoring of

lithium levels in patients receiving this type of treatment.

Zinc

Zinc (Zn) is the second most plentiful trace element in

the body. Zinc is important in the metabolic functions of

the body and is essential for the production and functioning

of over 40 enzymes that contain zinc [36]. Zinc is also

vital in the synthesis of DNA and RNA in every living cell.

Zinc plays a role in immune functions, in growth and

development, and in the synthesis and release of

testosterone. Zinc is especially important in expectant

mothers and in the growth of young children [52-53].

Zinc plays a major role in fighting infections and in

the healing process [47]. Those at risk for zinc deficiency

include women of child bearing age, young children, and the

elderly [54]. If the zinc level is too low it can cause

congenital malformations, including spina bifida and central

nervous system abnormalities. It can also cause severe

growth retardation, arrested sexual maturity and a loss of

appetite [36]. The level of zinc is especially critical in

the elderly because of the deterioration of immune function











with age. Low zinc levels can indicate diabetes because

zinc is important in the storage and release of insulin. A

zinc imbalance may be involved in hypertension.

Most cases of zinc toxicity have been related to food

poisoning incidents and to industrial pollution [53]. Too

much zinc causes anemia (reduced hemoglobin production),

elevated white blood cell count, muscular problems,

exhaustion, diarrhea, nausea and dizziness [52-53]. Very

high levels of zinc can impair metabolic functions that are

dependent on other trace elements [54]. High levels of zinc

can also interfere with the absorption of copper which can

provoke iron deficiency and anemia [47].

Maanesium

Magnesium (Mg) is essential in the transfer, storage,

and utilization of energy. Mg regulates and catalyzes over

300 enzyme systems in mammals [55-56]. Mg also maintains

the cardiovascular system, regulates DNA and RNA synthesis

and structure, and is important in cell growth,

reproduction, and membrane structure. Mg controls many

processes in the body including neuronal activity,

neuromuscular transmission, cardiac excitability, muscular

contraction, blood pressure, and peripheral blood flow [47,

55]

A deficiency of Mg promotes hyper coagulability of

blood, atherogenesis, vasoconstriction, cardiac arrhythmias









27

and also damage to the cardiac muscles. A Mg deficiency may

also be related to cardiovascular disease, hypertension,

diabetes, depression, and atherosclerosis [35, 52].



Major Elements

Sodium

Sodium is the principal cation of the extracellular

fluid. It is essential in maintaining the pH balance of the

fluid and is also important in nerve transmissions and

muscle contraction. Sodium levels can be depleted by

vomiting, diarrhea, or heavy sweating. If depletion occurs

it is critical to take measures to bring the sodium level

back up to a healthy level. If the sodium level is too high

it can result in hypertension, kidney disease, or heart

disease [47].

Potassium

Potassium is important in the body in its maintenance

of fluid and electrolyte balance and cell integrity.

Diabetic acidosis, dehydration, or prolonged vomiting or

diarrhea can cause low potassium levels. Symptoms of low

potassium levels are muscular weakness, paralysis, and

mental confusion. Too much potassium can also cause

muscular weakness, confusion, as well as numbness, slowed

heart rate, vomiting, and eventually cardiac arrest [47].












Methods of Analysis



Lead

The Centers for Disease Control and Prevention has set

forth a number of desirable characteristics for an improved

blood lead measurement system. These characteristics

include an accuracy and precision of 10 ppb at 100 ppb, a

detection limit of 10-20 ppb, a sample volume of less than

200 yL, a low cost-per-test, an analysis time under five

minutes, portability, and minimal operator training required

to perform the method.

Screening methods

Currently used screening methods for lead in blood

which measure the level of either erythrocyte protoporphyrin

(EP) [57] or zinc protoporphyrin [45] in blood as an

indication of lead poisoning are not sensitive enough to

measure blood lead levels below 250 ppb. The EP test is

based on the increase in the amount of EP caused by an

increase in Pb. Porphyrins are the metabolic intermediates

in the biosynthetic process that produces heme [52]. Lead

impairs heme synthesis, preventing the incorporation of iron

into the protoporphyrin. This allows free protoporphyrin to

chelate cytosolic zinc. The amount of free protoporphyrin

can be measured because it fluoresces deep red [58]. The

whole blood is diluted and matrix modifiers are added. The









29

porphyrins are then separated from the blood and measured by

molecular fluorometry. This test has been recommended by

the CDC since 1978 [57]. Hematofluorometers have also been

used to screen children for lead [59]. These are portable

instruments that measure the zinc protoporphyrin directly in

a single drop of blood.

Two current methods being developed as portable

screening methods are anodic stripping voltammetry (ASV)

[60-65] and potentiometric stripping analysis (PSA)[66-67].

In anodic stripping voltammetry, a decomplexing agent is

added to the blood sample to free up the lead for

electrolysis. The Pb is reduced at a controlled potential

causing it to plate out on the surface of a mercury

electrode. A voltage sweep of the electrode releases the

lead and produces a current between the working and

reference electrode. By measuring this current, the amount

of lead can be determined [64]. This method has the

problems of instrument instability, slow speed, and

variations in response due to other elements present in the

blood. ASV also requires a plating solution. The use of

ASV with microelectrode arrays and indium as an internal

standard has improved the detection limit and precision for

the analysis of lead in blood [61].

In potentiometric stripping analysis, the lead analyte

is preconcentrated in a mercury film on a glassy carbon









30

electrode. This occurs by potentiostatic deposition where

electrons are added to the metal. The stripping step is

then achieved chemically by adding an oxidant. During the

stripping, the potential of the working electrode as a

function of time is closely monitored. This will produce a

well-defined stripping plateau which can be used for the

analysis of lead. Whole blood has to be diluted by a factor

of ten for analysis by the method of standard additions

[67]. The total time for analysis is about 5 minutes.

Both ASV and PSA possess the required accuracy and

precision to detect low blood lead levels. Electro-chemical

methods are advantageous as a screening method because they

are both portable and inexpensive; however, they have the

disadvantage that they require the use of reagents and

sample pretreatment when analyzing whole blood.

Exeter Analytical (North Chelmsford, MA) has developed

a commercial atomic absorption spectrometry (AAS) instrument

that can be used for blood lead screening [68]. The lead

absorption line at 283.31 nm is used with near line

background correction using the non-absorbing 287.33 nm lead

line. This instrument used a 150 W tungsten coil filament

in an enclosed chamber. Tungsten coils are excellent

atomization sources because of their high heating rate and

their commercial availability. Tungsten coils that are made

for halogen projector lamps can be used so they are









31

relatively inexpensive. One coil can last for approximately

70 runs. The blood samples were diluted by a factor of ten

with 0.2 % nitric acid, 0.5% Triton x-100, and 0.2% NH4H2PO4.

Calibration is done with aqueous standards, and a detection

limit of 30 ppb with a RSD of 9.0% at 100 ppb is obtained.

This method produces results in less than 3 minutes, has a

low cost-per-test, and is easy to operate [68].

Recently, a portable, battery powered AAS was developed

by Jones and coworkers for lead in blood screening [69]. A

tungsten coil was used as the atomizer and a miniature fiber

optic spectrometer with a charge coupled device (CCD)

mounted on a input card of a personal computer was used as

the detector. The blood samples were digested in nitric

acid by microwave heating and then diluted with distilled

deionized water. A 20 pL sample was placed on the coil and

then dried for 2 minutes at 3.0 A and then atomized at a

current of 6.0 A. The absorption signal was collected using

a hollow cathode lamp and a fiber optic. The spectrometer

and multichannel detector allowed near-line background

correction technique to be used. The lead absorption line

at 283.3 nm was used for analysis and the average of the

nonabsorbing lead lines at 280.2 and 287.3 nm was used for

background correction. The total cost of this entire system

was below $6000. A detection limit of 1 ppb for lead was

determined. The linear dynamic range was 2 orders of









32

magnitude and the precision was 5%. The method was proven to

be accurate by analyzing NIST blood standards. The coil was

used in the analysis of up to 400 samples [69].

Clinical methods

Research is being done by many different government

agencies and universities to improve blood lead measurement.

Isotope dilution inductively coupled mass spectrometry (ID-

ICP-MS) [70] and graphite furnace atomic absorption

spectrometry (GFAAS) [71-72] are methods that are able to

detect trace amounts of lead in blood below the level of

concern (100 ppb). Both of these methods are very accurate

and precise, but have the disadvantages of requiring sample

pretreatment and expensive instrumentation. The expense of

testing is a major consideration since millions of children

would need to be tested in a large-scale public health

screening program.

Atomic absorption spectrometry (AAS). Graphite furnace

atomic absorption spectrometry (GFAAS) is one of the most

popular methods for lead in blood analysis [71-90]. GFAAS

has excellent sensitivity and selectivity, large throughput,

and is capable of analyzing very small volumes. Many GFAAS

methods use a L'vov platform which is a small platform

placed in the graphite tube to hold the sample and ensure

that the tube and sample come to the same temperature at the

same time. In 1991, the Centers for Disease Control (CDC)










33

surveyed the methods being used by clinical laboratories for

blood lead analysis. Of the laboratories surveyed, 61% used

GFAAS, 5% of the labs used Delves cup AAS, 7% used

extraction AAS, 1% used carbon rod AAS, and 26% used ASV

[81].

The methods used to analyze lead in blood by GFAAS

include: direct introduction of blood into the furnace;

dilution with either water, Triton X-100, or acid;

deproteinization with nitric acid; matrix modification;

solvent extraction; or a combination of several methods

[82]. The direct injection of blood samples into a graphite

furnace has many problems associated with it. The blood can

seep into the graphite and produce major memory effects [83-

84], and during drying and atomization, the blood residue

can cloud the viewing windows [85]. Also, a carbonaceous

residue from the proteins in the blood builds up in the

furnace and is unable to be vaporized even at high

temperatures [76, 83]. Diluting the blood samples with

water alone is not sufficient to reduce adequately the

amount of carbonaceous residue [86]. The presence of water

in the blood sample also gives rise to a slow precipitation

of the red cell membranes, reducing the homogeneity of the

sample [87]. Diluting the blood samples with a 0.5 to 2%

solution of Triton X-100, a surfactant, causes complete









34

lysis of the blood cells and produces a clear solution that

minimizes the negative effects of the blood matrix [88].

The problem of carbonaceous residue build up can be

virtually eliminated by deproteinization of the blood with

30-50% nitric acid. The supernatant of the resulting sample

can then be injected into the graphite tube. This procedure

destroys the bulk of the organic matter in the blood.

However, the use of nitric acid shortens the life of the

graphite tube because of the oxidation of the tube's

pyrolytic coating [89]. The blood could be deproteinized at

lower concentrations of acid, but the inorganic salts

present were removed, necessitating the use of standard

additions [90].

Adding matrix modifiers to the blood can help in

retaining the analyte while volatilizing away most of the

matrix. The most common matrix modifiers used in blood lead

analysis are diammonium hydrogen phosphate, ammonium

dihydrogenphosphate, and phosphoric acid [75, 82]. By

adding these matrix modifiers, higher furnace temperatures

can be used to ash away the matrix without significant loss

of the analyte. The method of solvent extraction can also

minimize matrix effects, but it is very tedious, prone to

contamination, and does not completely remove interference

[91-92].









35

A GFAAS method has been developed which allows aqueous

standards to be used for blood lead analysis [71]. Prior to

analysis, the blood is deproteinized with a 5% nitric acid

solution containing 0.1% Triton X-100. The supernatant is

collected and the concentration of lead is measured using

Zeeman GFAAS. Parsons and coworkers have also developed a

method capable of calibrating with aqueous standards [45,

75]. A transversely heated graphite tube/platform called a

stabilized temperature platform furnace (STPF) was used.

This method produced a nearly isothermal system which

reduced the time of analysis, increased the precision, and

eliminated many of the chemical and matrix interference.

Blood samples preserved in EDTA were diluted by a factor of

10 with a solution containing ammonium dihydrogen phosphate,

triton X-100 and nitric acid. The samples were directly

introduced into an autosampler where the mixing with the

solution occurs. Twelve micro-liter aliquots were injected

into the furnace and atomized. Each analysis took 90 s, and

the system was able to run approximately 100 samples per day

with duplicate injection. The precision was better than 5%.

While both of these methods are advantageous because aqueous

standards can be used for calibration, they have the

disadvantage of requiring appreciable sample treatment.

A flame AAS method has been developed that used 20 yL

of blood samples spotted on filter paper and then analyzed











in a Delves cup [93]. A Delves cup is a small nickel cup

that is positioned in the flame for analysis. The blood

sample must be allowed to dry on the filter paper and is

then ashed. The ashing step burned away the paper and then

the sample was introduced into the flame to be analyzed for

lead by measuring the absorption at a wavelength of 283.3

nm. The entire analysis time was 15 s per sample and a

limit of quantitation of 40 ppb was obtained. This method

gave excellent reproducibility and accuracy [93]. It has

the disadvantage that there was considerable variability in

the adsorptiveness of the papers which was detrimental to

the accuracy. Also, this method's requirement of allowing

the blood to dry on the filter paper resulted in the sample

being susceptible to contamination from airborne particles.

As a clinical method, flame AAS has the disadvantage that

the equipment is expensive and cumbersome and requires a

combustible gas source.

Inductively coupled plasma atomic emission spectrometry

(ICP-AES). A carbon rod atomizer has been used to analyze

blood samples with a ICP atomic emission spectrometer [94].

Blood samples were diluted by a factor of five with

distilled water. The samples were placed on the carbon rod

atomizer and then dried and volatilized. The resulting

vapor was carried into the plasma by the plasma gas. This

method of sample introduction was more efficient than











nebulization. An aqueous detection limit of 7 ppb was

reported for lead with a relative standard deviation (RSD)

of 0.2%.

Inductively coupled plasma mass spectrometry (ICP-MS).

ICP mass spectrometry is a very sensitive method for the

measurement of lead in blood [70, 95-96]. The main method

of sample introduction in an ICP-MS is a nebulizer. Aqueous

samples are transferred to a nebulizer by a peristaltic

pump. The aerosol produced by the nebulizer is carried to

the plasma by a flow of gas, typically argon. The high

temperature of the plasma vaporizes and ionizes the sample

and the ions are then detected in a mass spectrometer

according to their mass to charge ratio [97]. ICP-MS with

isotope dilution, is the method with lowest bias for

determining lead in whole blood and serum [70, 95]. Isotope

dilution mass spectrometry involves measuring the change in

the relative abundance of two isotopes of an analyte after

adding a known amount of one of the isotopes to the sample.

The CDC uses isotope dilution (ID) ICP-MS for the analysis

of its certified reference material, lead in bovine blood,

from its Blood Lead Laboratory Reference System. An aliquot

of the whole blood sample is spiked with a radiogenic lead

isotopic standard. This aliquot along with an unspiked

aliquot is then digested with ultrapure nitric acid in a

microwave oven. After cooling, both samples are diluted and











then aspirated into an ICP-MS. The isotope ratios of lead

at mass 206 and mass 208 are then measured. While this

method is very accurate and precise for determining lead in

blood, it is more suitable for determining reference values

than being used as a clinical method because of it's high

cost and low throughput (10 samples per day) [70, 95].



Primary and Trace Elements

The main methods for trace elemental analysis in the

clinical laboratory are absorption or emission spectro-

photometry. Typically, the blood is separated, and the

plasma or serum is used for analysis [4]. Methods capable

of performing trace elemental analysis include AAS, ICP-AES,

and ICP-MS. Other methods include electrochemical, neutron

activation, flame atomic fluorescence spectrometry,

molecular absorption spectrometry, X-ray fluorescence,

particle-induced X-ray emission and radiochemical techniques

[46]. However, many of these methods are not suitable for

routine use in a clinical setting. Neutron activation, for

example, is a very sensitive technique but requires the use

of a nuclear reactor and requires a very long time for

analysis [98]. Currently, AAS is the most widely used

method in clinical laboratories, usually employing

electrothermal sample introduction [46]. Recent reviews of

clinical methods of analysis have appeared in Analytical











Chemistry [99] and in the Journal of Analytical Atomic

Spectrometry [100].

Atomic absorption spectrometry (AAS)

Sodium, potassium, zinc, magnesium, and iron blood

levels can be determined by flame atomic absorption

spectrophotometry (FAAS) [47, 101]. The samples are diluted

and introduced into the flame. The analysis of each element

requires a hollow cathode lamp that produces light at a

wavelength specific for that element. The fraction of

absorbed light is used to determine the concentration of the

element present. Shang and Hong have used a microvolume

injection technique to measure the levels of Cu, Zn, Ca, Mg,

and Fe by FAAS [102]. The blood samples were treated with

triton x-100 and then diluted with a mixture of 0.18 M HC1,

0.003 M La203, and 0.013 M KC1. The injection volume used

was 10 pL. Atomic absorption has greater sensitivity than

either flame atomic emission spectrometry (FAES) or ion

selective electrodes (ISE), but it is less precise and not

as suitable for routine clinical analysis. It has a high

initial cost and the necessity for compressed gases and

flames are undesirable in the clinical laboratory.

GFAAS is a very popular method for elemental analysis

in blood. The various methods used for lead analysis are

also used for many other elements and have the same










40

advantages and disadvantages [90]. The levels of magnesium,

manganese, lithium and iron have all been determined by

GFAAS [47, 50, 52]. GFAAS has achieved a detection limit of

2 ppb for manganese in blood and is the most common method

for analysis of lithium in blood [50, 103]. The main

disadvantage of GFAAS as a clinical technique is its

limitation as a single element technique. Some researchers

have developed complex methods of determining two or three

elements simultaneously, but it is difficult and expensive,

requiring a complicated optical setup [74].

Atomic emission spectrometry (AES)

Sodium and potassium in serum are usually analyzed by

either flame atomic emission spectrometry (FAES) or by ion-

selective electrode potentiometry (ISE) [101]. FAES

requires a dilution of the sample by 100 to 200 times, often

adding lithium or cesium to the sample as an internal

standard and ionization suppressant. An air-propane flame

is used, and the sodium emission is monitored at 589 nm and

the potassium emission at 766 nm. Only 1 to 5% of the atoms

in the flame are excited to emission, but the concentration

of the elements is sufficient for accurate and precise

measurements [101]. Lithium levels can also be reliably

measured using flame emission spectrometry [104].

Flame photometric flow-injection analysis has been

successfully used to simultaneously measure the levels of











lithium, sodium and potassium in blood serum [105]. The

serum samples were diluted ten-fold with doubly-distilled

deionized water. The sample was then injected and split into

three portions so that each portion reached the detector at

a different time. Between the analysis of each sample

portion, the filter on the detector was changed to be

specific for each analyte. This method allowed the analysis

of 108 samples per hour [105].

ICP-AES has been used to measure the levels of Fe, K,

Mg, Na, Li and Zn in human serum and blood [106-108]. Serum

samples were digested in nitric acid or diluted with

deionized water. A microsampling system has been developed

for ICP-AES which uses <0.1 mL of sample [107]. By

digesting the blood or serum sample with acid, aqueous

analytical curves could be used for calibration.

SDectroohotometrv

Spectrophotometry involves selectively completing and

separating an analyte using either an inorganic or organic

colorimetric reagent. Various organic reagents have been

used as spectrophotometric agents for the analysis of

lithium, magnesium, and iron in blood and serum [51-52].

Calmagite, methylthymol blue and formazam dye, are some

examples of chromophores that have been used for the

analysis of magnesium. The level of iron in blood is

analyzed by exposing the blood sample to strong acids to









42

dissociate the iron from its binding proteins. A chromogen

is then added to the sample to produce a iron chromogen

complex that has an absorbance maximum in the visible

region. The concentration of lithium in serum can be

measured by observing shifts in the spectrum of a reagent

caused by the presence of lithium. The reagents must be

very specific for lithium because sodium, which is present

at high concentrations in blood, is generally an

interferent. Crown ethers can be used for lithium analysis.

By using different cage sizes, conformational flexibility,

and various side groups, crown ethers can be made to form a

complex selectively with the several analytes of interest.

The complex formed can be extracted into an organic solvent

with an anionic reagent that is colored allowing

spectrophotometric analysis [51].

A major disadvantage of spectrophotometry is the

limited selectivity due to overlapping absorption bands. It

is, however, easy to use, rapid, and can be readily

automated [4].

Inductively coupled plasma mass spectrometry (ICP-MS)

ICP-MS has been used for the measurement of trace

elements in whole blood and serum [33, 109-112]. The

advantages of using ICP-MS include high throughput (40

samples/hour), possibility of simultaneous analysis, and

good detection limits. Over 50 elements have detection











limits in the range of 0.01 to 0.1 ppb [33]. Adding an

internal standard can often correct for matrix effects and

instrument drift.

Blood and serum samples for ICP-MS are usually digested

with acid or diluted. The sample pretreatment often

includes a separation step. The amount of time needed for

sample preparation has been reported as 25 minutes for 50

specimens [33]. Barany and Bergdahl reported on a method

for ICP-MS of trace analysis in blood where whole blood was

diluted 50 to 100 times with an alkaline solution. Each

analysis required only 75 seconds. Even with dilution, some

problems were encountered with the buildup of denatured

proteins from the blood so the torch required occasional

cleaning. This method was used for the determination of 7

trace elements in blood. It was not suitable however for

Mn, Se, Hg, or Cr [113].

The major disadvantage of using ICP-MS is the high cost

of the instrument and the operator expertise needed. Also,

the analysis of lighter elements is difficult because of

more interference. Interferences arise from mass overlap

from either polyatomic ions, doubly charged ions, or

elements with the same isotopic masses. Currently, it is

not possible to analyze chromium, manganese, or iron by ICP-

MS in biological samples due to the presence of

interference [33, 109-110, 113].












X-ray fluorescence

X-ray spectrometry involves bombarding the sample with

radiation of distinct energy. This removes electrons from

the inner shells forming atoms in an excited state. The

electrons from the outer shells fall into the shells vacated

by the removed electrons according to specific transition

rules. The radiation emitted by this process is very

characteristic. The method of x-ray fluorescence can be

used for simultaneous multielement analysis on a very small

sample of blood (2-3 pL) without destroying the sample [114-

115]. The blood levels of potassium, calcium, chromium,

iron, nickel, zinc, selenium and lead can all be determined

in one measurement. Detection limits ranged from 21 ppm for

phosphorus to 30 ppb for lead in blood [114-116]. The

method of X-ray fluorescence has the disadvantage that it is

very difficult to match the composition of the calibration

standards to the matrix of the sample [4].

Electrochemical techniques

Voltammetry, an electrochemical method, is also capable

of measuring trace elements in blood. In voltammetry, the

measurements are based on the potential-current behavior of

a small electrode that is easily polarized [4]. Voltage is

applied to a microelectrode and the diffusion current is

measured as a function of the voltage. This allows both

quantitative and qualitative analysis of the trace element.











For this method, it is necessary to digest completely the

samples prior to analysis [4].

Ion selective electrodes (ISE) are capable of

determining the level of potassium, sodium, magnesium and

lithium in blood or serum by measuring the potentiometric

charge as a function of ion concentration [51, 55, 117-120].

The membranes of ISE's are ideally sensitive to only one

ion. Most membranes, however, respond to ions other than

the one for which they are designed. Polymer-bound liquid

membranes use a membrane that contains a sensing material

dissolved in the polymer support matrix. If the sensing

material is neutral in charge, then it must complex with the

analyte in some way to transfer it across the membrane or it

must be able to facilitate ion exchange. Neutral sensing

materials are called ionophores and are often some type of

crown ether. Crown ethers can be made in such a way that

they can selectively complex a given ion. The polymer

matrix containing the sensing material is often polyvinyl

chloride (PVC) [121]. Bulky crown ethers used in a PVC

membrane ISE can exhibit a selectivity up to 2000:1 for

lithium [51]. A glass ion-exchange membrane is used for the

analysis of sodium, and a valinomycin neutral-carrier

membrane is used for potassium [101].

The use of ISE's to analyze clinical samples involves

either the direct analysis of undiluted samples or the











indirect analysis of pre-diluted samples. Direct ISE

methods are subject to bias because of the difference in the

serum matrix and the aqueous samples used for calibration.

Indirect ISE is susceptible to error introduced by the

dilution.

ISE's to monitor Mg can yield rapid results on blood,

plasma, serum and aqueous solutions with sample sizes

ranging form 100 to 200 pL [55]. The Mg ISE's employ

ionophores using neutral carrier based membranes with

excellent precision reported at 2 to 4%. However, this

method does experience problems with very low levels of

magnesium because the analytical response is not linear at

these low concentrations [52].

ISE's compare favorably to the methods of atomic

absorption spectrometry and flame emission spectrometry for

the analysis of several elements. ISE's have the advantages

that they function in turbid solutions, have a wide dynamic

range, have a rapid response, are inexpensive, and are very

portable with current instruments weighing between 7 to 12

kg [117]. The rapid response is very beneficial in

monitoring dosages and compliance with medical treatment

such as lithium treatment in psychiatric patients. ISE's

have the disadvantages that they have limited sensitivity,

are subject to interference from other ions and memory

effects, and require frequent calibration.















Conclusion


The analysis of the primary and trace elements in blood

is very important in maintaining and monitoring the health

of individuals. Although there are many methods capable of

doing multi-element analysis in blood, there is still much

room for improvement. The most accurate and precise methods

all require some sort of sample pretreatment. Sample

treatment requires time and is a possible source of

contamination. Ideally a clinical method for blood analysis

would be able to analyze whole blood directly, without

sample pretreatment, and would be able to use simple

standards (i.e. aqueous) for calibration.
















CHAPTER 4
EXPERIMENTAL SETUP AND MATERIALS


Setup


The experimental setup is shown in figure 4-1. Each

component of the experimental setup will be described.



Microwave Plasma Electronics

The microwave plasma was generated by an 870 W

magnetron (Samsung OM75A) at 2450 MHz. This type of

magnetron is commonly found in domestic microwave ovens.

Magnetrons are capable of high power with low cost and high

efficiency. Magnetrons produce microwaves through the

combination of an anode, cathode, and magnet. Electrons are

emitted from the cathode and are introduced into a

combination of electric and magnetic fields which cause the

electrons to move around the cathode. The electrons then

move toward the anode and exchange potential energy,

building up the microwave field. When the electrons hit the

anode, the power is coupled directly to the output. The

output allows the microwaves to be taken out via an external























Removable Quartz
Chimney


Helium Flow in --


Teflon Tape


Figure 4-1. CMP-AES experimental setup.









50

transmission line [9]. A diagram of the magnetron is shown

in figure 4-2.

The magnetron was powered by a current regulated

analog-programmable power supply (Model 106-05R, Bertran

High Voltage, Hicksville, NY, USA). An A.C. power

transformer (Magnetek Triad, model F-28U, Newark

Electronics, Chicago, IL) was used to provide a high

current, low AC voltage for the magnetron filament.



Waveguide

The rectangular waveguide was made out of aluminum and

constructed in the laboratory. The waveguide had the

following dimensions: height = 47 mm, width = 98 mm, length

= 277 mm. The waveguide had a hole near one end on the top

allowing the output of the magnetron to be inserted, and

holes on the top and bottom near the other end allowing the

torch to be suspended within the waveguide. The hole

diameter for the torch was 44 mm, and the center of the hole

was 58 mm from the end.



Torch

The torch consisted of four concentric quartz tubes:

an outer quartz tube (outer diameter (o.d.) = 19 mm)

directed the flow of helium; a removable quartz tube (o.d. =

15 mm) reduced the dead volume of the torch; and an inner
















Heater leads
and cathode
leads


Cooling
fins


Magnets


Anode


Output antenna


Figure 4-2. Magnetron












quartz tube (o.d. = 5 mm) that supports a short piece of

quartz tubing (o.d. = 2 mm) in which the filament rests.

The inner quartz tube is used to decrease the volume of the

torch in order to reduce the amount of helium gas required.

The inner quartz tube is a separate piece of quartz tubing

held in place in the torch with teflon tape. In some

experiments, the inner tube is brought up around the plasma

so that it shields the plasma. The inner tube as a shield

is better than using the torch itself because the inner

quartz tube is easily replaced if the plasma attacks it and

makes it optically unclear. A quartz chimney surrounds the

top of the torch to reduce instabilities caused by air

currents.



Plasma Gases

Helium (BOC Gases, The BOC Group, Inc., Murray Hill,

N.J.) was used as the plasma gas. Helium was an excellent

plasma gas for atomic emission spectroscopy because of its

high ionization energy [122]. The ionization energy of

helium is 24.6 eV compared to 15.8 eV for argon [123]. The

high ionization energy enhanced the possibility of energy

transfer to the analyte. A helium plasma is able to excite

efficiently elements introduced into the plasma, and has low

background characteristics. Hydrogen (BOC Gases, The BOC

Group, Inc., Murray Hill, N.J.) was introduced into the












plasma at a flow rate of 250 cm3/min for the cleaning step.

The presence of hydrogen in the plasma helped to create a

reducing environment and increased the temperature of the

plasma [124]. The higher temperature and reducing

environment helped in the removal of the carbonaceous

residue left over from the blood sample.



Electrode

The graphite cup holder electrodes were made out of

spectroscopic grade carbon (Union Carbide, Carbon Products

Division, Cleveland, OH). The metals used for the cups and

the electrodes were obtained from Alfa Aesar/Johnson

Matthey, Ward Hill MA. The following metals were obtained

as rods and machined to make the various electrodes: nickel

(99.5% pure), titanium (99.99% pure), and tungsten (99.95%

pure). The tungsten screen used was obtained from Newark

Wire Cloth Co., Newark, NJ.

The tungsten wire (99.95% pure) used was also obtained

from Alfa Aesar/Johnson Matthey, Ward Hill, MA. Three

diameters of wire were used: 0.25 mm, 0.5 mm, and 0.75 mm.

The final filament used was made out of the 0.5 mm tungsten

wire. The top of the filament was a tight 2.5 turn spiral

with a diameter of 3 mm. The total length of the filament

was 6.5 cm.












Lens Setup

The initial lens setup (figure 4-3a) used two

planoconvex lenses. The first lens (diameter = 50.8 mm,

focal length = 125 mm) was placed 125 mm from the plasma to

collimate the emission from the plasma. The second lens

(diameter = 25.4 mm, focal length = 50.8 mm) was placed so

that the emission was focused onto the entrance slit of the

spectrometer.

In an attempt to improve the precision of the CCMP-AES,

the lens setup was changed after the lead-in-blood work was

completed. The lenses (figure 4-3b) were set up so that the

emission from the plasma filled the collimating mirror of

the spectrometer. Two lenses had to be used because a

single lens could not be placed close enough to the plasma

for the desired focusing. A first lens (focal length = 38.1

mm, diameter = 38.1 mm, Esco Products/Precision, Oak Ridge,

New Jersey) was used to form a one-to-one image of the

plasma at a proper distance away from the plasma. It is

placed 76 mm from the plasma. The second lens (focal length

= 25.4 mm, diameter = 25.4 mm, Esco Products/Precision, Oak

Ridge, New Jersey) was then used to magnify the image in

such a way that the collimating mirror of the spectrometer

was completely filled with emission. The second lens was

placed 102.78 mm from the first lens. The distance for each








Collimating
Lens


Focusing
Lens
.. .. .


Spectrometer


Lens 1


Lens 2


Spectrometer

To collimating
mirror of
spectrometer


1:1 Image
of Plasma


s I


Figure 4-3.


Lens setup (not to scale): a) lead in
blood work, b) multielement work.


Plasma


Plasma











lens was calculated from the equations:

1/f = 1/s + 1/s' and m = s'/s

where f is the focal length of the final lens, s is the

distance between the emission source and the final lens, s'

is the distance between the lens and the mirror, and m is

the resulting magnification of the image. In the

modification of this lens setup, s became the distance from

the second lens to the one-to-one image formed by the first

lens. This lens setup resulted in a magnification of the

plasma image of approximately 25 times.



Detector

The detector consisted of a 0.5 m spectrometer (Spex

1870, Edison, NJ, USA) and either a photodiode array (PDA)

or a charge coupled device (CCD). The spectrometer grating

contained 1200 grooves/mm with a blaze wavelength of 300 nm.

The preliminary work and the lead in blood research was done

using the PDA. The multielement work was done with the CCD.

The spectrometer slit width was adjusted for each

element. If greater sensitivity was needed, the slit width

was opened to as much as 40 gm. For elements requiring less

sensitivity and higher resolution, a slit width as small as

10 lm was used. The slit height was kept constant at 2 cm.

Both the PDA and the CCD gave a spectral window of 40 nm.












Photodiode array

The intensified photodiode array (Tracor Northern TN-

6122A, Middleton, WI, USA) consisted of 1024 silicon

photodiodes arranged linearly, each spaced 25.4 pm apart.

Each photodiode consisted of a layer of silicon doped with

atoms containing extra electrons (p-type semiconductors) on

top of a layer of silicon doped with atoms with one valence

electron less than silicon (n-type semiconductor). This

allows the current to flow in only one direction. A reverse

biased potential is applied across the diode so that when

exposed to light, electron hole pairs are created producing

a current that is proportional to the amount of light [125-

126].

Charge coupled device

The detector was changed from the photodiode array

(PDA) that was used for much of the lead-in-blood work, to a

charge coupled device (CCD) for all of the multielement

work. This change was necessary because of problems that

developed with the hardware and software that controlled the

PDA. The CCD detector has the advantage that it was two

dimensional and was cryogenically cooled to reduce the dark

current.

The CCD contained 296 x 1152 picture elements (pixels).

Each pixel was 20 pm square and consisted of a metal-oxide-

silicon (MOS) capacitor. The pixels were made out of an











insulating silicon dioxide layer over a p-type silicon

substrate. This was topped by a thin metal electrode [125,

127-128]. When a photon struck a pixel, it penetrated the

lattice breaking the covalent bonds between adjacent silicon

atoms. This created electron-hole pairs which were measured

as an electric charge. The radiation striking each pixel

was proportional to the resulting charge and was measured by

transferring the charge to a single point. The covalent

bonds could also be broken by thermal agitation. The

thermal generation of charge was reduced by cooling the CCD.

Figure 4-4 shows the effect of cooling on the CCD background

counts. The temperature was maintained constant by a

heating element in the CCD dewar. The temperature was

maintained at -110 C even though there was not much change

in the dark counts below a temperature of -40 "C. At

temperatures higher than -90 C the liquid nitrogen

evaporates too quickly. At temperatures lower than -140 C,

the charge transfer efficiency from pixel to pixel may be

lowered, degrading the CCD performance [126].

If the light levels reaching the CCD were too high,

blooming could occur. Blooming is the spillage of charge

from an over-illuminated pixel to an adjacent pixel [126,

128]. The signal to noise ratio and the dynamic range could

be improved by the process of inning. Binning combines the

charge from adjacent pixels during readout. The charge read












7
1.4x10



1.2x10


w-
ri)
1. Ox1o

(Id

i 8.0x10 6

0
o
u

1
S6.0x10

0
S4.0x10 6
U


2.0x10 -


0.0 -


U


U EEUEEEE EU---


-120-100 -80 -60 -40 -20 0 20
Temperature (OC)



Figure 4-4. CCD background dependence on temperature.










60

will increase by the number of pixels binned, but the noise

will stay the same. Binning has the disadvantage of

reducing the spatial resolution [126].

Originally, the CCD detector was not sensitive to

emission below 400 nm. The camera was sent to Spectral

Instruments (Tucson, Arizona) so that a UV enhancement

coating could be applied to the CCD element. The coating

was lumogen yellow, an organic phosphor. The phosphor

absorbs light in the UV range and re-emits it in the visible

range.



Computer Software

The programmable power supply and the triggering of the

detector were controlled by a computer (PC's Limited, model

28608L, PC's Limited, Austin, TX) and a computer interface

(Model SR 245, Stanford Research Systems, Palo Alto, CA,

USA) using a program written in Microsoft QuikBasic 4.50

(Copyright Microsoft Corporation, 1985).

The emission spectra were collected using CCD9000"

spectral acquisition software, version 2.2.2 (copyright

1990-1992, Photometrics, Ltd.). The peak areas were

determined using the program LabCalc" (copyright 1987-1992,

Galactic Industries Corporation). Analytical curves were

constructed using Origin" version 4.0 (copyright 1995,

Microcal" Software, Inc.).












Materials


Aqueous Standards

Aqueous standards were prepared by sequentially

diluting 1000 ppm reference standards for each element

(Fisher Chemical, Fisher Scientific, Fair Lawn, New Jersey).

The standards used in the standard additions of the blood

analysis were prepared from the salts of the elements being

analyzed. This was necessary because the standards needed

to be non-acidic to prevent denaturing of the blood. Also,

the concentrations required for some of the elements were

larger than the available aqueous standards. All the

aqueous standards were prepared using deionized water

(specific resistivity 18 MQ/cm) from a Milli-Q Plus water

system (Millipore Corporation, Bedford, MA). The aqueous

standards were introduced for analysis using a 2 kL air

displacement pipetter (Eppendorf, Brinkman Instruments Inc.,

Westbury, NY).



Blood Standards

The lead bovine blood standards used were Quality

Control Materials (QCM) produced and distributed by the CDC

Blood Lead Laboratory Reference System (BLLRS). The samples

were collected by the CDC from two cows kept at the CDC

livestock facility (Lawrenceville, GA) that were given









62

dosages of lead nitrate in gelatin capsules. The blood was

collected from the cows and the initial concentration was

determined using atomic absorption spectrometry. Varying

amounts of the two blood samples were then blended to give a

range of lead concentrations. The final concentrations of

the samples were determined using ID-ICP-MS [70].

Human whole blood was collected by venipuncture into a

Vacutainer (Becton Dickinson Vacutainer Systems, Franklin

Lakes, NJ, USA) coated with KEDTA as an anticoagulant. The

standard addition samples were made by adding varying

amounts of an aqueous standard to a 0.75 mL portion of whole

blood. Deionized water was added to the sample to produce a

final volume of 1.0 mL. This resulted in a sample that was

75% whole blood. The samples were gently rolled and then

sonicated for 5 minutes to thoroughly mix the aqueous

standard and the blood.

A lead-in-blood Standard Reference Material (SRM 955a)

was purchased from the National Institute of Standards and

Technology (NIST) (Gaithersburg, MD). This SRM consisted of

four vials of frozen bovine blood each containing a

different concentration of lead. The concentration of lead

in each SRM was determined by NIST using ID-ICP-MS and

confirmed using GFAAS and laser-excited atomic fluorescence

spectrometry. The concentrations are shown in Table 4-1.

The uncertainty reflects a confidence level of 95%.









63

It was necessary to keep the blood samples frozen when

not in use. By freezing the blood, the bacterial and

chemical interaction of the blood sample were greatly

reduced. If not frozen, the various elements can bind to

proteins in the blood and settle out. Although the content

of the element in the vial remains the same, the

concentration in the liquid portion will be less than the

target value for the standard. The proteins could also

denature leading to a change in the homogeneity of the blood

[129]. Prior to use, the blood samples were allowed to thaw

to room temperature, homogenized by gently rolling, and then

sonicated for 10 minutes.

The blood samples were introduced for analysis by a

positive displacement micropipetter (Drummond model 525,

Drummond Scientific Co., Broomall, PA). Before depositing

the sample, the outside of the glass capillary tip was wiped

with a KimwipeM to remove any blood that had adhered to the

tip. The pipetter was cleaned between sample runs by

repeatedly depressing the plunger first in a solution of 5%

nitric acid solution and then in deionized water.














Table 4-1. Concentration of lead in SRM 955a at 22C.


Vial Number Concentration (ppb)

955a-1 50.1 0.90

955a-2 135.3 1.3

955a-3 306.3 3.2

955a-4 544.3 3.8
















CHAPTER 5
SAMPLE INTRODUCTION


Introduction


Capacitively coupled microwave plasma atomic emission

spectrometry (CMP-AES) has been used to analyze various

types of samples directly. Discrete sample introduction in

a CMP is easier than in a microwave induced plasma or an

inductively coupled plasma because a CMP is the only one

that uses an electrode to support the plasma.

Investigations have involved the analysis of various

matrices including dry tomato leaf samples, coal fly ash,

steel, oil, and biological materials [1-3, 130-132]. A

variety of methods have been used for sample introduction

into a CMP. They have included nebulization, thermal

vaporization, and hydride generation.



Methods of Sample Introduction into a CMP


In the earliest work with a CMP as an atomic emission

source, solid electrodes were used to support the plasma.

The analyte solution was vaporized and carried into the

plasma by premixing the analyte carrier gas and the plasma

65












gas. Hanamura et al. used a platinum clad tungsten

electrode with this method of sample introduction [133].

The platinum coating was used because the platinum is

thermally stable, chemically inert, and has a low thermionic

emission rate. These properties of platinum increased the

electrode lifetime and reduced the contamination of the

plasma by elements present in the electrode. Interfering

emission lines from the electrode is one of the major

drawbacks of the single electrode CMP. Hanamura and

coworkers use this type of electrode to analyze hydrogen and

oxygen in metals and also mercury in water [133-134].



Nebulization

Several researchers have used a nebulizer to introduce

aqueous samples into a CMP [124, 135-137]. A nebulizer is

an easy and inexpensive way to introduce a solution into a

plasma. Nebulization is a process where the sample to be

analyzed is transferred by a peristaltic pump to a nebulizer

which converts the sample into an aerosol in a spray

chamber. The aerosol is then swept by a carrier gas through

the center of the electrode into the plasma. A disadvantage

of nebulization is that much of the sample is lost in the

spray chamber.









67

Patel et al. used pneumatic nebulization with a CMP to

analyze aqueous samples for 15 elements [135]. Sample

solutions were nebulized with a Meinhard nebulizer and a

laboratory-constructed spray chamber and desolvation system.

A tubular electrode made out of tantalum was used to support

the plasma. The analyte carrier gas passed through the

center of the hollow electrode and entered into the plasma

at the top of the electrode [25]. By introducing the sample

directly into the core of the plasma, the interactions

between the sample and plasma were improved. Also, the

concentration of the analyte in the plasma viewing region is

increased, improving the detection limits, signal to noise,

and signal to background. It was determined that this

method gave low detection limits with a wide linear dynamic

range for a number of different elements. Several other

tube materials and forms of electrodes were evaluated. The

electrode types included a platinum tube, a copper tube, a

platinum coated tungsten wire (0.5 mm o.d.) a molybdenum

rod, and a tungsten rod with platinum cladding [135].

Hwang et al. used graphite as the electrode material

[137]. This electrode had a lower emission background and

did not significantly contaminate the plasma in comparison

to the metal rod electrode. Excellent detection limits for

several elements in aqueous solutions were obtained [137].












Thermal Vaporization

Two previous methods of sample introduction by thermal

vaporization (TV) include a tungsten filament electrode

(figure 5-1a) [23, 131-132] and a cup holder electrode

(figure 5-1b) [1-3, 130, 138-139]. The sample was

introduced into the CMP by directly depositing it on the

filament or in the cup held by the electrode. Thermal

vaporization is advantageous over nebulization in that a

greater percentage of the sample is introduced into the

plasma. TV has the disadvantages of poorer precision,

greater interference effects, and a lower throughput of

samples.

Hanamura et al. used a another method of thermal

vaporization with a CMP to measure carbon, hydrogen,

nitrogen, oxygen and mercury in orchard leaves and tuna fish

[140]. A separate furnace vaporizer was used. The sample

was held in a quartz crucible which was heated. The carrier

gas was flown through the sample chamber to carry the

volatile constituents through the center tube of the torch

and into the plasma for analysis.

Cup electrode

A cup can be used to introduce both liquid and solid

samples into a CMP. In order to use a cup electrode, an

electrode must be fabricated such that the top of the


















[


Electrode designs: a) filament electrode,
b) cup holder electrode, c) platform electrode,
d) titanium electrode with nickel cap,
e) titanium electrode with titanium cap.


I..'


Figure 5-1.












electrode has a hollowed out portion that will snugly hold

the cup. The electrode must be made out of a material that

is conductive and has a higher melting point than the

thermal temperature of the plasma. Materials that can be

used for the electrode are graphite or various metals.

Graphite electrodes are cheaper and more resistive than

metal electrodes, and emission from the metal electrode can

also cause interference in analysis. Electrodes made out of

metal have several advantages over those made out of

graphite. Metal electrodes are more durable and last longer

than graphite electrodes. Also, graphite electrodes form

refractory carbides and produce gaseous molecular carbon

species which cause interference in emission measurements.

Cups made out of both graphite and tungsten have been

used to hold the sample. The cup was placed on the top of

the electrode and the electrode containing the cup was

placed into the central tube of the torch. The plasma was

ignited at a low power (around 100 W) to ash the sample and

was then raised to 400 700 W to atomize and excite the

analyte, enabling the measurement of the emission [1]. By

using a cup instead of a wire filament, higher powers could

be used so that there were fewer matrix effects and the

signal was larger. The disadvantage of using a cup was that

the atoms were dispersed over a wider volume so the number

density of excited atoms was smaller.









71

Ali et al. used CMP-AES with a cup electrode with both

the electrode and the cup made out of graphite. Detection

limits ranging between 10 and 210 pg were obtained for 12

elements with a precision better than 12% [138]. A sample

volume of only 5 gL was used. The graphite cup was coated

with tantalum carbide to reduce memory effects. Because

graphite was quite porous, memory effects were observed for

all the elements analyzed. The cups lasted 30-40 firings

and then had to be replaced due to etching of the cup rim by

the plasma. Multielement analysis with this system was

performed on coal fly ash and tomato leaves [1]. Spencer et

al. used a tungsten cup to analyze silicon in oils [3].

Tungsten was found to be an excellent cup material because

of its tolerance to high temperatures, long lifetime, low

emission background, and low memory effects.

More recently Pless et al. used a tungsten cup in a

graphite electrode for multielement analysis [139] The

cup had a total volume of 30 pL. Detection limits in the

low picogram range were obtained for 10 pL samples of

cadmium, magnesium, and zinc in aqueous solutions. Cadmium

in solids was also analyzed obtaining a detection limit in

the picogram range [130]. Various matrices were analyzed by

this system including coal fly ash, tomato leaves, soil,

bovine liver, and oyster tissue. The results achieved good











agreement with the certified values of the reference

materials.

Filament electrode

Ali and Winefordner evaluated a tungsten filament

electrode for multielement analysis in aqueous solutions

[23]. Filaments have the advantage that they are simple and

inexpensive. The sample was introduced into the plasma by

placing a few microliters of sample in a loop in the

filament. The sample was then dried at low microwave

power. The filament heated up rapidly creating a high rate

of volatilization. After the sample was dry, the plasma was

ignited and the sample was ashed if necessary by a low power

(30 W) microwave plasma The power of the plasma was

increased until the sample was atomized and excited so that

the emission could be measured. It was found that adding a

low flow rate (100 mL/min) of hydrogen gas with the plasma

gas reduced the background emission from the tungsten

filament. The absolute detection limits of 12 elements were

in the range of 1 to 100 pg and this compared favorably to

the method of graphite furnace atomic absorption

spectrometry (GFAAS). A linear dynamic range of 3 to 4

orders of magnitude was obtained and the precision was

better than 10%. Reported lifetimes for the filaments were

500-1000 runs [23].











Wensing et al. evaluated a CMP-AES for a lead blood

screening method using a tungsten loop (figure 5-la) as the

electrode [131-132]. A tungsten wire of 0.25 mm thickness

was tied in a knot, leaving a small loop in the center, and

the remaining ends of the wire were bent so that they could

be inserted into a piece of quartz tubing which was then

inserted into the plasma torch. The blood samples were held

in the loop by adhesion to the wire.

A 5 pL blood sample was placed in the filament loop and

subsequently dried, ashed, and atomized. Drying was

accomplished using microwave power to inductively heat the

electrode for 90 seconds. After drying, the helium gas flow

was turned on and a small plasma was ignited, ashing the

sample at a power of 55 W for two minutes. The sample was

then atomized in a helium plasma at a power of 170 W. The

lead emission at 405.8 nm was measured using a photodiode

array (PDA). A cleaning step was necessary in order to

remove the carbonaceous residue from the left over blood

sample. Cleaning was performed by increasing the power to

200 W and adding a flow of hydrogen gas to the helium

plasma. The cleaning procedure lasted for one minute and

effectively removed all blood residue from the filament.

The filament electrode CMP-AES method was able to meet

two of the criteria set forth by the Centers for Disease











Control (CDC) for a lead in blood screening method. The

detection limit for lead in blood was 7 ppb and the analysis

time was under five minutes. However, the filament

electrode was not accurate for blood lead concentrations

unless matrix effects were reduced by diluting the blood

with deionized water by a factor of approximately one half.

Even with dilution, the method was not sufficiently accurate

for blood lead concentrations below approximately 200 ppb

and the precision did not meet the requirements set forth by

the CDC for lead in blood screening methods.

Using the filament as the electrode had several drawbacks.

The filaments were handmade and so were difficult to make

reproducibly. It was also difficult to deposit the sample

in the filament loop with adhesion to the wire as the only

source of support for the sample. Finally, the lifetime of

the filament electrode was greatly shortened if the

microwave plasma power was raised above a certain point.



Hydride Generation

Hydride generation involved introducing the elemental

analytes to the CMP as a gas. An acidified aqueous solution

of the sample was added to a small volume of 1% sodium

borohydride in a reaction cell. After a certain amount of

time had passed, the resulting hydride of the element was

carried to the CMP by a flow of the plasma gas. Akatsuka











and Atsuya used a CMP with hydride generation to analyze

arsenic in sewage sludge, and iron in steels. They obtained

a detection limit of 0.25 ppb for arsenic in solution [141].

Uchida et al. used the method of hydride generation with a

CMP to analyze inorganic tin [142].



Development of Electrode for Blood Analysis



Cup Holder Electrode

A cup holder electrode (figure 5-1b) was investigated

for the analysis of lead in blood. A cup holder electrode

had several advantages over the filament electrode used by

Wensing et al. for lead blood analysis. Using a cup holder

electrode allowed the introduction of larger sample volumes

and made sample deposition easier and more reproducible.

Also, a cup holder electrode is a more robust electrode

allowing the atomization power to be increased, which could

lead to increased emission intensity.

Initially the electrode material chosen was graphite.

Graphite is a good material because it can sustain very high

temperatures, it is inexpensive, and it is easy to machine

to make modifications to the electrode. The easy

machinability of graphite allowed various parameters of the

electrode (length and penetration) to be optimized before










76

switching to a metal cup holder. The metal holder would be

more durable but not as easy to machine as graphite.

The graphite electrode contained a hole in the top

which held a nickel cup. A graphite cup would not be

suitable for blood analysis because the graphite could form

refractory compounds which would interfere with the lead

signal. Also, the blood could seep into the graphite

causing memory effects. A cup made out of metal would be a

better choice because there would be less of a chance of

interfering species and memory effects. Initially, nickel

was chosen as the cup material because it did not oxidize

easily, making it very durable. The cup had a sample

capacity of 20 yL.

Several parameters for the cup electrode were studied.

The change in electrode from the filament to the cup

electrode required reoptimizing the conditions of the

plasma. The coupling of the microwave energy and the

stability of the plasma were affected by the length of the

electrode, and the electrode's penetration into the

waveguide. The optimum coupling position of the electrode

was determined by varying the electrode length penetration

into the microwave field to find the parameters where the

minimum microwave power was needed to sustain the plasma.

The first parameter studied was the length of the

electrode. Initially the height of the electrode above the












waveguide was kept constant at 8 mm. This was the height

used in the work with the tungsten filament electrode.

Different lengths of the electrode were then used

determining the range of powers over which a stable plasma

would form. The power supplied to the magnetron was

gradually increased until a plasma would form. The power

was increased until the plasma was no longer stable and then

decreased until the plasma could no longer be sustained.

The lengths of the electrodes ranged from 3.5 cm to 7.0 cm

which corresponded to a depth of penetration into the

waveguide of 2.7 cm to 5.7 cm. This experiment was repeated

keeping the penetration depth of the electrode into the

waveguide constant at 3.2 cm and evaluating different

lengths of the electrodes. As the penetration depth was

increased, the plasma could be maintained at higher powers.

For some positions of the electrode, the maximum power of

700 W could not be achieved because the plasma started to

make a very loud whining noise. The length and penetration

that produced a stable plasma over the widest range of

powers was chosen as the optimum. Figure 5-2 shows some

examples of the data collected for the optimization of

electrode length and penetration.

Using the optimum conditions found for the electrode,

the analysis of aqueous lead solutions was studied. At an

atomization power of 370 W, the lead emission took




































S 3.5 cm Electrode









Penetration (cm)


Peneraton (c)
Penetration (cm)


" 4.5 cm Electrode




Puo





Penetration (cm)


S 7.0 cm Electrode


0 on






Penetration (cm)


Figure 5-2. Optimization of electrode length and
penetration depth of graphite electrode.









79

approximately 20 seconds to appear and then remained for 90

seconds for a 10 pL sample of a 50 ppm lead standard. At

such a high concentration and power, the signal should have

been much greater. Tungsten and titanium cups were

evaluated with the graphite cup holder, but these cups also

gave poor results.

The next electrode evaluated was a cup holder made out

of titanium with a nickel cup. Titanium metal instead of

graphite could improve the coupling of the microwaves to the

electrode, improving the efficiency of atomization and

excitation. After atomization with this system, the cup

remained very hot and required a long time to cool down. If

an aqueous sample was deposited in the cup before it was

sufficiently cooled, the sample would vaporize. No

improvement of the lead signal intensity was observed.



Platform Electrode

A cup holder electrode made out of titanium that had

not been drilled to hold a cup was then studied as the

method of sample introduction. This type of electrode was

labelled the platform electrode because the sample was

placed on the flat top portion of the electrode. The top

portion was approximately 6.5 mm long and 6 mm in diameter

and the post was ~ 3 mm in diameter. A 10 pL aqueous lead

sample was placed on the flat top of the electrode, dried










80
for 90 seconds at approximately 150 W and then atomized with

a plasma power of 300 W. The titanium platform electrode

gave a larger signal than had previously been obtained. The

signal still lasted a long time (figure 5-3a) but not as

long as with the graphite electrode and the nickel cup. The

signal increased (figure 5-3b) when the bulky top part of

the electrode (that was intended to hold the cup) was

removed, yielding a thin metal rod (Figure 5-2c). With this

electrode design, the plasma formed on the same surface that

the sample was on, increasing the interaction of the sample

and the plasma, yielding more efficient atomization and

excitation.

A significant problem was experienced with the titanium

electrode. After several runs, the lead signal would begin

to decrease in intensity and take longer to appear. It was

necessary to sand off the top of the electrode to regain the

larger signals. Each time the electrode was sanded, a

titanium atomic emission line appeared that interfered with

the lead line being used for measurement. The electrode had

to be tempered by igniting a plasma and then slowly taking

it to higher powers to eliminate the interference before

conducting another run after cleaning. The more the

electrode was used, the sooner in between runs it had to be

cleaned off. The interfering titanium line also limited the

amount of power that could be applied to the plasma. At







300-
250-
200-
S150-
C
100-
50-


0 10 20 30 40
Time (seconds)


Time (s)


Temporal profiles for lead signal for the
platform electrodes: a) platform with cup
holder portion, b) thin titanium rod platform.


Figure 5-3.


2\j\'











powers above 400 W, the interfering line appeared. It is

desirable to have an electrode that could last for an

indefinite period of time and would not have any emission

lines which would limit the powers used. For these reasons,

several other materials were tried for the platform

electrode.

Tungsten, which had been used for the filament

electrode, has a higher melting point and lower background

emission than titanium and so it was evaluated as the

electrode material. A 10 yL aqueous sample on the tungsten

electrode took approximately 5 minutes to dry at a microwave

power of 150 W. The lead signal, upon atomization, took

several seconds to appear and then lasted for about 30

seconds. The signal was small compared to the signal

obtained using the titanium electrode, even at higher

powers. Nickel was studied next, but it also produced

results similar to those obtained with the tungsten

electrode.

A titanium electrode with a nickel cap which screwed

into the top was then evaluated (figure 5-2d). This design

was used in an attempt to obtain a similar signal as that

obtained with the titanium electrode, but with a longer

lifetime because of the nickel cap. The signal obtained for

this electrode was similar to that obtained when the whole










83
electrode was nickel; a low intensity signal was delayed in

appearing and had a long temporal profile.

From the results obtained, the electrode made out of

pure titanium was the best platform electrode even though it

would have to be changed on a regular basis. The titanium

platform electrode lasted approximately 130 firings for

aqueous samples. The titanium platform gave good results

for aqueous lead samples (figure 5-4) achieving a detection

limit of 30 ppb for a 5 pL sample volume. However, the

precision was poor for concentrations of 100 ppb and below.

Analysis of lead in whole blood was performed using

whole blood quality control materials (QCMs). The

analytical curve for these standards (figure 5-5) was linear

(R = 0.997) and produced a detection limit of 50 ppb. After

running an individual analysis, it was necessary to clean

the electrode by scraping off the remaining blood residue.

This was not difficult, but added approximately one minute

to the analysis time. Occasionally, the blood sample would

interfere with the plasma yielding poor precision. The

interference of the blood samples with the plasma might be

due to a problem in depositing the sample. Since the

surface of the electrode was flat, it was difficult to

deposit the sample in the same way each time. The maximum































r-1



c) 400




200





0



0 100 200 300 400 500 600

Concentration (ppb)


Figure 5-4. Analytical curve for aqueous lead standards on
the titanium platform electrode.














2500






2000






1500-
r-




1000-





500-



0 100 200 300 400 500 600 700

Concentration (ppb)


Figure 5-5. Analytical curve for whole blood lead standards
on titanium platform electrode.











capacity of the titanium rod platform was 5 pL, and the

sample would sometimes run over the side.

In order to achieve reproducible sample deposition,

electrodes containing a depression in the top were used. It

was found that the size and shape of the depression was very

important in measuring the lead signal. If the depression

was too deep, the signal was small. If the volume of the

blood sample was too large, the blood would interfere with

the formation of the plasma. When blood samples were run

with the depression electrode, the inside of the depression

became dirty and was difficult to clean. Even for shallow

depressions, the lead signal was approximately one half of

the signal obtained by the electrode without the depression.

The electrode with the depression had a short lifetime of

only 30 firings for blood samples.

To reduce the amount of time required to clean the

electrode, a titanium electrode with a cap was used (figure

5-2e). This electrode design allowed one cap to be cleaned

while another cap was being used for analysis. Samples

could also be dried separately, and then placed on the cap

holder to use the microwave plasma for the ashing and

analysis. This shortened the analysis time by ninety

seconds and could be beneficial for the storage and

transport of the blood samples in the clinical setting.

Caps with various diameters and various sized depressions











were used. Some problems were experienced with the

uniformity of the plasma on the titanium cap electrode. At

lower microwave powers, the plasma would sometimes form on

one side of the cap and either stay at that side or flicker

around the edge of the cap. At higher microwave powers,

some of the caps yielded good signal, but it was difficult

to clean them when analyzing blood samples. The caps were

also difficult to reproducibly construct. Caps with the

same design did not produce the same signal.



Suspension Method

The results with the platform electrode demonstrated

that it is necessary for the plasma to interact directly

with the blood sample. Anytime the blood sample was below

the plasma in some sort of depression, the signal was

drastically reduced. However, when the blood sample was on

the surface of the electrode where the plasma formed, the

blood would often interfere with the stability of the

plasma. A method for which the sample was suspended above

the electrode was used to try to account for keeping the

sample in the plasma without being on the surface where the

plasma forms. A titanium rod electrode was used to support

the plasma and a macor holder was used to support a screen

or a wire mesh above the electrode (figure 5-6). Initially

stainless steel screens (10-20 and 40 mesh) were used.


















Top View


Macor Holdr Tungsten Mesh
Macor Holder




Titanium Electrode


Quartz Torch


Helium gas


Figure 5-6. Suspension method of sample introduction.











Platinum screens (40 mesh), tungsten screens (20 and 40

mesh), and a four-squared cross made out of tungsten wire

were also tried.

The sample would not dry with microwave power alone, so

a very low power plasma was ignited below the screen. For

blood samples, the drying caused some problems because if

the plasma was too close to the sample or too high in power,

it would cause the sample to bubble and spatter. The

titanium electrode was changed to a pointed tungsten

electrode which could sustain a very low power plasma which

dried the blood more effectively. The power of the plasma

was increased for ashing, and then further increased for

atomization. This method worked well for aqueous standards

and greatly decreased the background during atomization

because the macor holder shielded most of the emission from

the plasma. However, this method of sample introduction did

not work well for blood samples. The mesh became very

brittle at higher plasma powers and broke very easily.



Spiral Filament Electrode

Each method of sample introduction tried had various

advantages to it. The cup holder electrode held the sample

the best, the filament electrode was easiest to clean, the

platform electrode gave the best signal, and the macor

holder resulted in the lowest background. Various features












of several of these methods were combined to design an

improved filament electrode. A thicker (0.5 mm in diameter)

tungsten wire was used which was more durable and could

sustain higher powers than the original filament (0.25 mm in

diameter) could. Initially a single loop was made at the

top of the wire to hold the sample, but it was difficult to

deposit the sample in the loop. A two and a half turn

spiral was then made at the top of the electrode The spiral

served as sort of a platform and held a 2 pL blood sample

very well. The spiral filament electrode (figure 5-7)

performed well for both aqueous and blood samples (chapter

6) and was easy to clean. The filament was, however,

difficult to make because the tungsten wire was very brittle

and would often split during the construction of the spiral.

An attempt was made to use commercial tungsten light

bulb filaments to hold the sample. A 20 turn, rectangular

light bulb filament was placed over the loop of a filament

electrode. This method would remove the necessity of having

the spiral at the top of the electrode and could also help

make the electrodes more reproducible. The method worked

well for aqueous samples (figure 5-8) giving a detection

limit of 44 ppb, but was very hard to clean after the

analysis of blood samples. It also eroded quickly under the

high plasma powers used to clean the blood from the

electrode.
















~3 mm








65 mm
Wire Diameter = 0.5 mm


Figure 5-7. Tungsten spiral filament.




Full Text
xml version 1.0 encoding UTF-8
REPORT xmlns http:www.fcla.edudlsmddaitss xmlns:xsi http:www.w3.org2001XMLSchema-instance xsi:schemaLocation http:www.fcla.edudlsmddaitssdaitssReport.xsd
INGEST IEID EQBYJZLR1_7U40W7 INGEST_TIME 2014-04-18T23:39:07Z PACKAGE AA00014247_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES



PAGE 1

08/7,(/(0(17 $1$/<6,6 ,1 :+2/( %/22' 86,1* $ &$3$&,7,9(/< &283/(' 0,&52:$9( 3/$60$ $720,& (0,66,21 63(&7520(7(5 %\ $57+85 '$9,' %(67(0$1 $ ',66(57$7,21 35(6(17(' 72 7+( *5$'8$7( 6&+22/ 2) 7+( 81,9(56,7< 2) )/25,'$ ,1 3$57,$/ )8/),//0(17 2) 7+( 5(48,5(0(176 )25 7+( '(*5(( 2) '2&725 2) 3+,/2623+< 81,9(56,7< 2) )/25,'$

PAGE 2

, ZRXOG OLNH WR GHGLFDWH WKLV GLVVHUWDWLRQ WR P\ SDUHQWV $UWKXU DQG $XGUH\ %HVWHPDQ 7KHLU ORYH DQG VXSSRUW KDV PHDQW VR PXFK WR PH DP YHU\ EOHVVHG WR KDYH WKHP DV P\ SDUHQWV

PAGE 3

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
PAGE 4

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

PAGE 5

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

PAGE 6

,QGXFWLYHO\ FRXSOHG SODVPD PDVV VSHFWURPHWU\ ;UD\ IOXRUHVFHQFH (OHFWURFKHPLFDO WHFKQLTXHV &RQFOXVLRQ (;3(5,0(17$/ 6(783 $1' 0$7(5,$/6 6HWXS 0LFURZDYH 3ODVPD (OHFWURQLFV :DYHJXLGH 7RUFK 3ODVPD *DVHV (OHFWURGH /HQV 6HWXS 'HWHFWRU 3KRWRGLRGH DUUD\ &KDUJH FRXSOHG GHYLFH &RPSXWHU 6RIWZDUH 0DWHULDOV $TXHRXV 6WDQGDUGV %ORRG 6WDQGDUGV 6$03/( ,1752'8&7,21 ,QWURGXFWLRQ 0HWKRGV RI 6DPSOH ,QWURGXFWLRQ LQWR D &03 1HEXOL]DWLRQ 7KHUPDO 9DSRUL]DWLRQ &XS HOHFWURGH )LODPHQW HOHFWURGH +\GULGH *HQHUDWLRQ 'HYHORSPHQW RI (OHFWURGH IRU %ORRG $QDO\VLV &XS +ROGHU (OHFWURGH 3ODWIRUP (OHFWURGH 6XVSHQVLRQ 0HWKRG 6SLUDO )LODPHQW (OHFWURGH &RQFOXVLRQ $1$/<6,6 2) /($' ,1 %/22' ,QWURGXFWLRQ 2SWLPL]DWLRQ RI 3DUDPHWHUV +HOLXP )ORZ 5DWH 'U\LQJ DQG $VKLQJ &RQGLWLRQV &OHDQLQJ 6DPSOH 6L]H 6RXUFHV RI 1RLVH $QDO\VLV $TXHRXV 6WDQGDUGV %RYLQH %ORRG 6WDQGDUGV 1,67 6WDQGDUGV YL

PAGE 7

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

PAGE 8

$EVWUDFW RI 'LVVHUWDWLRQ 3UHVHQWHG WR WKH *UDGXDWH 6FKRRO RI WKH 8QLYHUVLW\ RI )ORULGD LQ 3DUWLDO )XOILOOPHQW RI WKH 5HTXLUHPHQWV IRU WKH 'HJUHH RI 'RFWRU RI 3KLORVRSK\ 08/7,(/(0(17 $1$/<6,6 ,1 :+2/( %/22' 86,1* $ &$3$&,7,9(/< &283/(' 0,&52:$9( 3/$60$ $720,& (0,66,21 63(&7520(7(5 %\ $UWKXU 'DYLG %HVWHPDQ 'HFHPEHU &KDLUSHUVRQ -DPHV :LQHIRUGQHU 0DMRU 'HSDUWPHQW &KHPLVWU\ $ FDSDFLWLYHO\ FRXSOHG PLFURZDYH SODVPD DWRPLF HPLVVLRQ VSHFWURPHWHU &03$(6f KDV EHHQ HYDOXDWHG DV D FOLQLFDO PHWKRG IRU WKH GLUHFW DQDO\VLV RI VHYHUDO RI WKH SULPDU\ DQG WUDFH HOHPHQWV LQ ZKROH EORRG $ WXQJVWHQ ILODPHQW VSLUDO HOHFWURGH ZDV XVHG ZLWK WKH &03 DQG ZKROH EORRG VDPSOHV ZHUH GHSRVLWHG RQ WKH HOHFWURGH DQG VXEVHTXHQWO\ GULHG DVKHG DQG DWRPL]HG 7KH HPLVVLRQ ZDV PHDVXUHG ZLWK D VSHFWURPHWHU DQG HLWKHU D SKRWR GLRGH DUUD\ RU D FKDUJH FRXSOHG GHYLFH GHWHFWRU $ VDPSOH VL]H RI RQO\ c/ ZDV UHTXLUHG DQG WKH WLPH IRU HDFK VDPSOH UXQ ZDV XQGHU PLQXWHV 7KLV PHWKRG KDV D ZLGH G\QDPLF UDQJH DOORZLQJ WKH GHWHUPLQDWLRQ RI ERWK WKH SULPDU\ HOHPHQWV LQ EORRG DQG WKH HOHPHQWV SUHVHQW LQ WUDFH TXDQWLWLHV

PAGE 9

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

PAGE 10

&+$37(5 ,1752'8&7,21 7KH UHVHDUFK SURMHFW LQYROYHG GHYHORSLQJ D FDSDFLWLYHO\ FRXSOHG PLFURZDYH SODVPD DWRPLF HPLVVLRQ VSHFWURPHWHU &03 $(6f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

PAGE 11

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nVf *RRG DJUHHPHQW ZDV REWDLQHG ZLWK 650nV ZLWK FRQFHQWUDWLRQV JUHDWHU WKDQ 33E 7KH &03$(6 PHWKRG ZDV WKHQ XVHG IRU WKH DQDO\VLV RI VHYHUDO RI WKH PHGLFDOO\ VLJQLILFDQW SULPDU\ DQG WUDFH

PAGE 12

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

PAGE 13

&+$37(5 %$&.*5281' $WRPLF (PLVVLRQ 6SHFWURPHWU\ $WRPLF HPLVVLRQ VSHFWURPHWU\ LV D XVHIXO PHWKRG IRU HOHPHQWDO DQDO\VLV ,W LV YHU\ VSHFLILF KDV D ZLGH G\QDPLF UDQJH DQG KDV WKH FDSDELOLW\ RI PHDVXULQJ PDQ\ HOHPHQWV VLPXOWDQHRXVO\ 7\SLFDOO\ LWV GLVDGYDQWDJHV LQFOXGH SRRU VHQVLWLYLWLHV DQG VHULRXV PDWUL[ HIIHFWV >@ $WRPLF HPLVVLRQ LV WKH SURFHVV RI DQ DWRP EHLQJ EURXJKW WR DQ H[FLWHG VWDWH 7KH UHOD[DWLRQ RI WKH DWRP IURP WKH H[FLWHG VWDWH UHVXOWV LQ WKH HPLVVLRQ RI UDGLDWLRQ 7KH RXWHU VKHOO YDOHQFHf HOHFWURQV DUH WKH FRPSRQHQWV RI WKH DWRP WKDW DUH H[FLWHG 7KH HOHFWURQV FDQ EH H[FLWHG WR D QXPEHU RI GLIIHUHQW OHYHOV 7KH SKRWRQV HPLWWHG IURP WKH HOHFWURQV DV WKH\ UHOD[ IURP WKH GLIIHUHQW HQHUJ\ OHYHOV KDYH FKDUDFWHULVWLF IUHTXHQFLHV Yf JLYLQJ ULVH WR PDQ\ ZDYHOHQJWKV IRU HDFK HOHPHQW 7KH HQHUJ\ OHYHOV RI HDFK HOHPHQW DUH GLIIHUHQW ZKLFK UHVXOWV LQ D GLVWLQFW HPLVVLRQ VSHFWUXP IRU HDFK HOHPHQW 7KH HQHUJ\ (f DVVRFLDWHG ZLWK HDFK HPLWWHG SKRWRQ LV GHWHUPLQHG E\ WKH SURGXFW RI 3ODQFNnV FRQVWDQW K [ &7 -Vf DQG WKH IUHTXHQF\

PAGE 14

( KY KF; ZKHUH F WKH VSHHG RI OLJKW [ PV LQ D YDFXXPf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f RI DQDO\WH DWRPV LQ D JLYHQ H[FLWHG VWDWH bf FDQ EH UHODWHG WR WKH WRWDO QXPEHU GHQVLW\ RI DQDO\WH DWRPV QWf E\ WKH %ROW]PDQQ GLVWULEXWLRQ ] Uf 7KH WHPSHUDWXUH 7f LV WKH DEVROXWH WHPSHUDWXUH .f (M LV WKH H[FLWDWLRQ HQHUJ\ -f UHODWLYH WR WKH JURXQG VWDWH DQG Js LV WKH VWDWLVWLFDO ZHLJKW RI VWDWH L = UHSUHVHQWV WKH HOHFWURQLF SDUWLWLRQ IXQFWLRQ = 7f e JLH(N7

PAGE 15

)LJXUH (QHUJ\ GLDJUDP IRU H[FLWDWLRQ DQG HPLVVLRQ >@

PAGE 16

7KH UDGLDQW SRZHU RI HPLVVLRQ W!(f EHWZHHQ WZR VWDWHV IURP VWDWH L WR VWDWH Mf LV JLYHQ E\ WKH SURGXFW RI WKH SRSXODWLRQ GHQVLW\ RI WKH H[FLWHG DWRPV QDf WKH WUDQVLWLRQ SUREDELOLW\ $MO Vaf WKDW DQ H[FLWHG DWRP ZLOO XQGHUJR WKH WUDQVLWLRQ IURP M WR L WKH HQHUJ\ RI WKH HPLWWHG SKRWRQ KYAf DQG WKH YROXPH HOHPHQW REVHUYHG 9 LQ FPf e!H QMKYf $ Y 7KLV YDOXH DV ZHOO DV WKH QXPEHU GHQVLW\ RI H[FLWHG DWRPV LV SURSRUWLRQDO WR WKH DQDO\WH FRQFHQWUDWLRQ LQ WKH VDPSOH 7KLV UHODWLRQVKLS LV JRRG RQO\ IRU ORZ FRQFHQWUDWLRQV %\ PHDVXULQJ WKH LQWHQVLW\ RI HPLVVLRQ IURP VWDQGDUGV RI YDULRXV FRQFHQWUDWLRQV RI WKH DQDO\WH WKH H[DFW UHODWLRQVKLS EHWZHHQ DQDO\WH FRQFHQWUDWLRQ DQG p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

PAGE 17

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f DUH FXUUHQWO\ WKH PRVW ZLGHO\ XVHG 0LFURZDYH SODVPDV DUH DOVR HIIHFWLYH DWRPLF HPLVVLRQ VRXUFHV 7ZR W\SHV RI PLFURZDYH SODVPDV DUH WKH PLFURZDYH LQGXFHG SODVPD 0,3f DQG WKH FDSDFLWLYHO\ FRXSOHG PLFURZDYH SODVPD &03f &KRLFH RI (PLVVLRQ/LQHV 7KH DWRPLF HPLVVLRQ OLQHV DUH VSHFWUDOO\ VHSDUDWHG E\ XVLQJ DQ RSWLFDO GLVSHUVLRQ GHYLFH W\SLFDOO\ D JUDWLQJ RU D SULVP 7KH HPLVVLRQ OLQHV PXVW EH FKRVHQ FDUHIXOO\ IRU

PAGE 18

RSWLPXP VLJQDOWRQRLVH 61f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n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

PAGE 19

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

PAGE 20

VHSDUDWHG E\ D FRQWLQXRXV VROLG GLHOHFWULF 7KH PLFURZDYHV WUDYHO WKURXJK WKH GLHOHFWULF >@ &RD[LDO FDEOHV DUH FDSDEOH RI D ODUJH EDQGZLGWK DQG DUH VPDOO LQ VL]H EXW KDYH WKH GLVDGYDQWDJHV RI KLJK DWWHQXDWLRQ DQG FDQQRW KDQGOH KLJK SRZHUV 7KH ZDYHJXLGH FDQ EH HLWKHU D FLUFXODU RU UHFWDQJXODU KROORZ SLSH ,W LV FDSDEOH RI KDQGOLQJ KLJK SRZHUV ZLWK ORZ ORVV EXW LV ODUJH LQ VL]H DQG RQO\ KDV D QDUURZ EDQGZLGWK 7KH ILUVW PLFURZDYH GLVFKDUJH ZDV REVHUYHG LQ WKH nV E\ HOHFWULFDO HQJLQHHUV DQG SK\VLFLVWV ZRUNLQJ RQ UDGDU HTXLSPHQW >@ ,W ZDV YLHZHG DV D QXLVDQFH LQVWHDG RI D SRWHQWLDO WHFKQRORJLFDO DGYDQFHPHQW ,Q &RELQH DQG :LOEXU GHVFULEHG VRPH RI WKH IHDWXUHV RI D PLFURZDYH SODVPD >@ 7KH\ GHVFULEHG WKH SODVPD XVLQJ KHOLXP DUJRQ DLU R[\JHQ DQG QLWURJHQ DV WKH VXSSRUW JDVHV ,Q %URLGD DQG &KDSPDQ XVHG D PLFURZDYHLQGXFHG SODVPD 0,3f WR DQDO\]H QLWURJHQ LVRWRSHV >@ .HVVOHU DQG *HEKDUGW XVHG D FDSDFLWLYHO\ FRXSOHG PLFURZDYH SODVPD &03f WR DQDO\]H OLPHVWRQH LQ >@ 0DYURGLQHDQX DQG +XJKHV XVHG D PLFURZDYH SODVPD WRUFK LQ WR YLHZ WKH HPLVVLRQ VSHFWUD RI VHYHUDO HOHPHQWV E\ LQWURGXFLQJ VROXWLRQV LQWR WKH FUDWHU RI D JUDSKLWH GLVFKDUJH WLS >@ )DOOJDWWHU HW DO H[DPLQHG DQ DUJRQ PLFURZDYH SODVPD DV DQ H[FLWDWLRQ VRXUFH IRU DWRPLF HPLVVLRQ VSHFWURPHWU\ LQ >@ 7KH

PAGE 21

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f )RU D &03 D PDJQHWURQ PLFURZDYH SRZHU WXEHf JHQHUDWHV WKH PLFURZDYHV ZKLFK DUH FRQGXFWHG WKURXJK D FRD[LDO ZDYH JXLGH :LWKLQ WKH ZDYHJXLGH D VWDQGLQJ ZDYH LV SURGXFHG ZKLFK EXLOGV XS PLFURZDYH HQHUJ\ WKDW LV WUDQVIHUUHG WR WKH WLS RI D FHQWUDO VLQJOH HOHFWURGH %\ RVFLOODWLQJ LQ WKH PLFURZDYH ILHOG WKH HOHFWURQV JDLQ HQRXJK NLQHWLF HQHUJ\ WR FROOLVLRQDOO\ LRQL]H WKH VXSSRUW JDV 7KLV SURGXFHV D IODPHOLNH SODVPD DW WKH WLS RI WKH HOHFWURGH 7KH SODVPD WKDW LV SURGXFHG LV FDSDEOH RI DWRPL]LQJ DQG H[FLWLQJ WKH DQDO\WH LQ D VDPSOH 7KH VLJQDO LV PHDVXUHG E\ IRFXVLQJ WKH HPLVVLRQ RQ WKH HQWUDQFH VOLW RI D VSHFWURPHWHU 7KH PXOWLHOHPHQW HPLVVLRQ LV XVXDOO\ PHDVXUHG ZLWK D SKRWRGLRGH DUUD\ 3'$f RU D FKDUJH FRXSOHG GHYLFH &&'f

PAGE 22

6HYHUDO SDUDPHWHUV PXVW EH RSWLPL]HG LQ RUGHU WR REWDLQ VDWLVIDFWRU\ UHVXOWV ZLWK D &03 7KHVH SDUDPHWHUV LQFOXGH WKH PLFURZDYH SRZHU WKH SODVPD JDV IORZ UDWH DQG WKH SRVLWLRQ RI WKH HOHFWURGH ZLWK UHVSHFW WR WKH GHWHFWRU 2SWLPXP PLFURZDYH SRZHUV GLIIHU GHSHQGLQJ RQ WKH W\SH RI VDPSOHV DQG WKH PHWKRG RI VDPSOH LQWURGXFWLRQ +HOLXP LV XVHG PRVW RIWHQ DV WKH VXSSRUW JDV ZLWK IORZ UDWHV UDQJLQJ IURP WR /PLQ >@ 6SHQFHU HW DO VWXGLHG YDULRXV SDUDPHWHUV IRU D KLJK IORZ UDWH /PLQf &03 >@ 7KH WHPSHUDWXUH PHDVXUHPHQWV ZHUH PDGH ZLWK WKH IROORZLQJ SODVPD FRQGLWLRQV /PLQ KHOLXP FPPLQ K\GURJHQ DQG : RI DSSOLHG SRZHU 7KH IROORZLQJ UHVXOWV ZHUH REWDLQHG IRU WKH DQDO\VLV RI DTXHRXV VROXWLRQV H[FLWDWLRQ WHPSHUDWXUH DQG HOHFWURQ QXPEHU GHQVLW\ [ FPn 7KH\ GHWHUPLQHG WKDW WKH YDOXHV RI 7H[F DQG QH DUH QRW VWDWLVWLFDOO\ GLIIHUHQW IRU WKH LQWURGXFWLRQ RI DTXHRXV DQG RUJDQLF VROXWLRQV LQWR WKH SODVPD 0LFURZDYH ,QGXFHG 3ODVPD 0,3f 0LFURZDYH LQGXFHG SODVPDV 0,3f DUH FUHDWHG E\ XVLQJ DQ H[WHUQDO UHVRQDQW FDYLW\ RU VRPH RWKHU VWUXFWXUH WR FRXSOH PLFURZDYH HQHUJ\ WR D VWUHDP RI JDV LQ D TXDUW] WXEH 0,3nV DUH VXVWDLQHG DW ORZ SRZHUV WR :f ZLWK DUJRQ RU

PAGE 23

KHOLXP DV WKH VXSSRUW JDV >@ $ PLFURZDYH SRZHU VXSSO\ LV DWWDFKHG WR DQ DQWHQQD RU FLUFXLW ORRS E\ D FRD[LDO FDEOH 7KH HQHUJ\ JRHV WKURXJK WKH DQWHQQD RU ORRS DQG LV LQWURGXFHG LQWR WKH UHVRQDQW FDYLW\ JHQHUDWLQJ D VWDQGLQJ ZDYH $ TXDUW] WXEH LV SODFHG LQ WKH FDYLW\ LQ VXFK D ZD\ WKDW LWV D[LV LV SDUDOOHO WR WKH OLQH RI HOHFWULF ILHOG RVFLOODWLRQ 0,3nV WKDW XVH DQ HOHFWURWKHUPDO W\SH RI DWRPL]HU KDYH UHVXOWHG LQ WKH EHVW GHWHFWLRQ OLPLWV >@ 0LFURZDYH LQGXFHG SODVPDV DUH PRUH ZLGHO\ XVHG WKDQ FDSDFLWLYHO\ FRXSOHG PLFURZDYH SODVPDV EHFDXVH 0,3nV UHTXLUH ORZHU SRZHU DQG FDQ EH RSHUDWHG DW DWPRVSKHULF SUHVVXUH ,Q DGGLWLRQ &03nV LQYROYH WKH XVH RI DQ HOHFWURGH ZKLFK FDQ FDXVH VSHFWURVFRSLF FRQWDPLQDWLRQ DQG PHPRU\ HIIHFWV LI LW HURGHV >@ +RZHYHU &03nV GR KDYH VHYHUDO DGYDQWDJHV RYHU 0,3nV 0,3nV FDQ RQO\ EH RSHUDWHG DW ORZ SRZHUV ZKLOH &03nV DUH VWDEOH RYHU D ZLGH UDQJH RI SRZHU OHYHOV :f $W KLJKHU SRZHUV WKHUH DUH IHZHU PDWUL[ HIIHFWV DQG PRUH LQWHQVH VLJQDOV $OVR D ZLGH UDQJH RI JDVHV FDQ EH XVHG WR VXVWDLQ &03nV DQG &03nV DUH PRUH WROHUDQW WR WKH LQWURGXFWLRQ RI IRUHLJQ PDWHULDOV WKDQ 0,3nV >@ 6DPSOH LQWURGXFWLRQ SUREOHPV KDYH KLQGHUHG WKH GHYHORSPHQW RI FRPPHUFLDO 0,3 LQVWUXPHQWV >@ 0HPRU\ HIIHFWV DUH DOVR D SUREOHP LQ 0,3 DWRPLF HPLVVLRQ VSHFWURVFRS\ >@ 7KH PHPRU\ HIIHFWV DUH SUREDEO\ D UHVXOW RI HWFKLQJ RI WKH TXDUW] WXEH E\ WKH SODVPD SURYLGLQJ D UHJLRQ ZKHUH DQDO\WH

PAGE 24

DWRPV FDQ FROOHFW $Q 0,3 LV PRVW XVHIXO DV DQ H[FLWDWLRQ VRXUFH ZKHQ LW LV FRPELQHG ZLWK D VHSDUDWH VDPSOH DWRPL]HU 0LFURZDYH 3ODVPD 7RUFK -LQ HW DO GHYHORSHG D QHZ W\SH RI PLFURZDYH SODVPD FDOOHG WKH PLFURZDYH SODVPD WRUFK 037f >@ $ 037 FRQWDLQV WKUHH FRQFHQWULF WXEHV ZLWK WKH RXWHU WXEH PDGH RI EUDVV DQG WKH LQQHU WXEHV PDGH RI FRSSHU 7KH RXWHU WXEH VHUYHV DV WKH PLFURZDYH FDYLW\ ZKLFK FRXSOHV WKH PLFURZDYH HQHUJ\ WR WKH WRUFK IRUPLQJ D SODVPD DW WKH WRS RI WKH WRUFK 7KH FDUULHU JDV FRQWDLQLQJ WKH VDPSOH DHURVRO HQWHUV WKH LQQHU WXEH DQG WKH SODVPD JDV KHOLXP RU DUJRQf IORZV WKURXJK WKH PLGGOH WXEH 7KLV PLFURZDYH SODVPD LV YHU\ VWDEOH DQG KDV D KLJK WROHUDQFH WR WKH LQWURGXFWLRQ RI IRUHLJQ PDWHULDOV >@ 7KH OLQHDU G\QDPLF UDQJH IRU WKH 037 ZDV JHQHUDOO\ PRUH WKDQ WKUHH RUGHUV RI PDJQLWXGH DQG WKH GHWHFWLRQ OLPLWV IRU UDUH HDUWK HOHPHQWV ZHUH LQ WKH SDUWSHUELOOLRQ SSEf UDQJH >@ 7KLV LV D VLJQLILFDQW DGYDQFHPHQW RYHU WKH 0,3 EHFDXVH WKH 037 FDQ ZLWKVWDQG WKH LQWURGXFWLRQ RI ZHW DHURVROV 6ROXWLRQV DUH QHEXOL]HG E\ DQ XOWUDVRQLF QHEXOL]HU DQG WKH UHVXOWLQJ DHURVRO LV LQWURGXFHG WKURXJK D GHVROYDWLRQGHVVLFDWRU V\VWHP 7KH 037 GRHV KRZHYHU VXIIHU IURP PDWUL[ HIIHFWV DQG DLU HQWUDLQPHQW LQ WKH WRUFK

PAGE 25

&RPSDULVRQ WR WKH ,QGXFWLYHO\ &RXSOHG 3ODVPD 7&3f 7KH LQGXFWLYHO\ FRXSOHG SODVPD ,&3f LV ZLGHO\ XVHG LQ LQGXVWU\ DQG UHVHDUFK 7KH ,&3 KDV D VRPHZKDW KLJKHU WHPSHUDWXUH WKDQ WKH PLFURZDYH SODVPD DQG SURGXFHV D KLJK GHJUHH RI H[FLWDWLRQ 7KH ,&3 FRQVLVWV RI VHYHUDO FRPSRQHQWV $ JDV W\SLFDOO\ DUJRQ IORZV WKURXJK D WRUFK PDGH RXW RI WKUHH FRQFHQWULF TXDUW] WXEHV 7KH WRS RI WKH WRUFK LV LPPHUVHG LQ D KLJK HQHUJ\ LQGXFWLRQ FRLO ZKLFK FDUULHV UDGLRIUHTXHQF\ SRZHU DW RU 0+]f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

PAGE 26

&03 LV EHWWHU DEOH WR DQDO\]H FRPSOH[ PDWULFHV 7KLV IHDWXUH RI WKH &03 FDQ EH XVHG IRU GLUHFW HOHPHQWDO DQDO\VLV LQ EORRG

PAGE 27

7DEOH &RPSDULVRQ RI LQGXFWLYHO\ FRXSOHG SODVPD ,&3f FDSDFLWLYHO\ FRXSOHG PLFURZDYH SODVPD &03f PLFURZDYH LQGXFHG SODVPD ,&3f DQG PLFURZDYH SODVPD WRUFK 037f IRU DWRPLF HPLVVLRQ VSHFWURPHWU\ >@ ,&3 &03 0,3 037 *DV $UJRQ +HOLXP $UJRQ RU +HOLXP $UJRQ RU +HOLXP 3RZHU :f *DV WHPSHUDWXUH .f 5HODWLYH VWDQGDUG GHYLDWLRQ b b b b /LQHDU G\QDPLF UDQJH a a a a /LPLW RI GHWHFWLRQ SSEf

PAGE 28

&+$37(5 &/,1,&$/ (/(0(17$/ $1$/<6,6 ,1 %/22' ,QWURGXFWLRQ 7KH KXPDQ ERG\ UHTXLUHV D GHOLFDWH EDODQFH RI WKH OHYHOV RI YDULRXV HOHPHQWV 7RR PXFK RU WRR OLWWOH RI D SDUWLFXODU HOHPHQW FDQ KDYH GHYDVWDWLQJ SK\VLRORJLFDO HIIHFWV 6RPH W\SLFDO DLOPHQWV DUH D UHVXOW RI DQ LPEDODQFH RI HOHPHQWV LQ WKH ERG\ +LJK OHYHOV RI VRGLXP DQG ORZ OHYHOV RI SRWDVVLXP PDJQHVLXP DQG FDOFLXP DOO OHDG WR K\SHUWHQVLRQ KLJK EORRG SUHVVXUHf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

PAGE 29

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

PAGE 30

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f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

PAGE 31

VDPH ZD\ FDOFLXP LV @ ,Q EORRG b RI WKH OHDG LV ERXQG WR WKH KHPRJORELQ :LWKLQ WKH SDVW ILYH \HDUV LW KDV EHHQ IRXQG WKDW OHDG FRQFHQWUDWLRQV DV ORZ DV SSE LQ WKH EORRG FDQ EH GHWULPHQWDO WR WKH KHDOWK DQG LQWHOOHFWXDO GHYHORSPHQW RI D FKLOG > @ )LJXUH VKRZV WKH KHDOWK HIIHFWV RI YDULRXV OHYHOV LQ WKH EORRG >@ $FXWH OHDG SRLVRQLQJ FDQ UHVXOW LQ DQRUH[LD G\VSHSVLD DQG FRQVWLSDWLRQ IROORZHG E\ DEGRPLQDO SDLQ >@ 7KH GHWULPHQWDO HIIHFW RI OHDG SRLVRQLQJ RQ \RXQJ FKLOGUHQ KDV OHG WKH &HQWHUV IRU 'LVHDVH &RQWURO DQG 3UHYHQWLRQ &'&f WR ORZHU WKH DFFHSWDEOH OHYHO RI OHDG FRQFHQWUDWLRQV LQ WKH EORRG RI FKLOGUHQ WR SSE FRPSDUHG WR D OHYHO RI SSE FRQVLGHUHG DFFHSWDEOH IURP WR 7KH V\PSWRPV RI OHDG SRLVRQLQJ DUH RIWHQ LQYLVLEOH DW ILUVW SUHYHQWLQJ WKH GLDJQRVLV DQG WUHDWPHQW RI PRVW FDVHV 7KH QXPEHU RI OHDG SRLVRQLQJ FDVHV FDQ EH JUHDWO\ UHGXFHG LI D ODUJH VFDOH VFUHHQLQJ SURJUDP LV LPSOHPHQWHG 7KLV ZRXOG UHTXLUH DQ LQH[SHQVLYH HDV\WRXVH PHWKRG WR GHWHFW WUDFH DPRXQWV RI OHDG LQ EORRG

PAGE 32

&RQFHQWUDWLRQ RI OHDG LQ EORRG +s!f +HDOWK HIIHFW LQ KXPDQV 'HDWK &KLOGUHQf %UDLQ DQG NLGQH\ GDPDJH DGXOWVf %UDLQ DQG NLGQH\ GDPDJH FKLOGUHQf ,QFUHDVHG EORRG SUHVVXUH PLGGOHDJHG PHQf 'HFUHDVHG ,4 DQG JURZWK LQ \RXQJ FKLOGUHQ 3UHWHUP ELUWK UHGXFHG ELUWK ZHLJKW DQG GHFUHDVHG PHQWDO DELOLW\ LQ LQIDQWV IURP PRWKHUnV H[SRVXUH GXULQJ SUHJQDQF\ )LJXUH +HDOWK HIIHFWV RI OHDG SRLVRQLQJ f

PAGE 33

0DQJDQHVH 0DQJDQHVH 0Qf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f LV XVHG LQ WKH WUHDWPHQW RI PDQLF GHSUHVVLYH SV\FKRVLV >@ /LWKLXP LV DGPLQLVWHUHG LQ WKH IRUP RI OLWKLXP FDUERQDWH RU DQRWKHU OLWKLXP VDOW ZLWK DV

PAGE 34

PXFK DV PJ WDNHQ GDLO\ >@ %ORRG QRUPDOO\ RQO\ FRQWDLQV OLWKLXP DW D OHYHO RI ORZ SSE EXW IRU WKHUDSHXWLF OLWKLXP OHYHOV D UDQJH RI P0 LV PDLQWDLQHG LQ WKH EORRG >@ 7KLV LV FORVH WR WKH WR[LF OHYHO DQG D OHYHO RI P0 FDQ EH OHWKDO 7KLV QHFHVVLWDWHV WKH PRQLWRULQJ RI OLWKLXP OHYHOV LQ SDWLHQWV UHFHLYLQJ WKLV W\SH RI WUHDWPHQW =LQF =LQF =Qf LV WKH VHFRQG PRVW SOHQWLIXO WUDFH HOHPHQW LQ WKH ERG\ =LQF LV LPSRUWDQW LQ WKH PHWDEROLF IXQFWLRQV RI WKH ERG\ DQG LV HVVHQWLDO IRU WKH SURGXFWLRQ DQG IXQFWLRQLQJ RI RYHU HQ]\PHV WKDW FRQWDLQ ]LQF >@ =LQF LV DOVR YLWDO LQ WKH V\QWKHVLV RI '1$ DQG 51$ LQ HYHU\ OLYLQJ FHOO =LQF SOD\V D UROH LQ LPPXQH IXQFWLRQV LQ JURZWK DQG GHYHORSPHQW DQG LQ WKH V\QWKHVLV DQG UHOHDVH RI WHVWRVWHURQH =LQF LV HVSHFLDOO\ LPSRUWDQW LQ H[SHFWDQW PRWKHUV DQG LQ WKH JURZWK RI \RXQJ FKLOGUHQ >@ =LQF SOD\V D PDMRU UROH LQ ILJKWLQJ LQIHFWLRQV DQG LQ WKH KHDOLQJ SURFHVV >@ 7KRVH DW ULVN IRU ]LQF GHILFLHQF\ LQFOXGH ZRPHQ RI FKLOG EHDULQJ DJH \RXQJ FKLOGUHQ DQG WKH HOGHUO\ >@ ,I WKH ]LQF OHYHO LV WRR ORZ LW FDQ FDXVH FRQJHQLWDO PDOIRUPDWLRQV LQFOXGLQJ VSLQD ELILGD DQG FHQWUDO QHUYRXV V\VWHP DEQRUPDOLWLHV ,W FDQ DOVR FDXVH VHYHUH JURZWK UHWDUGDWLRQ DUUHVWHG VH[XDO PDWXULW\ DQG D ORVV RI DSSHWLWH >@ 7KH OHYHO RI ]LQF LV HVSHFLDOO\ FULWLFDO LQ WKH HOGHUO\ EHFDXVH RI WKH GHWHULRUDWLRQ RI LPPXQH IXQFWLRQ

PAGE 35

ZLWK DJH /RZ ]LQF OHYHOV FDQ LQGLFDWH GLDEHWHV EHFDXVH ]LQF LV LPSRUWDQW LQ WKH VWRUDJH DQG UHOHDVH RI LQVXOLQ $ ]LQF LPEDODQFH PD\ EH LQYROYHG LQ K\SHUWHQVLRQ 0RVW FDVHV RI ]LQF WR[LFLW\ KDYH EHHQ UHODWHG WR IRRG SRLVRQLQJ LQFLGHQWV DQG WR LQGXVWULDO SROOXWLRQ >@ 7RR PXFK ]LQF FDXVHV DQHPLD UHGXFHG KHPRJORELQ SURGXFWLRQf HOHYDWHG ZKLWH EORRG FHOO FRXQW PXVFXODU SUREOHPV H[KDXVWLRQ GLDUUKHD QDXVHD DQG GL]]LQHVV >@ 9HU\ KLJK OHYHOV RI ]LQF FDQ LPSDLU PHWDEROLF IXQFWLRQV WKDW DUH GHSHQGHQW RQ RWKHU WUDFH HOHPHQWV >@ +LJK OHYHOV RI ]LQF FDQ DOVR LQWHUIHUH ZLWK WKH DEVRUSWLRQ RI FRSSHU ZKLFK FDQ SURYRNH LURQ GHILFLHQF\ DQG DQHPLD >@ 0DJQHVLXP 0DJQHVLXP 0Jf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

PAGE 36

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

PAGE 37

0HWKRGV RI $QDO\VLV /HDG 7KH &HQWHUV IRU 'LVHDVH &RQWURO DQG 3UHYHQWLRQ KDV VHW IRUWK D QXPEHU RI GHVLUDEOH FKDUDFWHULVWLFV IRU DQ LPSURYHG EORRG OHDG PHDVXUHPHQW V\VWHP 7KHVH FKDUDFWHULVWLFV LQFOXGH DQ DFFXUDF\ DQG SUHFLVLRQ RI s SSE DW SSE D GHWHFWLRQ OLPLW RI SSE D VDPSOH YROXPH RI OHVV WKDQ IL/ D ORZ FRVWSHUWHVW DQ DQDO\VLV WLPH XQGHU ILYH PLQXWHV SRUWDELOLW\ DQG PLQLPDO RSHUDWRU WUDLQLQJ UHTXLUHG WR SHUIRUP WKH PHWKRG 6FUHHQLQJ PHWKRGV &XUUHQWO\ XVHG VFUHHQLQJ PHWKRGV IRU OHDG LQ EORRG ZKLFK PHDVXUH WKH OHYHO RI HLWKHU HU\WKURF\WH SURWRSRUSK\ULQ (3f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

PAGE 38

SRUSK\ULQV DUH WKHQ VHSDUDWHG IURP WKH EORRG DQG PHDVXUHG E\ PROHFXODU IOXRURPHWU\ 7KLV WHVW KDV EHHQ UHFRPPHQGHG E\ WKH &'& VLQFH >@ +HPDWRIOXRURPHWHUV KDYH DOVR EHHQ XVHG WR VFUHHQ FKLOGUHQ IRU OHDG >@ 7KHVH DUH SRUWDEOH LQVWUXPHQWV WKDW PHDVXUH WKH ]LQF SURWRSRUSK\ULQ GLUHFWO\ LQ D VLQJOH GURS RI EORRG 7ZR FXUUHQW PHWKRGV EHLQJ GHYHORSHG DV SRUWDEOH VFUHHQLQJ PHWKRGV DUH DQRGLF VWULSSLQJ YROWDPPHWU\ $69f >@ DQG SRWHQWLRPHWULF VWULSSLQJ DQDO\VLV 36$f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

PAGE 39

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f KDV GHYHORSHG D FRPPHUFLDO DWRPLF DEVRUSWLRQ VSHFWURPHWU\ $$6f LQVWUXPHQW WKDW FDQ EH XVHG IRU EORRG OHDG VFUHHQLQJ >@ 7KH OHDG DEVRUSWLRQ OLQH DW QP LV XVHG ZLWK QHDU OLQH EDFNJURXQG FRUUHFWLRQ XVLQJ WKH QRQDEVRUELQJ QP OHDG OLQH 7KLV LQVWUXPHQW XVHG D : WXQJVWHQ FRLO ILODPHQW LQ DQ HQFORVHG FKDPEHU 7XQJVWHQ FRLOV DUH H[FHOOHQW DWRPL]DWLRQ VRXUFHV EHFDXVH RI WKHLU KLJK KHDWLQJ UDWH DQG WKHLU FRPPHUFLDO DYDLODELOLW\ 7XQJVWHQ FRLOV WKDW DUH PDGH IRU KDORJHQ SURMHFWRU ODPSV FDQ EH XVHG VR WKH\ DUH

PAGE 40

UHODWLYHO\ LQH[SHQVLYH 2QH FRLO FDQ ODVW IRU DSSUR[LPDWHO\ UXQV 7KH EORRG VDPSOHV ZHUH GLOXWHG E\ D IDFWRU RI WHQ ZLWK b QLWULF DFLG b 7ULWRQ [ DQG b 1++3 &DOLEUDWLRQ LV GRQH ZLWK DTXHRXV VWDQGDUGV DQG D GHWHFWLRQ OLPLW RI SSE ZLWK D 56' RI b DW SSE LV REWDLQHG 7KLV PHWKRG SURGXFHV UHVXOWV LQ OHVV WKDQ PLQXWHV KDV D ORZ FRVWSHUWHVW DQG LV HDV\ WR RSHUDWH >@ 5HFHQWO\ D SRUWDEOH EDWWHU\ SRZHUHG $$6 ZDV GHYHORSHG E\ -RQHV DQG FRZRUNHUV IRU OHDG LQ EORRG VFUHHQLQJ >@ $ WXQJVWHQ FRLO ZDV XVHG DV WKH DWRPL]HU DQG D PLQLDWXUH ILEHU RSWLF VSHFWURPHWHU ZLWK D FKDUJH FRXSOHG GHYLFH &&'f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

PAGE 41

PDJQLWXGH DQG WKH SUHFLVLRQ ZDV b 7KH PHWKRG ZDV SURYHQ WR EH DFFXUDWH E\ DQDO\]LQJ 1,67 EORRG VWDQGDUGV 7KH FRLO ZDV XVHG LQ WKH DQDO\VLV RI XS WR VDPSOHV >@ &OLQLFDO PHWKRGV 5HVHDUFK LV EHLQJ GRQH E\ PDQ\ GLIIHUHQW JRYHUQPHQW DJHQFLHV DQG XQLYHUVLWLHV WR LPSURYH EORRG OHDG PHDVXUHPHQW ,VRWRSH GLOXWLRQ LQGXFWLYHO\ FRXSOHG PDVV VSHFWURPHWU\ ,' ,&306f >@ DQG JUDSKLWH IXUQDFH DWRPLF DEVRUSWLRQ VSHFWURPHWU\ *)$$6f >@ DUH PHWKRGV WKDW DUH DEOH WR GHWHFW WUDFH DPRXQWV RI OHDG LQ EORRG EHORZ WKH OHYHO RI FRQFHUQ SSEf %RWK RI WKHVH PHWKRGV DUH YHU\ DFFXUDWH DQG SUHFLVH EXW KDYH WKH GLVDGYDQWDJHV RI UHTXLULQJ VDPSOH SUHWUHDWPHQW DQG H[SHQVLYH LQVWUXPHQWDWLRQ 7KH H[SHQVH RI WHVWLQJ LV D PDMRU FRQVLGHUDWLRQ VLQFH PLOOLRQV RI FKLOGUHQ ZRXOG QHHG WR EH WHVWHG LQ D ODUJHVFDOH SXEOLF KHDOWK VFUHHQLQJ SURJUDP $WRPLF DEVRUSWLRQ VSHFWURPHWU\ $$6f *UDSKLWH IXUQDFH DWRPLF DEVRUSWLRQ VSHFWURPHWU\ *)$$6f LV RQH RI WKH PRVW SRSXODU PHWKRGV IRU OHDG LQ EORRG DQDO\VLV >@ *)$$6 KDV H[FHOOHQW VHQVLWLYLW\ DQG VHOHFWLYLW\ ODUJH WKURXJKSXW DQG LV FDSDEOH RI DQDO\]LQJ YHU\ VPDOO YROXPHV 0DQ\ *)$$6 PHWKRGV XVH D /nYRY SODWIRUP ZKLFK LV D VPDOO SODWIRUP SODFHG LQ WKH JUDSKLWH WXEH WR KROG WKH VDPSOH DQG HQVXUH WKDW WKH WXEH DQG VDPSOH FRPH WR WKH VDPH WHPSHUDWXUH DW WKH VDPH WLPH ,Q WKH &HQWHUV IRU 'LVHDVH &RQWURO &'&f

PAGE 42

VXUYH\HG WKH PHWKRGV EHLQJ XVHG E\ FOLQLFDO ODERUDWRULHV IRU EORRG OHDG DQDO\VLV 2I WKH ODERUDWRULHV VXUYH\HG b XVHG *)$$6 b RI WKH ODEV XVHG 'HOYHV FXS $$6 b XVHG H[WUDFWLRQ $$6 b XVHG FDUERQ URG $$6 DQG b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b VROXWLRQ RI 7ULWRQ ; D VXUIDFWDQW FDXVHV FRPSOHWH

PAGE 43

O\VLV RI WKH EORRG FHOOV DQG SURGXFHV D FOHDU VROXWLRQ WKDW PLQLPL]HV WKH QHJDWLYH HIIHFWV RI WKH EORRG PDWUL[ >@ 7KH SUREOHP RI FDUERQDFHRXV UHVLGXH EXLOG XS FDQ EH YLUWXDOO\ HOLPLQDWHG E\ GHSURWHLQL]DWLRQ RI WKH EORRG ZLWK b QLWULF DFLG 7KH VXSHUQDWDQW RI WKH UHVXOWLQJ VDPSOH FDQ WKHQ EH LQMHFWHG LQWR WKH JUDSKLWH WXEH 7KLV SURFHGXUH GHVWUR\V WKH EXON RI WKH RUJDQLF PDWWHU LQ WKH EORRG +RZHYHU WKH XVH RI QLWULF DFLG VKRUWHQV WKH OLIH RI WKH JUDSKLWH WXEH EHFDXVH RI WKH R[LGDWLRQ RI WKH WXEHn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

PAGE 44

$ *)$$6 PHWKRG KDV EHHQ GHYHORSHG ZKLFK DOORZV DTXHRXV VWDQGDUGV WR EH XVHG IRU EORRG OHDG DQDO\VLV >@ 3ULRU WR DQDO\VLV WKH EORRG LV GHSURWHLQL]HG ZLWK D b QLWULF DFLG VROXWLRQ FRQWDLQLQJ b 7ULWRQ ; 7KH VXSHUQDWDQW LV FROOHFWHG DQG WKH FRQFHQWUDWLRQ RI OHDG LV PHDVXUHG XVLQJ =HHPDQ *)$$6 3DUVRQV DQG FRZRUNHUV KDYH DOVR GHYHORSHG D PHWKRG FDSDEOH RI FDOLEUDWLQJ ZLWK DTXHRXV VWDQGDUGV > @ $ WUDQVYHUVHO\ KHDWHG JUDSKLWH WXEHSODWIRUP FDOOHG D VWDELOL]HG WHPSHUDWXUH SODWIRUP IXUQDFH 673)f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b :KLOH ERWK RI WKHVH PHWKRGV DUH DGYDQWDJHRXV EHFDXVH DTXHRXV VWDQGDUGV FDQ EH XVHG IRU FDOLEUDWLRQ WKH\ KDYH WKH GLVDGYDQWDJH RI UHTXLULQJ DSSUHFLDEOH VDPSOH WUHDWPHQW $ IODPH $$6 PHWKRG KDV EHHQ GHYHORSHG WKDW XVHG / RI EORRG VDPSOHV VSRWWHG RQ ILOWHU SDSHU DQG WKHQ DQDO\]HG

PAGE 45

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n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

PAGE 46

QHEXOL]DWLRQ $Q DTXHRXV GHWHFWLRQ OLPLW RI SSE ZDV UHSRUWHG IRU OHDG ZLWK D UHODWLYH VWDQGDUG GHYLDWLRQ 56'f RI b ,QGXFWLYHO\ FRXSOHG SODVPD PDVV VSHFWURPHWU\ ,&306f‘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f ,&306 IRU WKH DQDO\VLV RI LWV FHUWLILHG UHIHUHQFH PDWHULDO OHDG LQ ERYLQH EORRG IURP LWV %ORRG /HDG /DERUDWRU\ 5HIHUHQFH 6\VWHP $Q DOLTXRW RI WKH ZKROH EORRG VDPSOH LV VSLNHG ZLWK D UDGLRJHQLF OHDG LVRWRSLF VWDQGDUG 7KLV DOLTXRW DORQJ ZLWK DQ XQVSLNHG DOLTXRW LV WKHQ GLJHVWHG ZLWK XOWUDSXUH QLWULF DFLG LQ D PLFURZDYH RYHQ $IWHU FRROLQJ ERWK VDPSOHV DUH GLOXWHG DQG

PAGE 47

WKHQ DVSLUDWHG LQWR DQ ,&306 7KH LVRWRSH UDWLRV RI OHDG DW PDVV DQG PDVV DUH WKHQ PHDVXUHG :KLOH WKLV PHWKRG LV YHU\ DFFXUDWH DQG SUHFLVH IRU GHWHUPLQLQJ OHDG LQ EORRG LW LV PRUH VXLWDEOH IRU GHWHUPLQLQJ UHIHUHQFH YDOXHV WKDQ EHLQJ XVHG DV D FOLQLFDO PHWKRG EHFDXVH RI LWnV KLJK FRVW DQG ORZ WKURXJKSXW VDPSOHV SHU GD\f > @ 3ULPDU\ DQG 7UDFH (OHPHQWV 7KH PDLQ PHWKRGV IRU WUDFH HOHPHQWDO DQDO\VLV LQ WKH FOLQLFDO ODERUDWRU\ DUH DEVRUSWLRQ RU HPLVVLRQ VSHFWURn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

PAGE 48

&KHPLVWU\ >@ DQG LQ WKH -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ >@ $WRPLF DEVRUSWLRQ VSHFWURPHWU\ $$6f 6RGLXP SRWDVVLXP ]LQF PDJQHVLXP DQG LURQ EORRG OHYHOV FDQ EH GHWHUPLQHG E\ IODPH DWRPLF DEVRUSWLRQ VSHFWURSKRWRPHWU\ )$$6f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f RU LRQ VHOHFWLYH HOHFWURGHV ,6(f EXW LW LV OHVV SUHFLVH DQG QRW DV VXLWDEOH IRU URXWLQH FOLQLFDO DQDO\VLV ,W KDV D KLJK LQLWLDO FRVW DQG WKH QHFHVVLW\ IRU FRPSUHVVHG JDVHV DQG IODPHV DUH XQGHVLUDEOH LQ WKH FOLQLFDO ODERUDWRU\ *)$$6 LV D YHU\ SRSXODU PHWKRG IRU HOHPHQWDO DQDO\VLV LQ EORRG 7KH YDULRXV PHWKRGV XVHG IRU OHDG DQDO\VLV DUH DOVR XVHG IRU PDQ\ RWKHU HOHPHQWV DQG KDYH WKH VDPH

PAGE 49

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f 6RGLXP DQG SRWDVVLXP LQ VHUXP DUH XVXDOO\ DQDO\]HG E\ HLWKHU IODPH DWRPLF HPLVVLRQ VSHFWURPHWU\ )$(6f RU E\ LRQ VHOHFWLYH HOHFWURGH SRWHQWLRPHWU\ ,6(f >@ )$(6 UHTXLUHV D GLOXWLRQ RI WKH VDPSOH E\ WR WLPHV RIWHQ DGGLQJ OLWKLXP RU FHVLXP WR WKH VDPSOH DV DQ LQWHUQDO VWDQGDUG DQG LRQL]DWLRQ VXSSUHVVDQW $Q DLUSURSDQH IODPH LV XVHG DQG WKH VRGLXP HPLVVLRQ LV PRQLWRUHG DW QP DQG WKH SRWDVVLXP HPLVVLRQ DW QP 2QO\ WR b RI WKH DWRPV LQ WKH IODPH DUH H[FLWHG WR HPLVVLRQ EXW WKH FRQFHQWUDWLRQ RI WKH HOHPHQWV LV VXIILFLHQW IRU DFFXUDWH DQG SUHFLVH PHDVXUHPHQWV >@ /LWKLXP OHYHOV FDQ DOVR EH UHOLDEO\ PHDVXUHG XVLQJ IODPH HPLVVLRQ VSHFWURPHWU\ >@ )ODPH SKRWRPHWULF IORZLQMHFWLRQ DQDO\VLV KDV EHHQ VXFFHVVIXOO\ XVHG WR VLPXOWDQHRXVO\ PHDVXUH WKH OHYHOV RI

PAGE 50

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

PAGE 51

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f ,&306 KDV EHHQ XVHG IRU WKH PHDVXUHPHQW RI WUDFH HOHPHQWV LQ ZKROH EORRG DQG VHUXP > @ 7KH DGYDQWDJHV RI XVLQJ ,&306 LQFOXGH KLJK WKURXJKSXW VDPSOHVKRXUf SRVVLELOLW\ RI VLPXOWDQHRXV DQDO\VLV DQG JRRG GHWHFWLRQ OLPLWV 2YHU HOHPHQWV KDYH GHWHFWLRQ

PAGE 52

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

PAGE 53

;UDY IOXRUHVFHQFH ;UD\ VSHFWURPHWU\ LQYROYHV ERPEDUGLQJ WKH VDPSOH ZLWK UDGLDWLRQ RI GLVWLQFW HQHUJ\ 7KLV UHPRYHV HOHFWURQV IURP WKH LQQHU VKHOOV IRUPLQJ DWRPV LQ DQ H[FLWHG VWDWH 7KH HOHFWURQV IURP WKH RXWHU VKHOOV IDOO LQWR WKH VKHOOV YDFDWHG E\ WKH UHPRYHG HOHFWURQV DFFRUGLQJ WR VSHFLILF WUDQVLWLRQ UXOHV 7KH UDGLDWLRQ HPLWWHG E\ WKLV SURFHVV LV YHU\ FKDUDFWHULVWLF 7KH PHWKRG RI [UD\ IOXRUHVFHQFH FDQ EH XVHG IRU VLPXOWDQHRXV PXOWLHOHPHQW DQDO\VLV RQ D YHU\ VPDOO VDPSOH RI EORRG QKf ZLWKRXW GHVWUR\LQJ WKH VDPSOH >f§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

PAGE 54

)RU WKLV PHWKRG LW LV QHFHVVDU\ WR GLJHVW FRPSOHWHO\ WKH VDPSOHV SULRU WR DQDO\VLV >@ ,RQ VHOHFWLYH HOHFWURGHV ,6(f DUH FDSDEOH RI GHWHUPLQLQJ WKH OHYHO RI SRWDVVLXP VRGLXP PDJQHVLXP DQG OLWKLXP LQ EORRG RU VHUXP E\ PHDVXULQJ WKH SRWHQWLRPHWULF FKDUJH DV D IXQFWLRQ RI LRQ FRQFHQWUDWLRQ > @ 7KH PHPEUDQHV RI ,6(n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f >@ %XON\ FURZQ HWKHUV XVHG LQ D 39& PHPEUDQH ,6( FDQ H[KLELW D VHOHFWLYLW\ XS WR IRU OLWKLXP >@ $ JODVV LRQH[FKDQJH PHPEUDQH LV XVHG IRU WKH DQDO\VLV RI VRGLXP DQG D YDOLQRP\FLQ QHXWUDOFDUULHU PHPEUDQH LV XVHG IRU SRWDVVLXP >@ 7KH XVH RI ,6(nV WR DQDO\]H FOLQLFDO VDPSOHV LQYROYHV HLWKHU WKH GLUHFW DQDO\VLV RI XQGLOXWHG VDPSOHV RU WKH

PAGE 55

LQGLUHFW DQDO\VLV RI SUHGLOXWHG VDPSOHV 'LUHFW ,6( PHWKRGV DUH VXEMHFW WR ELDV EHFDXVH RI WKH GLIIHUHQFH LQ WKH VHUXP PDWUL[ DQG WKH DTXHRXV VDPSOHV XVHG IRU FDOLEUDWLRQ ,QGLUHFW ,6( LV VXVFHSWLEOH WR HUURU LQWURGXFHG E\ WKH GLOXWLRQ ,6(nV WR PRQLWRU 0J FDQ \LHOG UDSLG UHVXOWV RQ EORRG SODVPD VHUXP DQG DTXHRXV VROXWLRQV ZLWK VDPSOH VL]HV UDQJLQJ IRUP WR / >@ 7KH 0J ,6(nV HPSOR\ LRQRSKRUHV XVLQJ QHXWUDO FDUULHU EDVHG PHPEUDQHV ZLWK H[FHOOHQW SUHFLVLRQ UHSRUWHG DW WR b +RZHYHU WKLV PHWKRG GRHV H[SHULHQFH SUREOHPV ZLWK YHU\ ORZ OHYHOV RI PDJQHVLXP EHFDXVH WKH DQDO\WLFDO UHVSRQVH LV QRW OLQHDU DW WKHVH ORZ FRQFHQWUDWLRQV >@ ,6(nV FRPSDUH IDYRUDEO\ WR WKH PHWKRGV RI DWRPLF DEVRUSWLRQ VSHFWURPHWU\ DQG IODPH HPLVVLRQ VSHFWURPHWU\ IRU WKH DQDO\VLV RI VHYHUDO HOHPHQWV ,6(nV KDYH WKH DGYDQWDJHV WKDW WKH\ IXQFWLRQ LQ WXUELG VROXWLRQV KDYH D ZLGH G\QDPLF UDQJH KDYH D UDSLG UHVSRQVH DUH LQH[SHQVLYH DQG DUH YHU\ SRUWDEOH ZLWK FXUUHQW LQVWUXPHQWV ZHLJKLQJ EHWZHHQ WR NJ >@ 7KH UDSLG UHVSRQVH LV YHU\ EHQHILFLDO LQ PRQLWRULQJ GRVDJHV DQG FRPSOLDQFH ZLWK PHGLFDO WUHDWPHQW VXFK DV OLWKLXP WUHDWPHQW LQ SV\FKLDWULF SDWLHQWV ,6(nV KDYH WKH GLVDGYDQWDJHV WKDW WKH\ KDYH OLPLWHG VHQVLWLYLW\ DUH VXEMHFW WR LQWHUIHUHQFHV IURP RWKHU LRQV DQG PHPRU\ HIIHFWV DQG UHTXLUH IUHTXHQW FDOLEUDWLRQ

PAGE 56

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f IRU FDOLEUDWLRQ

PAGE 57

&+$37(5 (;3(5,0(17$/ 6(783 $1' 0$7(5,$/6 6HWXS 7KH H[SHULPHQWDO VHWXS LV VKRZQ LQ ILJXUH (DFK FRPSRQHQW RI WKH H[SHULPHQWDO VHWXS ZLOO EH GHVFULEHG 0LFURZDYH 3ODVPD (OHFWURQLFV 7KH PLFURZDYH SODVPD ZDV JHQHUDWHG E\ DQ : PDJQHWURQ 6DPVXQJ 0$f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

PAGE 58

+LJK 9ROWDJH 3RZHU 6XSSO\ $&'& 7UDQVIRUPHU (OHFWURGH 0DJQHWURQ f§ 5HFWDQJXODU :DYHJXLGH +HOLXP )ORZ LQ 5HPRYDEOH 4XDUW] &KLPQH\ 7HIORQ 7DSH )LJXUH &03$(6 H[SHULPHQWDO VHWXS 6SHFWURPHWHU 3'$ RU &&'

PAGE 59

WUDQVPLVVLRQ OLQH >@ $ GLDJUDP RI WKH PDJQHWURQ LV VKRZQ LQ ILJXUH 7KH PDJQHWURQ ZDV SRZHUHG E\ D FXUUHQW UHJXODWHG DQDORJSURJUDPPDEOH SRZHU VXSSO\ 0RGHO 5 %HUWU£Q +LJK 9ROWDJH +LFNVYLOOH 1< 86$f $Q $& SRZHU WUDQVIRUPHU 0DJQHWHN 7ULDG PRGHO )8 1HZDUN (OHFWURQLFV &KLFDJR ,/f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f PPf GLUHFWHG WKH IORZ RI KHOLXP D UHPRYDEOH TXDUW] WXEH RG PPf UHGXFHG WKH GHDG YROXPH RI WKH WRUFK DQG DQ LQQHU

PAGE 60

+HDWHU OHDGV DQG FDWKRGH OHDGV )LJXUH 0DJQHWURQ

PAGE 61

TXDUW] WXEH RG PPf WKDW VXSSRUWV D VKRUW SLHFH RI TXDUW] WXELQJ RG PPf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f ZDV XVHG DV WKH SODVPD JDV +HOLXP ZDV DQ H[FHOOHQW SODVPD JDV IRU DWRPLF HPLVVLRQ VSHFWURVFRS\ EHFDXVH RI LWV KLJK LRQL]DWLRQ HQHUJ\ >@ 7KH LRQL]DWLRQ HQHUJ\ RI KHOLXP LV H9 FRPSDUHG WR H9 IRU DUJRQ >@ 7KH KLJK LRQL]DWLRQ HQHUJ\ HQKDQFHG WKH SRVVLELOLW\ RI HQHUJ\ WUDQVIHU WR WKH DQDO\WH $ KHOLXP SODVPD LV DEOH WR H[FLWH HIILFLHQWO\ HOHPHQWV LQWURGXFHG LQWR WKH SODVPD DQG KDV ORZ EDFNJURXQG FKDUDFWHULVWLFV +\GURJHQ %2& *DVHV 7KH %2& *URXS ,QF 0XUUD\ +LOO 1-f ZDV LQWURGXFHG LQWR WKH

PAGE 62

SODVPD DW D IORZ UDWH RI FP9PLQ IRU WKH FOHDQLQJ VWHS 7KH SUHVHQFH RI K\GURJHQ LQ WKH SODVPD KHOSHG WR FUHDWH D UHGXFLQJ HQYLURQPHQW DQG LQFUHDVHG WKH WHPSHUDWXUH RI WKH SODVPD >@ 7KH KLJKHU WHPSHUDWXUH DQG UHGXFLQJ HQYLURQPHQW KHOSHG LQ WKH UHPRYDO RI WKH FDUERQDFHRXV UHVLGXH OHIW RYHU IURP WKH EORRG VDPSOH (OHFWURGH 7KH JUDSKLWH FXS KROGHU HOHFWURGHV ZHUH PDGH RXW RI VSHFWURVFRSLF JUDGH FDUERQ 8QLRQ &DUELGH &DUERQ 3URGXFWV 'LYLVLRQ &OHYHODQG 2+f 7KH PHWDOV XVHG IRU WKH FXSV DQG WKH HOHFWURGHV ZHUH REWDLQHG IURP $OID $HVDU-RKQVRQ 0DWWKH\ :DUG +LOO 0$ 7KH IROORZLQJ PHWDOV ZHUH REWDLQHG DV URGV DQG PDFKLQHG WR PDNH WKH YDULRXV HOHFWURGHV QLFNHO b SXUHf WLWDQLXP b SXUHf DQG WXQJVWHQ b SXUHf 7KH WXQJVWHQ VFUHHQ XVHG ZDV REWDLQHG IURP 1HZDUN :LUH &ORWK &R 1HZDUN 17KH WXQJVWHQ ZLUH b SXUHf XVHG ZDV DOVR REWDLQHG } IURP $OID $HVDU-RKQVRQ 0DWWKH\ :DUG +LOO 0$ 7KUHH GLDPHWHUV RI ZLUH ZHUH XVHG PP PP DQG PP 7KH ILQDO ILODPHQW XVHG ZDV PDGH RXW RI WKH PP WXQJVWHQ ZLUH 7KH WRS RI WKH ILODPHQW ZDV D WLJKW WXUQ VSLUDO ZLWK D GLDPHWHU RI PP 7KH WRWDO OHQJWK RI WKH ILODPHQW ZDV FP

PAGE 63

/HQV 6HWXS 7KH LQLWLDO OHQV VHWXS ILJXUH Df XVHG WZR SODQRFRQYH[ OHQVHV 7KH ILUVW OHQV GLDPHWHU PP IRFDO OHQJWK PPf ZDV SODFHG PP IURP WKH SODVPD WR FROOLPDWH WKH HPLVVLRQ IURP WKH SODVPD 7KH VHFRQG OHQV GLDPHWHU PP IRFDO OHQJWK PPf ZDV SODFHG VR WKDW WKH HPLVVLRQ ZDV IRFXVHG RQWR WKH HQWUDQFH VOLW RI WKH VSHFWURPHWHU ,Q DQ DWWHPSW WR LPSURYH WKH SUHFLVLRQ RI WKH &&03$(6 WKH OHQV VHWXS ZDV FKDQJHG DIWHU WKH OHDGLQEORRG ZRUN ZDV FRPSOHWHG 7KH OHQVHV ILJXUH Ef ZHUH VHW XS VR WKDW WKH HPLVVLRQ IURP WKH SODVPD ILOOHG WKH FROOLPDWLQJ PLUURU RI WKH VSHFWURPHWHU 7ZR OHQVHV KDG WR EH XVHG EHFDXVH D VLQJOH OHQV FRXOG QRW EH SODFHG FORVH HQRXJK WR WKH SODVPD IRU WKH GHVLUHG IRFXVLQJ $ ILUVW OHQV IRFDO OHQJWK PP GLDPHWHU PP (VFR 3URGXFWV3UHFLVLRQ 2DN 5LGJH 1HZ -HUVH\f ZDV XVHG WR IRUP D RQHWRRQH LPDJH RI WKH SODVPD DW D SURSHU GLVWDQFH DZD\ IURP WKH SODVPD ,W LV SODFHG PP IURP WKH SODVPD 7KH VHFRQG OHQV IRFDO OHQJWK PP GLDPHWHU PP (VFR 3URGXFWV3UHFLVLRQ 2DN 5LGJH 1HZ -HUVH\f ZDV WKHQ XVHG WR PDJQLI\ WKH LPDJH LQ VXFK D ZD\ WKDW WKH FROOLPDWLQJ PLUURU RI WKH VSHFWURPHWHU ZDV FRPSOHWHO\ ILOOHG ZLWK HPLVVLRQ 7KH VHFRQG OHQV ZDV SODFHG PP IURP WKH ILUVW OHQV 7KH GLVWDQFH IRU HDFK

PAGE 64

3ODVPD 2 Df 3ODVPD 2 Ef &ROOLPDWLQJ /HQV )RFXVLQJ /HQV 6SHFWURPHWHU /HQV /HQV U ? ,PDJH RI 3ODVPD ,If§r V I 6SHFWURPHWHU 7R FROOLPDWLQJ PLUURU RI VSHFWURPHWHU V n )LJXUH /HQV VHWXS QRW WR VFDOHf Df OHDG LQ EORRG ZRUN Ef PXOWLHOHPHQW ZRUN

PAGE 65

OHQV ZDV FDOFXODWHG IURP WKH HTXDWLRQV I V Vn DQG P VnV ZKHUH I LV WKH IRFDO OHQJWK RI WKH ILQDO OHQV V LV WKH GLVWDQFH EHWZHHQ WKH HPLVVLRQ VRXUFH DQG WKH ILQDO OHQV Vn LV WKH GLVWDQFH EHWZHHQ WKH OHQV DQG WKH PLUURU DQG P LV WKH UHVXOWLQJ PDJQLILFDWLRQ RI WKH LPDJH ,Q WKH PRGLILFDWLRQ RI WKLV OHQV VHWXS V EHFDPH WKH GLVWDQFH IURP WKH VHFRQG OHQV WR WKH RQHWRRQH LPDJH IRUPHG E\ WKH ILUVW OHQV 7KLV OHQV VHWXS UHVXOWHG LQ D PDJQLILFDWLRQ RI WKH SODVPD LPDJH RI DSSUR[LPDWHO\ WLPHV 'HWHFWRU 7KH GHWHFWRU FRQVLVWHG RI D P VSHFWURPHWHU 6SH[ (GLVRQ 186$f DQG HLWKHU D SKRWRGLRGH DUUD\ 3'$f RU D FKDUJH FRXSOHG GHYLFH &&'f 7KH VSHFWURPHWHU JUDWLQJ FRQWDLQHG JURRYHVPP ZLWK D EOD]H ZDYHOHQJWK RI QP 7KH SUHOLPLQDU\ ZRUN DQG WKH OHDG LQ EORRG UHVHDUFK ZDV GRQH XVLQJ WKH 3'$ 7KH PXOWLHOHPHQW ZRUN ZDV GRQH ZLWK WKH &&' 7KH VSHFWURPHWHU VOLW ZLGWK ZDV DGMXVWHG IRU HDFK HOHPHQW ,I JUHDWHU VHQVLWLYLW\ ZDV QHHGHG WKH VOLW ZLGWK ZDV RSHQHG WR DV PXFK DV P )RU HOHPHQWV UHTXLULQJ OHVV VHQVLWLYLW\ DQG KLJKHU UHVROXWLRQ D VOLW ZLGWK DV VPDOO DV DQ ZDV XVHG 7KH VOLW KHLJKW ZDV NHSW FRQVWDQW DW FP %RWK WKH 3'$ DQG WKH &&' JDYH D VSHFWUDO ZLQGRZ RI QP

PAGE 66

3KRWRGLRGH DUUD\ 7KH LQWHQVLILHG SKRWRGLRGH DUUD\ 7UDFRU 1RUWKHUQ 71 $ 0LGGOHWRQ :, 86$f FRQVLVWHG RI VLOLFRQ SKRWRGLRGHV DUUDQJHG OLQHDUO\ HDFK VSDFHG DSDUW (DFK SKRWRGLRGH FRQVLVWHG RI D OD\HU RI VLOLFRQ GRSHG ZLWK DWRPV FRQWDLQLQJ H[WUD HOHFWURQV SW\SH VHPLFRQGXFWRUVf RQ WRS RI D OD\HU RI VLOLFRQ GRSHG ZLWK DWRPV ZLWK RQH YDOHQFH HOHFWURQ OHVV WKDQ VLOLFRQ QW\SH VHPLFRQGXFWRUf 7KLV DOORZV WKH FXUUHQW WR IORZ LQ RQO\ RQH GLUHFWLRQ $ UHYHUVH ELDVHG SRWHQWLDO LV DSSOLHG DFURVV WKH GLRGH VR WKDW ZKHQ H[SRVHG WR OLJKW HOHFWURQ KROH SDLUV DUH FUHDWHG SURGXFLQJ D FXUUHQW WKDW LV SURSRUWLRQDO WR WKH DPRXQW RI OLJKW > @ &KDUJH FRXSOHG GHYLFH 7KH GHWHFWRU ZDV FKDQJHG IURP WKH SKRWRGLRGH DUUD\ 3'$f WKDW ZDV XVHG IRU PXFK RI WKH OHDGLQEORRG ZRUN WR D FKDUJH FRXSOHG GHYLFH &&'f IRU DOO RI WKH PXOWLHOHPHQW ZRUN 7KLV FKDQJH ZDV QHFHVVDU\ EHFDXVH RI SUREOHPV WKDW GHYHORSHG ZLWK WKH KDUGZDUH DQG VRIWZDUH WKDW FRQWUROOHG WKH 3'$ 7KH &&' GHWHFWRU KDV WKH DGYDQWDJH WKDW LW ZDV WZR GLPHQVLRQDO DQG ZDV FU\RJHQLFDOO\ FRROHG WR UHGXFH WKH GDUN FXUUHQW 7KH &&' FRQWDLQHG [ SLFWXUH HOHPHQWV SL[HOVf (DFK SL[HO ZDV cMP VTXDUH DQG FRQVLVWHG RI D PHWDOR[LGH VLOLFRQ 026f FDSDFLWRU 7KH SL[HOV ZHUH PDGH RXW RI DQ

PAGE 67

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r& HYHQ WKRXJK WKHUH ZDV QRW PXFK FKDQJH LQ WKH GDUN FRXQWV EHORZ D WHPSHUDWXUH RI r& $W WHPSHUDWXUHV KLJKHU WKDQ r& WKH OLTXLG QLWURJHQ HYDSRUDWHV WRR TXLFNO\ $W WHPSHUDWXUHV ORZHU WKDQ r& WKH FKDUJH WUDQVIHU HIILFLHQF\ IURP SL[HO WR SL[HO PD\ EH ORZHUHG GHJUDGLQJ WKH &&' SHUIRUPDQFH >@ ,I WKH OLJKW OHYHOV UHDFKLQJ WKH &&' ZHUH WRR KLJK EORRPLQJ FRXOG RFFXU %ORRPLQJ LV WKH VSLOODJH RI FKDUJH IURP DQ RYHULOOXPLQDWHG SL[HO WR DQ DGMDFHQW SL[HO > @ 7KH VLJQDO WR QRLVH UDWLR DQG WKH G\QDPLF UDQJH FRXOG EH LPSURYHG E\ WKH SURFHVV RI ELQQLQJ %LQQLQJ FRPELQHV WKH FKDUJH IURP DGMDFHQW SL[HOV GXULQJ UHDGRXW 7KH FKDUJH UHDG

PAGE 68

%DFNJURXQG &RXQW 9DOXHV )LJXUH &&' EDFNJURXQG GHSHQGHQFH RQ WHPSHUDWXUH

PAGE 69

ZLOO LQFUHDVH E\ WKH QXPEHU RI SL[HOV ELQQHG EXW WKH QRLVH ZLOO VWD\ WKH VDPH %LQQLQJ KDV WKH GLVDGYDQWDJH RI UHGXFLQJ WKH VSDWLDO UHVROXWLRQ >@ 2ULJLQDOO\ WKH &&' GHWHFWRU ZDV QRW VHQVLWLYH WR HPLVVLRQ EHORZ QP 7KH FDPHUD ZDV VHQW WR 6SHFWUDO ,QVWUXPHQWV 7XFVRQ $UL]RQDf VR WKDW D 89 HQKDQFHPHQW FRDWLQJ FRXOG EH DSSOLHG WR WKH &&' HOHPHQW 7KH FRDWLQJ ZDV OXPRJHQ \HOORZ DQ RUJDQLF SKRVSKRU 7KH SKRVSKRU DEVRUEV OLJKW LQ WKH 89 UDQJH DQG UHHPLWV LW LQ WKH YLVLEOH UDQJH &RPSXWHU 6RIWZDUH 7KH SURJUDPPDEOH SRZHU VXSSO\ DQG WKH WULJJHULQJ RI WKH GHWHFWRU ZHUH FRQWUROOHG E\ D FRPSXWHU 3&nV /LPLWHG PRGHO / 3&nV /LPLWHG $XVWLQ 7;f DQG D FRPSXWHU LQWHUIDFH 0RGHO 65 6WDQIRUG 5HVHDUFK 6\VWHPV 3DOR $OWR &$ 86$f XVLQJ D SURJUDP ZULWWHQ LQ 0LFURVRIW 4XLN%DVLF &RS\ULJKW 0LFURVRIW &RUSRUDWLRQ f 7KH HPLVVLRQ VSHFWUD ZHUH FROOHFWHG XVLQJ &&'r1 VSHFWUDO DFTXLVLWLRQ VRIWZDUH YHUVLRQ FRS\ULJKW 3KRWRPHWULHV /WGf 7KH SHDN DUHDV ZHUH GHWHUPLQHG XVLQJ WKH SURJUDP /DE&DOFr1 FRS\ULJKW *DODFWLF ,QGXVWULHV &RUSRUDWLRQf $QDO\WLFDO FXUYHV ZHUH FRQVWUXFWHG XVLQJ 2ULJLQr1 YHUVLRQ FRS\ULJKW 0LFURFDOr1 6RIWZDUH ,QFf

PAGE 70

0DWHULDOV $TXHRXV 6WDQGDUGV $TXHRXV VWDQGDUGV ZHUH SUHSDUHG E\ VHTXHQWLDOO\ GLOXWLQJ SSP UHIHUHQFH VWDQGDUGV IRU HDFK HOHPHQW )LVKHU &KHPLFDO )LVKHU 6FLHQWLILF )DLU /DZQ 1HZ -HUVH\f 7KH VWDQGDUGV XVHG LQ WKH VWDQGDUG DGGLWLRQV RI WKH EORRG DQDO\VLV ZHUH SUHSDUHG IURP WKH VDOWV RI WKH HOHPHQWV EHLQJ DQDO\]HG 7KLV ZDV QHFHVVDU\ EHFDXVH WKH VWDQGDUGV QHHGHG WR EH QRQDFLGLF WR SUHYHQW GHQDWXULQJ RI WKH EORRG $OVR WKH FRQFHQWUDWLRQV UHTXLUHG IRU VRPH RI WKH HOHPHQWV ZHUH ODUJHU WKDQ WKH DYDLODEOH DTXHRXV VWDQGDUGV $OO WKH DTXHRXV VWDQGDUGV ZHUH SUHSDUHG XVLQJ GHLRQL]HG ZDWHU VSHFLILF UHVLVWLYLW\ 04FPf IURP D 0LOOL4 3OXV ZDWHU V\VWHP 0LOOLSRUH &RUSRUDWLRQ %HGIRUG 0$f 7KH DTXHRXV VWDQGDUGV ZHUH LQWURGXFHG IRU DQDO\VLV XVLQJ D / DLU GLVSODFHPHQW SLSHWWHU (SSHQGRUI %ULQNPDQ ,QVWUXPHQWV ,QF :HVWEXU\ 1
PAGE 71

GRVDJHV RI OHDG QLWUDWH LQ JHODWLQ FDSVXOHV 7KH EORRG ZDV FROOHFWHG IURP WKH FRZV DQG WKH LQLWLDO FRQFHQWUDWLRQ ZDV GHWHUPLQHG XVLQJ DWRPLF DEVRUSWLRQ VSHFWURPHWU\ 9DU\LQJ DPRXQWV RI WKH WZR EORRG VDPSOHV ZHUH WKHQ EOHQGHG WR JLYH D UDQJH RI OHDG FRQFHQWUDWLRQV 7KH ILQDO FRQFHQWUDWLRQV RI WKH VDPSOHV ZHUH GHWHUPLQHG XVLQJ ,',&306 >@ +XPDQ ZKROH EORRG ZDV FROOHFWHG E\ YHQLSXQFWXUH LQWR D 9DFXWDLQHU %HFWRQ 'LFNLQVRQ 9DFXWDLQHU 6\VWHPV )UDQNOLQ /DNHV 186$f FRDWHG ZLWK .('7$ DV DQ DQWLFRDJXODQW 7KH VWDQGDUG DGGLWLRQ VDPSOHV ZHUH PDGH E\ DGGLQJ YDU\LQJ DPRXQWV RI DQ DTXHRXV VWDQGDUG WR D P/ SRUWLRQ RI ZKROH EORRG 'HLRQL]HG ZDWHU ZDV DGGHG WR WKH VDPSOH WR SURGXFH D ILQDO YROXPH RI P/ 7KLV UHVXOWHG LQ D VDPSOH WKDW ZDV b ZKROH EORRG 7KH VDPSOHV ZHUH JHQWO\ UROOHG DQG WKHQ VRQLFDWHG IRU PLQXWHV WR WKRURXJKO\ PL[ WKH DTXHRXV VWDQGDUG DQG WKH EORRG $ OHDGLQEORRG 6WDQGDUG 5HIHUHQFH 0DWHULDO 650 Df ZDV SXUFKDVHG IURP WKH 1DWLRQDO ,QVWLWXWH RI 6WDQGDUGV DQG 7HFKQRORJ\ 1,67f *DLWKHUVEXUJ 0'f 7KLV 650 FRQVLVWHG RI IRXU YLDOV RI IUR]HQ ERYLQH EORRG HDFK FRQWDLQLQJ D GLIIHUHQW FRQFHQWUDWLRQ RI OHDG 7KH FRQFHQWUDWLRQ RI OHDG LQ HDFK 650 ZDV GHWHUPLQHG E\ 1,67 XVLQJ ,',&306 DQG FRQILUPHG XVLQJ *)$$6 DQG ODVHUH[FLWHG DWRPLF IOXRUHVFHQFH VSHFWURPHWU\ 7KH FRQFHQWUDWLRQV DUH VKRZQ LQ 7DEOH 7KH XQFHUWDLQW\ UHIOHFWV D FRQILGHQFH OHYHO RI b

PAGE 72

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p PRGHO 'UXPPRQG 6FLHQWLILF &R %URRPDOO 3$f %HIRUH GHSRVLWLQJ WKH VDPSOH WKH RXWVLGH RI WKH JODVV FDSLOODU\ WLS ZDV ZLSHG ZLWK D .LPZLSHr1 WR UHPRYH DQ\ EORRG WKDW KDG DGKHUHG WR WKH WLS 7KH SLSHWWHU ZDV FOHDQHG EHWZHHQ VDPSOH UXQV E\ UHSHDWHGO\ GHSUHVVLQJ WKH SOXQJHU ILUVW LQ D VROXWLRQ RI b QLWULF DFLG VROXWLRQ DQG WKHQ LQ GHLRQL]HG ZDWHU

PAGE 73

7DEOH &RQFHQWUDWLRQ RI OHDG LQ 650 D DW r& 9LDO 1XPEHU &RQFHQWUDWLRQ SSEf DO s D s D s D s

PAGE 74

&+$37(5 6$03/( ,1752'8&7,21 ,QWURGXFWLRQ &DSDFLWLYHO\ FRXSOHG PLFURZDYH SODVPD DWRPLF HPLVVLRQ VSHFWURPHWU\ &03$(6f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

PAGE 75

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

PAGE 76

3DWHO HW DO XVHG SQHXPDWLF QHEXOL]DWLRQ ZLWK D &03 WR DQDO\]H DTXHRXV VDPSOHV IRU HOHPHQWV >@ 6DPSOH VROXWLRQV ZHUH QHEXOL]HG ZLWK D 0HLQKDUG QHEXOL]HU DQG D ODERUDWRU\FRQVWUXFWHG VSUD\ FKDPEHU DQG GHVROYDWLRQ V\VWHP $ WXEXODU HOHFWURGH PDGH RXW RI WDQWDOXP ZDV XVHG WR VXSSRUW WKH SODVPD 7KH DQDO\WH FDUULHU JDV SDVVHG WKURXJK WKH FHQWHU RI WKH KROORZ HOHFWURGH DQG HQWHUHG LQWR WKH SODVPD DW WKH WRS RI WKH HOHFWURGH >@ %\ LQWURGXFLQJ WKH VDPSOH GLUHFWO\ LQWR WKH FRUH RI WKH SODVPD WKH LQWHUDFWLRQV EHWZHHQ WKH VDPSOH DQG SODVPD ZHUH LPSURYHG $OVR WKH FRQFHQWUDWLRQ RI WKH DQDO\WH LQ WKH SODVPD YLHZLQJ UHJLRQ LV LQFUHDVHG LPSURYLQJ WKH GHWHFWLRQ OLPLWV VLJQDO WR QRLVH DQG VLJQDO WR EDFNJURXQG ,W ZDV GHWHUPLQHG WKDW WKLV PHWKRG JDYH ORZ GHWHFWLRQ OLPLWV ZLWK D ZLGH OLQHDU G\QDPLF UDQJH IRU D QXPEHU RI GLIIHUHQW HOHPHQWV 6HYHUDO RWKHU WXEH PDWHULDOV DQG IRUPV RI HOHFWURGHV ZHUH HYDOXDWHG 7KH HOHFWURGH W\SHV LQFOXGHG D SODWLQXP WXEH D FRSSHU WXEH D SODWLQXP FRDWHG WXQJVWHQ ZLUH PP RGf D PRO\EGHQXP URG DQG D WXQJVWHQ URG ZLWK SODWLQXP FODGGLQJ >@ +ZDQJ HW DO XVHG JUDSKLWH DV WKH HOHFWURGH PDWHULDO >@ 7KLV HOHFWURGH KDG D ORZHU HPLVVLRQ EDFNJURXQG DQG GLG QRW VLJQLILFDQWO\ FRQWDPLQDWH WKH SODVPD LQ FRPSDULVRQ WR WKH PHWDO URG HOHFWURGH ([FHOOHQW GHWHFWLRQ OLPLWV IRU VHYHUDO HOHPHQWV LQ DTXHRXV VROXWLRQV ZHUH REWDLQHG >@

PAGE 77

7KHUPDO 9DSRUL]DWLRQ 7ZR SUHYLRXV PHWKRGV RI VDPSOH LQWURGXFWLRQ E\ WKHUPDO YDSRUL]DWLRQ 79f LQFOXGH D WXQJVWHQ ILODPHQW HOHFWURGH ILJXUH ODf > @ DQG D FXS KROGHU HOHFWURGH ILJXUH OEf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

PAGE 78

‘‘‘ Df Ef Ff )LJXUH (OHFWURGH GHVLJQV Df ILODPHQW HOHFWURGH Ef FXS KROGHU HOHFWURGH Ff SODWIRUP HOHFWURGH Gf WLWDQLXP HOHFWURGH ZLWK QLFNHO FDS Hf WLWDQLXP HOHFWURGH ZLWK WLWDQLXP FDS

PAGE 79

HOHFWURGH KDV D KROORZHG RXW SRUWLRQ WKDW ZLOO VQXJO\ KROG WKH FXS 7KH HOHFWURGH PXVW EH PDGH RXW RI D PDWHULDO WKDW LV FRQGXFWLYH DQG KDV D KLJKHU PHOWLQJ SRLQW WKDQ WKH WKHUPDO WHPSHUDWXUH RI WKH SODVPD 0DWHULDOV WKDW FDQ EH XVHG IRU WKH HOHFWURGH DUH JUDSKLWH RU YDULRXV PHWDOV *UDSKLWH HOHFWURGHV DUH FKHDSHU DQG PRUH UHVLVWLYH WKDQ PHWDO HOHFWURGHV DQG HPLVVLRQ IURP WKH PHWDO HOHFWURGH FDQ DOVR FDXVH LQWHUIHUHQFH LQ DQDO\VLV (OHFWURGHV PDGH RXW RI PHWDO KDYH VHYHUDO DGYDQWDJHV RYHU WKRVH PDGH RXW RI JUDSKLWH 0HWDO HOHFWURGHV DUH PRUH GXUDEOH DQG ODVW ORQJHU WKDQ JUDSKLWH HOHFWURGHV $OVR JUDSKLWH HOHFWURGHV IRUP UHIUDFWRU\ FDUELGHV DQG SURGXFH JDVHRXV PROHFXODU FDUERQ VSHFLHV ZKLFK FDXVH LQWHUIHUHQFH LQ HPLVVLRQ PHDVXUHPHQWV &XSV PDGH RXW RI ERWK JUDSKLWH DQG WXQJVWHQ KDYH EHHQ XVHG WR KROG WKH VDPSOH 7KH FXS ZDV SODFHG RQ WKH WRS RI WKH HOHFWURGH DQG WKH HOHFWURGH FRQWDLQLQJ WKH FXS ZDV SODFHG LQWR WKH FHQWUDO WXEH RI WKH WRUFK 7KH SODVPD ZDV LJQLWHG DW D ORZ SRZHU DURXQG :f WR DVK WKH VDPSOH DQG ZDV WKHQ UDLVHG WR : WR DWRPL]H DQG H[FLWH WKH DQDO\WH HQDEOLQJ WKH PHDVXUHPHQW RI WKH HPLVVLRQ >@ %\ XVLQJ D FXS LQVWHDG RI D ZLUH ILODPHQW KLJKHU SRZHUV FRXOG EH XVHG VR WKDW WKHUH ZHUH IHZHU PDWUL[ HIIHFWV DQG WKH VLJQDO ZDV ODUJHU 7KH GLVDGYDQWDJH RI XVLQJ D FXS ZDV WKDW WKH DWRPV ZHUH GLVSHUVHG RYHU D ZLGHU YROXPH VR WKH QXPEHU GHQVLW\ RI H[FLWHG DWRPV ZDV VPDOOHU

PAGE 80

$OL HW DO XVHG &03$(6 ZLWK D FXS HOHFWURGH ZLWK ERWK WKH HOHFWURGH DQG WKH FXS PDGH RXW RI JUDSKLWH 'HWHFWLRQ OLPLWV UDQJLQJ EHWZHHQ DQG SJ ZHUH REWDLQHG IRU HOHPHQWV ZLWK D SUHFLVLRQ EHWWHU WKDQ b >@ $ VDPSOH YROXPH RI RQO\ m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

PAGE 81

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f PLFURZDYH SODVPD 7KH SRZHU RI WKH SODVPD ZDV LQFUHDVHG XQWLO WKH VDPSOH ZDV DWRPL]HG DQG H[FLWHG VR WKDW WKH HPLVVLRQ FRXOG EH PHDVXUHG ,W ZDV IRXQG WKDW DGGLQJ D ORZ IORZ UDWH P/PLQf RI K\GURJHQ JDV ZLWK WKH SODVPD JDV UHGXFHG WKH EDFNJURXQG HPLVVLRQ IURP WKH WXQJVWHQ ILODPHQW 7KH DEVROXWH GHWHFWLRQ OLPLWV RI HOHPHQWV ZHUH LQ WKH UDQJH RI WR SJ DQG WKLV FRPSDUHG IDYRUDEO\ WR WKH PHWKRG RI JUDSKLWH IXUQDFH DWRPLF DEVRUSWLRQ VSHFWURPHWU\ *)$$6f $ OLQHDU G\QDPLF UDQJH RI WR RUGHUV RI PDJQLWXGH ZDV REWDLQHG DQG WKH SUHFLVLRQ ZDV EHWWHU WKDQ b 5HSRUWHG OLIHWLPHV IRU WKH ILODPHQWV ZHUH UXQV >@

PAGE 82

:HQVLQJ HW DO HYDOXDWHG D &03$(6 IRU D OHDG EORRG VFUHHQLQJ PHWKRG XVLQJ D WXQJVWHQ ORRS ILJXUH ODf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f $ FOHDQLQJ VWHS ZDV QHFHVVDU\ LQ RUGHU WR UHPRYH WKH FDUERQDFHRXV UHVLGXH IURP WKH OHIW RYHU EORRG VDPSOH &OHDQLQJ ZDV SHUIRUPHG E\ LQFUHDVLQJ WKH SRZHU WR : DQG DGGLQJ D IORZ RI K\GURJHQ JDV WR WKH KHOLXP SODVPD 7KH FOHDQLQJ SURFHGXUH ODVWHG IRU RQH PLQXWH DQG HIIHFWLYHO\ UHPRYHG DOO EORRG UHVLGXH IURP WKH ILODPHQW 7KH ILODPHQW HOHFWURGH &03$(6 PHWKRG ZDV DEOH WR PHHW WZR RI WKH FULWHULD VHW IRUWK E\ WKH &HQWHUV IRU 'LVHDVH

PAGE 83

&RQWURO &'&f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b VRGLXP ERURK\GULGH LQ D UHDFWLRQ FHOO $IWHU D FHUWDLQ DPRXQW RI WLPH KDG SDVVHG WKH UHVXOWLQJ K\GULGH RI WKH HOHPHQW ZDV FDUULHG WR WKH &03 E\ D IORZ RI WKH SODVPD JDV $NDWVXND

PAGE 84

DQG $WVX\D XVHG D &03 ZLWK K\GULGH JHQHUDWLRQ WR DQDO\]H DUVHQLF LQ VHZDJH VOXGJH DQG LURQ LQ VWHHOV 7KH\ REWDLQHG D GHWHFWLRQ OLPLW RI SSE IRU DUVHQLF LQ VROXWLRQ >@ 8FKLGD HW DO XVHG WKH PHWKRG RI K\GULGH JHQHUDWLRQ ZLWK D &03 WR DQDO\]H LQRUJDQLF WLQ >@ 'HYHORSPHQW RI (OHFWURGH IRU %ORRG $QDO\VLV &XS +ROGHU (OHFWURGH $ FXS KROGHU HOHFWURGH ILJXUH OEf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f WR EH RSWLPL]HG EHIRUH

PAGE 85

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cL/ 6HYHUDO SDUDPHWHUV IRU WKH FXS HOHFWURGH ZHUH VWXGLHG 7KH FKDQJH LQ HOHFWURGH IURP WKH ILODPHQW WR WKH FXS HOHFWURGH UHTXLUHG UHRSWLPL]LQJ WKH FRQGLWLRQV RI WKH SODVPD 7KH FRXSOLQJ RI WKH PLFURZDYH HQHUJ\ DQG WKH VWDELOLW\ RI WKH SODVPD ZHUH DIIHFWHG E\ WKH OHQJWK RI WKH HOHFWURGH DQG WKH HOHFWURGHnV SHQHWUDWLRQ LQWR WKH ZDYHJXLGH 7KH RSWLPXP FRXSOLQJ SRVLWLRQ RI WKH HOHFWURGH ZDV GHWHUPLQHG E\ YDU\LQJ WKH HOHFWURGH OHQJWK SHQHWUDWLRQ LQWR WKH PLFURZDYH ILHOG WR ILQG WKH SDUDPHWHUV ZKHUH WKH PLQLPXP PLFURZDYH SRZHU ZDV QHHGHG WR VXVWDLQ WKH SODVPD 7KH ILUVW SDUDPHWHU VWXGLHG ZDV WKH OHQJWK RI WKH HOHFWURGH ,QLWLDOO\ WKH KHLJKW RI WKH HOHFWURGH DERYH WKH

PAGE 86

ZDYHJXLGH ZDV NHSW FRQVWDQW DW PP 7KLV ZDV WKH KHLJKW XVHG LQ WKH ZRUN ZLWK WKH WXQJVWHQ ILODPHQW HOHFWURGH 'LIIHUHQW OHQJWKV RI WKH HOHFWURGH ZHUH WKHQ XVHG GHWHUPLQLQJ WKH UDQJH RI SRZHUV RYHU ZKLFK D VWDEOH SODVPD ZRXOG IRUP 7KH SRZHU VXSSOLHG WR WKH PDJQHWURQ ZDV JUDGXDOO\ LQFUHDVHG XQWLO D SODVPD ZRXOG IRUP 7KH SRZHU ZDV LQFUHDVHG XQWLO WKH SODVPD ZDV QR ORQJHU VWDEOH DQG WKHQ GHFUHDVHG XQWLO WKH SODVPD FRXOG QR ORQJHU EH VXVWDLQHG 7KH OHQJWKV RI WKH HOHFWURGHV UDQJHG IURP FP WR FP ZKLFK FRUUHVSRQGHG WR D GHSWK RI SHQHWUDWLRQ LQWR WKH ZDYHJXLGH RI FP WR FP 7KLV H[SHULPHQW ZDV UHSHDWHG NHHSLQJ WKH SHQHWUDWLRQ GHSWK RI WKH HOHFWURGH LQWR WKH ZDYHJXLGH FRQVWDQW DW FP DQG HYDOXDWLQJ GLIIHUHQW OHQJWKV RI WKH HOHFWURGHV $V WKH SHQHWUDWLRQ GHSWK ZDV LQFUHDVHG WKH SODVPD FRXOG EH PDLQWDLQHG DW KLJKHU SRZHUV )RU VRPH SRVLWLRQV RI WKH HOHFWURGH WKH PD[LPXP SRZHU RI : FRXOG QRW EH DFKLHYHG EHFDXVH WKH SODVPD VWDUWHG WR PDNH D YHU\ ORXG ZKLQLQJ QRLVH 7KH OHQJWK DQG SHQHWUDWLRQ WKDW SURGXFHG D VWDEOH SODVPD RYHU WKH ZLGHVW UDQJH RI SRZHUV ZDV FKRVHQ DV WKH RSWLPXP )LJXUH VKRZV VRPH H[DPSOHV RI WKH GDWD FROOHFWHG IRU WKH RSWLPL]DWLRQ RI HOHFWURGH OHQJWK DQG SHQHWUDWLRQ 8VLQJ WKH RSWLPXP FRQGLWLRQV IRXQG IRU WKH HOHFWURGH WKH DQDO\VLV RI DTXHRXV OHDG VROXWLRQV ZDV VWXGLHG $W DQ DWRPL]DWLRQ SRZHU RI : WKH OHDG HPLVVLRQ WRRN

PAGE 87

)LJXUH 2SWLPL]DWLRQ RI HOHFWURGH OHQJWK DQG SHQHWUDWLRQ GHSWK RI JUDSKLWH HOHFWURGH

PAGE 88

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a PP LQ GLDPHWHU $ LL/ DTXHRXV OHDG VDPSOH ZDV SODFHG RQ WKH IODW WRS RI WKH HOHFWURGH GULHG

PAGE 89

IRU VHFRQGV DW DSSUR[LPDWHO\ : DQG WKHQ DWRPL]HG ZLWK D SODVPD SRZHU RI : 7KH WLWDQLXP SODWIRUP HOHFWURGH JDYH D ODUJHU VLJQDO WKDQ KDG SUHYLRXVO\ EHHQ REWDLQHG 7KH VLJQDO VWLOO ODVWHG D ORQJ WLPH ILJXUH Df EXW QRW DV ORQJ DV ZLWK WKH JUDSKLWH HOHFWURGH DQG WKH QLFNHO FXS 7KH VLJQDO LQFUHDVHG ILJXUH Ef ZKHQ WKH EXON\ WRS SDUW RI WKH HOHFWURGH WKDW ZDV LQWHQGHG WR KROG WKH FXSf ZDV UHPRYHG \LHOGLQJ D WKLQ PHWDO URG )LJXUH Ff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

PAGE 90

VLJQDO 6LJQDO )LJXUH 7HPSRUDO SURILOHV IRU OHDG VLJQDO IRU WKH SODWIRUP HOHFWURGHV Df SODWIRUP ZLWK FXS KROGHU SRUWLRQ Ef WKLQ WLWDQLXP URG SODWIRUP

PAGE 91

SRZHUV DERYH : WKH LQWHUIHULQJ OLQH DSSHDUHG ,W LV GHVLUDEOH WR KDYH DQ HOHFWURGH WKDW FRXOG ODVW IRU DQ LQGHILQLWH SHULRG RI WLPH DQG ZRXOG QRW KDYH DQ\ HPLVVLRQ OLQHV ZKLFK ZRXOG OLPLW WKH SRZHUV XVHG )RU WKHVH UHDVRQV VHYHUDO RWKHU PDWHULDOV ZHUH WULHG IRU WKH SODWIRUP HOHFWURGH 7XQJVWHQ ZKLFK KDG EHHQ XVHG IRU WKH ILODPHQW HOHFWURGH KDV D KLJKHU PHOWLQJ SRLQW DQG ORZHU EDFNJURXQG HPLVVLRQ WKDQ WLWDQLXP DQG VR LW ZDV HYDOXDWHG DV WKH HOHFWURGH PDWHULDO $ 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f 7KLV GHVLJQ ZDV XVHG LQ DQ DWWHPSW WR REWDLQ D VLPLODU VLJQDO DV WKDW REWDLQHG ZLWK WKH WLWDQLXP HOHFWURGH EXW ZLWK D ORQJHU OLIHWLPH EHFDXVH RI WKH QLFNHO FDS 7KH VLJQDO REWDLQHG IRU WKLV HOHFWURGH ZDV VLPLODU WR WKDW REWDLQHG ZKHQ WKH ZKROH

PAGE 92

HOHFWURGH ZDV QLFNHO D ORZ LQWHQVLW\ VLJQDO ZDV GHOD\HG LQ DSSHDULQJ DQG KDG D ORQJ WHPSRUDO SURILOH )URP WKH UHVXOWV REWDLQHG WKH HOHFWURGH PDGH RXW RI SXUH WLWDQLXP ZDV WKH EHVW SODWIRUP HOHFWURGH HYHQ WKRXJK LW ZRXOG KDYH WR EH FKDQJHG RQ D UHJXODU EDVLV 7KH WLWDQLXP SODWIRUP HOHFWURGH ODVWHG DSSUR[LPDWHO\ ILULQJV IRU DTXHRXV VDPSOHV 7KH WLWDQLXP SODWIRUP JDYH JRRG UHVXOWV IRU DTXHRXV OHDG VDPSOHV ILJXUH f DFKLHYLQJ D GHWHFWLRQ OLPLW RI SSE IRU D S/ VDPSOH YROXPH +RZHYHU WKH SUHFLVLRQ ZDV SRRU IRU FRQFHQWUDWLRQV RI SSE DQG EHORZ $QDO\VLV RI OHDG LQ ZKROH EORRG ZDV SHUIRUPHG XVLQJ ZKROH EORRG TXDOLW\ FRQWURO PDWHULDOV 4&0Vf 7KH DQDO\WLFDO FXUYH IRU WKHVH VWDQGDUGV ILJXUH f ZDV OLQHDU 5 f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

PAGE 93

&RQFHQWUDWLRQ SSEf )LJXUH $QDO\WLFDO FXUYH IRU DTXHRXV OHDG VWDQGDUGV RQ WKH WLWDQLXP SODWIRUP HOHFWURGH

PAGE 94

)LJXUH $QDO\WLFDO FXUYH IRU ZKROH EORRG OHDG VWDQGDUGV RQ WLWDQLXP SODWIRUP HOHFWURGH

PAGE 95

FDSDFLW\ RI WKH WLWDQLXP URG SODWIRUP ZDV S/ DQG WKH VDPSOH ZRXOG VRPHWLPHV UXQ RYHU WKH VLGH ,Q RUGHU WR DFKLHYH UHSURGXFLEOH VDPSOH GHSRVLWLRQ HOHFWURGHV FRQWDLQLQJ D GHSUHVVLRQ LQ WKH WRS ZHUH XVHG ,W ZDV IRXQG WKDW WKH VL]H DQG VKDSH RI WKH GHSUHVVLRQ ZDV YHU\ LPSRUWDQW LQ PHDVXULQJ WKH OHDG VLJQDO ,I WKH GHSUHVVLRQ ZDV WRR GHHS WKH VLJQDO ZDV VPDOO ,I WKH YROXPH RI WKH EORRG VDPSOH ZDV WRR ODUJH WKH EORRG ZRXOG LQWHUIHUH ZLWK WKH IRUPDWLRQ RI WKH SODVPD :KHQ EORRG VDPSOHV ZHUH UXQ ZLWK WKH GHSUHVVLRQ HOHFWURGH WKH LQVLGH RI WKH GHSUHVVLRQ EHFDPH GLUW\ DQG ZDV GLIILFXOW WR FOHDQ (YHQ IRU VKDOORZ GHSUHVVLRQV WKH OHDG VLJQDO ZDV DSSUR[LPDWHO\ RQH KDOI RI WKH VLJQDO REWDLQHG E\ WKH HOHFWURGH ZLWKRXW WKH GHSUHVVLRQ 7KH HOHFWURGH ZLWK WKH GHSUHVVLRQ KDG D VKRUW OLIHWLPH RI RQO\ ILULQJV IRU EORRG VDPSOHV 7R UHGXFH WKH DPRXQW RI WLPH UHTXLUHG WR FOHDQ WKH HOHFWURGH D WLWDQLXP HOHFWURGH ZLWK D FDS ZDV XVHG ILJXUH Hf 7KLV HOHFWURGH GHVLJQ DOORZHG RQH FDS WR EH FOHDQHG ZKLOH DQRWKHU FDS ZDV EHLQJ XVHG IRU DQDO\VLV 6DPSOHV FRXOG DOVR EH GULHG VHSDUDWHO\ DQG WKHQ SODFHG RQ WKH FDS KROGHU WR XVH WKH PLFURZDYH SODVPD IRU WKH DVKLQJ DQG DQDO\VLV 7KLV VKRUWHQHG WKH DQDO\VLV WLPH E\ QLQHW\ VHFRQGV DQG FRXOG EH EHQHILFLDO IRU WKH VWRUDJH DQG WUDQVSRUW RI WKH EORRG VDPSOHV LQ WKH FOLQLFDO VHWWLQJ &DSV ZLWK YDULRXV GLDPHWHUV DQG YDULRXV VL]HG GHSUHVVLRQV

PAGE 96

ZHUH XVHG 6RPH SUREOHPV ZHUH H[SHULHQFHG ZLWK WKH XQLIRUPLW\ RI WKH SODVPD RQ WKH WLWDQLXP FDS HOHFWURGH $W ORZHU PLFURZDYH SRZHUV WKH SODVPD ZRXOG VRPHWLPHV IRUP RQ RQH VLGH RI WKH FDS DQG HLWKHU VWD\ DW WKDW VLGH RU IOLFNHU DURXQG WKH HGJH RI WKH FDS $W KLJKHU PLFURZDYH SRZHUV VRPH RI WKH FDSV \LHOGHG JRRG VLJQDO EXW LW ZDV GLIILFXOW WR FOHDQ WKHP ZKHQ DQDO\]LQJ EORRG VDPSOHV 7KH FDSV ZHUH DOVR GLIILFXOW WR UHSURGXFLEO\ FRQVWUXFW &DSV ZLWK WKH VDPH GHVLJQ GLG QRW SURGXFH WKH VDPH VLJQDO ‘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f ,QLWLDOO\ VWDLQOHVV VWHHO VFUHHQV DQG PHVKf ZHUH XVHG

PAGE 97

)LJXUH 6XVSHQVLRQ PHWKRG RI VDPSOH LQWURGXFWLRQ

PAGE 98

3ODWLQXP VFUHHQV PHVKf WXQJVWHQ VFUHHQV DQG PHVKf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

PAGE 99

RI VHYHUDO RI WKHVH PHWKRGV ZHUH FRPELQHG WR GHVLJQ DQ LPSURYHG ILODPHQW HOHFWURGH $ WKLFNHU PP LQ GLDPHWHUf WXQJVWHQ ZLUH ZDV XVHG ZKLFK ZDV PRUH GXUDEOH DQG FRXOG VXVWDLQ KLJKHU SRZHUV WKDQ WKH RULJLQDO ILODPHQW PP LQ GLDPHWHUf FRXOG ,QLWLDOO\ D VLQJOH ORRS ZDV PDGH DW WKH WRS RI WKH ZLUH WR KROG WKH VDPSOH EXW LW ZDV GLIILFXOW WR GHSRVLW WKH VDPSOH LQ WKH ORRS $ WZR DQG D KDOI WXUQ VSLUDO ZDV WKHQ PDGH DW WKH WRS RI WKH HOHFWURGH 7KH VSLUDO VHUYHG DV VRUW RI D SODWIRUP DQG KHOG D EORRG VDPSOH YHU\ ZHOO 7KH VSLUDO ILODPHQW HOHFWURGH ILJXUH f SHUIRUPHG ZHOO IRU ERWK DTXHRXV DQG EORRG VDPSOHV FKDSWHU f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f JLYLQJ D GHWHFWLRQ OLPLW RI SSE EXW ZDV YHU\ KDUG WR FOHDQ DIWHU WKH DQDO\VLV RI EORRG VDPSOHV ,W DOVR HURGHG TXLFNO\ XQGHU WKH KLJK SODVPD SRZHUV XVHG WR FOHDQ WKH EORRG IURP WKH HOHFWURGH

PAGE 100

a PP r PP :LUH 'LDPHWHU PP r )LJXUH 7XQJVWHQ VSLUDO ILODPHQW

PAGE 101

&RQFHQWUDWLRQ SSEf )LJXUH $QDO\WLFDO FXUYH IRU DTXHRXV OHDG VWDQGDUGV WKH FRPPHUFLDO WXQJVWHQ ILODPHQW

PAGE 102

&RQFOXVLRQ 7KH EHVW PHWKRG RI VDPSOH LQWURGXFWLRQ ZDV WKH VSLUDO ILODPHQW HOHFWURGH 7KH VSLUDO SURYLGHG D VXUIDFH ZKLFK FRXOG KROG WKH VDPSOH DQG VXSSRUW WKH SODVPD VR WKDW WKH VDPSOH ZDV GLUHFWO\ LQ WKH SODVPD 7KH VDPSOH FRXOG HDVLO\ EH GHSRVLWHG RQ WKH VSLUDO UHSURGXFLEO\ 7KH ILODPHQW ZDV DOVR VLPSOH WR FOHDQ DIWHU HDFK DQDO\VLV

PAGE 103

&+$37(5 $1$/<6,6 2) /($' ,1 %/22' ,QWURGXFWLRQ 7KH LQLWLDO JRDO RI WKH UHVHDUFK ZDV WR GHYHORS WKH &03$(6 DV D VFUHHQLQJ PHWKRG IRU OHDG LQ ZKROH EORRG 7KH JXLGHOLQHV VHW IRUWK E\ WKH &HQWHUV IRU 'LVHDVH &RQWURO &'&f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

PAGE 104

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

PAGE 105

7KH SRZHU RI WKH SODVPD DQG WKH WLPH XVHG IRU DVKLQJ ZHUH YHU\ LPSRUWDQW ,I WKH SRZHU ZDV WRR ORZ RU WKH WLPH ZDV WRR VKRUW QRW HQRXJK RI WKH EORRG PDWHULDO ZDV UHPRYHG FDXVLQJ WKH SUREOHPV MXVW GLVFXVVHG ,I WKH DVKLQJ SRZHU ZDV WRR KLJK RU WKH WLPH ZDV WRR ORQJ WKH DQDO\WH FRXOG EH YRODWLOL]HG DQG ORVW GHFUHDVLQJ WKH VLJQDO 9DULRXV DVKLQJ SRZHUV ILJXUH f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

PAGE 106

6LJQDO )LJXUH (IIHFW RI DVKLQJ SRZHU RQ EORRG OHDG VLJQDO

PAGE 107

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

PAGE 108

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/ ZDV FKRVHQ EHFDXVH WKLV YROXPH JDYH JRRG SUHFLVLRQ DQG ZDV QRW GLIILFXOW WR UHSURGXFLEO\ GHSRVLW RQ WKH HOHFWURGH

PAGE 109

6RXUFHV RI 1RLVH 7KH ODUJHVW VRXUFH RI QRLVH IRU WKH &03$(6 ZDV LQYHVWLJDWHG 6DPSOH UXQV ZHUH SHUIRUPHG WLPHV HDFK IRU DTXHRXV VDPSOHV EORRG VDPSOHV DQG DQ HPSW\ ILODPHQW 7KH QRLVH IURP WKH GDUN FXUUHQW DQG IURP IOXFWXDWLRQV LQ WKH SODVPD ZLWK LW FRQWLQXDOO\ UXQQLQJ ZHUH DOVR LQYHVWLJDWHG 7KH GDUN FXUUHQW ZDV WKH VPDOOHVW VRXUFH RI QRLVH 7KH QRLVH IURP UXQV ZLWK DQ HPSW\ ILODPHQW DQG ZLWK DTXHRXV EODQNV ZDV WKUHH WLPHV WKDW RI WKH GDUN FXUUHQW %ORRG VDPSOHV SURGXFHG D OHYHO RI QRLVH WHQ WLPHV JUHDWHU WKDQ WKH GDUN FXUUHQW 7KH UHVXOWV GHPRQVWUDWH WKDW WKH LQVWDELOLW\ RI WKH HPLVVLRQ EDFNJURXQG IURP WKH EORRG ZDV WKH JUHDWHVW VRXUFH RI QRLVH LQ WKH EORRG DQDO\VLV $QDO\VLV $TXHRXV 6WDQGDUGV $TXHRXV DQDO\WLFDO FXUYHV ZHUH FRQVWUXFWHG XVLQJ S/ VDPSOHV 7KH VDPSOH ZDV GULHG IRU V DW : 7KH SRZHU ZDV GHFUHDVHG WR : DQG D IORZ RI /PLQ RI KHOLXP ZDV LQWURGXFHG 7KH SODVPD ZDV LJQLWHG DQG LPPHGLDWHO\ WKH SRZHU ZDV LQFUHDVHG WR : IRU DWRPL]DWLRQ DQG HPLVVLRQ 7KH OHDG HPLVVLRQ ZDV LQWHJUDWHG RYHU WHQ VHFRQG WLPH LQWHUYDOV 7KH SHDN DUHD RI WKH OHDG VLJQDO DW D ZDYHOHQJWK RI QP ZDV FDOFXODWHG IRU HDFK WLPH LQWHUYDO DQG WKH

PAGE 110

SHDN DUHDV ZHUH DGGHG RYHU WKH OLIHWLPH RI WKH OHDG VLJQDO WR REWDLQ D SHDN YROXPH 7KH VLJQDO ZDV WKHQ SORWWHG YV WKH FRQFHQWUDWLRQ 7KH UHVXOWLQJ DQDO\WLFDO FXUYH LV VKRZQ LQ ILJXUH $ GHWHFWLRQ OLPLW RI SSE ZDV REWDLQHG 7KH FRUUHODWLRQ FRHIILFLHQW RI WKH DQDO\WLFDO FXUYH ZDV DQG WKH ORJORJ VORSH ZDV 7KH SUHFLVLRQ ZDV b IRU FRQFHQWUDWLRQV JUHDWHU WKDQ SSE DQG b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f ZDV DQDO\]HG E\ WKH PHWKRG XVHG IRU DTXHRXV VWDQGDUGV )LJXUH VKRZV WKH WHPSRUDO SURILOH IRU D S/ SSE OHDG EORRG VWDQGDUG (DFK EORRG VWDQGDUG ZDV DQDO\]HG VL[ WLPHV 7KH DQDO\WLFDO FXUYH REWDLQHG E\ UXQQLQJ WKH &'& ERYLQH EORRG VWDQGDUGV LV VKRZQ LQ ILJXUH 7KH HUURU EDUV UHSUHVHQW D b FRQILGHQFH LQWHUYDO 7KH UHODWLYH VWDQGDUG GHYLDWLRQ 56'f IRU EORRG OHDG

PAGE 111

)LJXUH $QDO\WLFDO FXUYH IRU DTXHRXV OHDG VWDQGDUGV RQ VSLUDO HOHFWURGH

PAGE 112

7DEOH 0LFURZDYH SODVPD SRZHU VHWWLQJV IRU EORRG OHDG GHWHUPLQDWLRQ 6WHS 7LPH Vf 3RZHU :f +HOLXP *DV )ORZ 5DWH /PLQf 'U\LQJ 'U\LQJ 'U\LQJ $VKLQJ $VKLQJ $VKLQJ $VKLQJ $WRPL]DWLRQ &OHDQLQJ &OHDQLQJ

PAGE 113

6LJQDO :DYHOHQJWK QPf )LJXUH (PLVVLRQ VSHFWUXP QPf IRU D _L/ ZKROH EORRG VDPSOH FRQWDLQLQJ SSE OHDG

PAGE 114

6LJQDO R R 7LPH Vf )LJXUH 7HPSRUDO SURILOH IRU OHDG HPLVVLRQ VLJQDO LQ EORRG

PAGE 115

)LJXUH $QDO\WLFDO FXUYH IRU ERYLQH EORRG OHDG VWDQGDUGV

PAGE 116

FRQFHQWUDWLRQV RI L SSE LV OHVV WKDQ b 7KH 56' IRU EORRG OHDG FRQFHQWUDWLRQV RI SSE WR SSE LV OHVV WKDQ b 7KH DQDO\WLFDO FXUYH LV OLQHDU ZLWK D FRUUHODWLRQ FRHIILFLHQW RI DQG D ORJORJ VORSH RI 1,67 6WDQGDUGV 7KH 6WDQGDUG 5HIHUHQFH 0DWHULDOV ZHUH DQDO\]HG DQG FRPSDUHG WR WKH DQDO\WLFDO FXUYH REWDLQHG IURP WKH &'& EORRG VWDQGDUGV 7KH PHDVXUHG FRQFHQWUDWLRQV DUH VKRZQ QH[W WR WKH FHUWLILHG FRQFHQWUDWLRQ YDOXHV LQ WDEOH 7KH PHDVXUHG YDOXHV DJUHH ZLWK WKH FHUWLILHG YDOXHV ZLWK b FRQILGHQFH IRU DOO WKH 650nV H[FHSW IRU WKH ORZHVW FRQFHQWUDWLRQ 7KH DFFXUDF\ DW WKLV FRQFHQWUDWLRQ LV UHDVRQDEOH FRQVLGHULQJ WKDW SSE LV YHU\ QHDU WKH GHWHFWLRQ OLPLW RI SSE +XPDQ %ORRG 6WDQGDUG $ KXPDQ EORRG VWDQGDUG RI XQNQRZQ OHDG FRQFHQWUDWLRQ ZDV DOVR DQDO\]HG XVLQJ WKH UHVXOWV IURP WKH OHDG ERYLQH EORRG VWDQGDUGV DV WKH DQDO\WLFDO FXUYH $ YDOXH RI s SSE ZDV GHWHUPLQHG 7KH PHWKRG RI HOHFWURWKHUPDO YDSRUL]DWLRQODVHU HQKDQFHG LRQL]DWLRQ VSHFWURPHWU\ (79 /(,6f ZDV DOVR XVHG WR DQDO\]H WKH VDPH KXPDQ EORRG VWDQGDUG >@ $ OHDG FRQFHQWUDWLRQ RI s SSE ZDV GHWHUPLQHG E\ WKLV PHWKRG

PAGE 117

7DEOH 0HDVXUHPHQW RI 1,67 OHDG LQ ZKROH EORRG VWDQGDUG UHIHUHQFH PDWHULDO 9LDO 1XPEHU &HUWLILHG &RQFHQWUDWLRQ SSEf 0HDVXUHG &RQFHQWUDWLRQ 33Ef b%LDV 6DO s s D s s D s D s s

PAGE 118

%ORRG DQG $TXHRXV 6WDQGDUGV $ GHVLUDEOH FKDUDFWHULVWLF RI WKH PHWKRG ZRXOG EH WKH FDSDELOLW\ RI XVLQJ DTXHRXV VWDQGDUGV IRU WKH DQDO\WLFDO FXUYH 7KH GHSHQGHQFH RI WKH OHDG VLJQDO RQ SODVPD SRZHU GLIIHUHG IRU DTXHRXV DQG EORRG OHDG VWDQGDUGV $V WKH DWRPL]DWLRQ SRZHU IRU DQ DTXHRXV VWDQGDUG ZDV LQFUHDVHG WKH VLJQDO LQFUHDVHG XQWLO LW UHDFKHG D SODWHDX )RU EORRG VWDQGDUGV KRZHYHU WKH VLJQDO LQLWLDOO\ LQFUHDVHG ZLWK LQFUHDVLQJ SRZHU EXW WKHQ UHDFKHG D PD[LPXP DQG VWDUWHG WR VORZO\ GHFUHDVH $W DQ DWRPL]DWLRQ SRZHU RI : WKH VLJQDO IRU ERWK W\SHV RI VWDQGDUGV ZDV WKH VDPH DV VKRZQ LQ ILJXUH 7KLV ZRXOG DOORZ WKH XVH RI DTXHRXV VWDQGDUGV IRU WKH GHWHUPLQDWLRQ RI WKH OHDG OHYHOV LQ ZKROH EORRG VWDQGDUGV )LJXUH VKRZV DQ DQDO\WLFDO FXUYH LQ ZKLFK ERWK EORRG DQG DTXHRXV VWDQGDUGV ZHUH XVHG 7KLV FXUYH VKRZV JRRG DJUHHPHQW 5 f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

PAGE 119

6LJQDO QR n n n n n n n $WRPL]DWLRQ 3RZHU :f )LJXUH 3RZHU FRPSDULVRQ IRU EORRG DQG DTXHRXV OHDG VWDQGDUGV

PAGE 120

,OO &RQFHQWUDWLRQ SSEf )LJXUH $QDO\WLFDO FXUYH IRU EORRG DQG DTXHRXV OHDG VWDQGDUGV

PAGE 121

VWDQGDUG RI WKH VDPH FRQFHQWUDWLRQ RI OHDG ZHUH PL[HG LQ YDULRXV DPRXQWV WR SURGXFH EORRG VDPSOHV WKDW ZHUH DQG b ZKROH EORRG $OWKRXJK WKH VDPSOH FRPSRVLWLRQ ZDV GLIIHUHQW IRU HDFK VWDQGDUG WKH FRQFHQWUDWLRQ RI OHDG UHPDLQHG WKH VDPH 7KH LQWHQVLW\ RI OHDG VLJQDO IRU WKHVH VDPSOHV DQG IRU SXUH EORRG DQG DTXHRXV VDPSOHV ZDV PHDVXUHG DW VHYHUDO DWRPL]DWLRQ SRZHUV UDQJLQJ IURP WR : 7KH WHPSRUDO SURILOHV IRU WKH ZKROH EORRG WKH b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

PAGE 122

Ef )LJXUH 7LPH Vf 7HPSRUDO SURILOHV IRU WKH OHDG VLJQDO LQ VDPSOHV RI YDU\LQJ EORRG FRPSRVLWLRQ DW DWRPL]DWLRQ SRZHUV RI Df Z DQG Ef :

PAGE 123

OHDG DQDO\WH FRXOG EH ORVW GXULQJ WKH DVKLQJ VWHS 7KLV ZRXOG H[SODLQ ZK\ WKH VLJQDO IRU DTXHRXV VDPSOHV LQFUHDVHG EH\RQG WKDW RI WKH EORRG VDPSOHV IRU KLJK DWRPL]DWLRQ SRZHUV &RQFOXVLRQ 7KH FXUUHQW V\VWHP VDWLVILHV RU DSSURDFKHV PDQ\ RI WKH UHTXLUHPHQWV RI WKH &'& 7KH DFFXUDF\ DQG SUHFLVLRQ DSSURDFK s SSE DW SSE ZLWK D ORZHU GHWHFWLRQ OLPLW DSSURDFKLQJ SSE 7KH UHTXLUHG EORRG VSHFLPHQ YROXPH LV RQO\ 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

PAGE 124

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

PAGE 125

6LJQDO )LJXUH (PLVVLRQ VSHFWUXP RI ZKROH EORRG

PAGE 126

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f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

PAGE 127

DTXHRXV VWDQGDUGV ILJXUH f DW DQ DWRPL]DWLRQ SRZHU RI : )LJXUH VKRZV WKH DQDO\WLFDO VLJQDO IRU ]LQF LQ EORRG 7KH /2' IRU ]LQF LQ EORRG ZDV SSP DW DQ DWRPL]DWLRQ SRZHU RI : 7KH GHWHFWLRQ OLPLW UHPDLQHG DSSUR[LPDWHO\ WKH VDPH SSPf IRU DQ DWRPL]DWLRQ SRZHU RI : 7KH PHDVXUHG FRQFHQWUDWLRQ RI ]LQF LQ KXPDQ EORRG ZDV s SSP DW DQ DWRPL]DWLRQ SRZHU RI : ILJXUH f DQG s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f $ UHG JODVV ILOWHU ZDV SODFHG LQ IURQW RI WKH VSHFWURPHWHU DQG WKLV JUHDWO\ UHGXFHG WKH EDFNJURXQG ILJXUH Ef 7KH PHDVXUHG FRQFHQWUDWLRQ RI OLWKLXP LQ EORRG ZDV s SSE ZLWK D GHWHFWLRQ OLPLW RI SSE ILJXUH f 7KH PHDVXUHG FRQFHQWUDWLRQ RI OLWKLXP LQ EORRG FRUUHVSRQGV ZLWK UHIHUHQFH YDOXHV +RZHYHU WKH DPRXQW RI

PAGE 128

6LJQDO &RQFHQWUDWLRQ SSPf )LJXUH $QDO\WLFDO FXUYH IRU DTXHRXV ]LQF VWDQGDUGV DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 129

,QWHQVLW\ )LJXUH 6SHFWUXP RI D S/ SSP ]LQF EORRG VDPSOH DW DQ DWRPL]DWLRQ SRZHU RI :

PAGE 130

6LJQDO &RQFHQWUDWLRQ SSPf )LJXUH 6WDQGDUG DGGLWLRQV IRU ]LQF LQ EORRG DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 131

&RQFHQWUDWLRQ SSEf )LJXUH $QDO\WLFDO FXUYH IRU DTXHRXV OLWKLXP VWDQGDUGV DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 132

,QWHQVLW\ ,QWHQVLW\ :DYHOHQJWK Ef :DYHOHQJWK QPf )LJXUH 6SHFWUD RI D / SSE OLWKLXP EORRG VDPSOH DW DQ DWRPL]DWLRQ SRZHU RI : EHIRUH Df DQG DIWHU Ef DGGLWLRQ RI UHG JODVV ILOWHU

PAGE 133

$ 6LJQDO }f UR FQ R R R R R R R / $ f§Lf§Lf§Lf§Lf§Lf§Lf§Lf§Lf§Lf§L &RQFHQWUDWLRQ SSEf )LJXUH 6WDQGDUG DGGLWLRQV IRU OLWKLXP LQ EORRG DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 134

OLWKLXP LQ WKH EORRG RI SDWLHQWV UHFHLYLQJ OLWKLXP WUHDWPHQW LV XVXDOO\ VHYHUDO SSP $ ZHDNHU OLWKLXP OLQH DW UDQ ZDV XVHG WR LQYHVWLJDWH WKH OLQHDULW\ RI DQDO\VLV LQ WKLV KLJKHU FRQFHQWUDWLRQ UDQJH $TXHRXV VWDQGDUGV ZHUH ILUVW DQDO\]HG XVLQJ DQ DWRPL]DWLRQ SRZHU RI : )LJXUH VKRZV WKDW WKH OLQHDU G\QDPLF LQFOXGHV WKH UHJLRQ RI LQWHUHVW ZLWK D GHWHFWLRQ OLPLW RI SSE DQG D FRUUHODWLRQ FRHIILFLHQW RI %ORRG VDPSOHV FRQWDLQLQJ KLJKHU OLWKLXP FRQFHQWUDWLRQV ZHUH DOVR DQDO\]HG ILJXUH f $ GHWHFWLRQ OLPLW RI SSE ZLWK D FRUUHODWLRQ FRHIILFLHQW RI ZDV REWDLQHG 7KH UHODWLYH VWDQGDUG GHYLDWLRQ ZDV EHWWHU WKDQ b IRU DOO FRQFHQWUDWLRQV PHDVXUHG IRU ERWK EORRG DQG DTXHRXV VWDQGDUGV 0DJQHVLXP 7KH QP DWRPLF HPLVVLRQ OLQH ZDV XVHG IRU WKH DQDO\VLV RI PDJQHVLXP ILJXUH f 7KH ORZ SRZHU XVHG IRU DWRPL]DWLRQ RI WKH RWKHU HOHPHQWV ZDV QRW VXIILFLHQW IRU WKH PDJQHVLXP $Q DWRPL]DWLRQ SRZHU RI : ZDV XVHG 7KH /2'nV ZHUH SSP IRU DTXHRXV VWDQGDUGV DQG SSP IRU EORRG 7KH PHDVXUHG OHYHO RI 0J LQ WKH KXPDQ EORRG VDPSOH ZDV s SSP ILJXUH f

PAGE 135

&RQFHQWUDWLRQ SSPf )LJXUH $QDO\WLFDO FXUYH IRU DTXHRXV OLWKLXP VWDQGDUGV DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 136

&RQFHQWUDWLRQ SSPf )LJXUH $QDO\WLFDO FXUYH IRU EORRG OLWKLXP VWDQGDUGV DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI Z

PAGE 137

,QWHQVLW\ )LJXUH 6SHFWUXP RI D S/ SSP PDJQHVLXP EORRG VDPSOH DW DQ DWRPL]DWLRQ SRZHU RI : WR &'

PAGE 138

&RQFHQWUDWLRQ SSPf )LJXUH 6WDQGDUG DGGLWLRQV IRU PDJQHVLXP LQ EORRG DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 139

0DQJDQHVH 0DQJDQHVH 0Qf KDV WKUHH FORVHO\ VSDFHG DWRPLF HPLVVLRQ OLQHV DW DQG QP 7KH VSHFWURPHWHU ZDV QRW DEOH WR IXOO\ UHVROYH WKHVH OLQHV VR WKH FRPELQHG DUHD RI DOO WKUHH SHDNV ZDV XVHG IRU DQDO\VLV $Q LQWHUIHULQJ SHDN DSSHDUHG YHU\ FORVH WR WKH 0Q SHDN DQG ZDV DFFRXQWHG IRU E\ EODQN VXEWUDFWLRQ 7KH LQWHJUDWLRQ WLPH ZDV UHGXFHG IURP WZR VHFRQGV WR RQH VHFRQG DQG WKLV UHGXFHG WKH DPRXQW RI EDFNJURXQG ZLWKRXW UHGXFLQJ WKH DPRXQW RI 0Q VLJQDO 7KH DQDO\VLV RI PDQJDQHVH UHTXLUHG DQ DWRPL]DWLRQ SRZHU RI : 7KH /2'nV IRU 0Q ZHUH SSE IRU DTXHRXV VWDQGDUGV ILJXUH f DQG SSE IRU EORRG VWDQGDUGV ILJXUH f $ FRQFHQWUDWLRQ RI s SSE ZDV PHDVXUHG LQ WKH KXPDQ EORRG VDPSOH 3ULPDU\ (OHPHQWV 6RGLXP 7KH UHVRQDQFH OLQHV RI VRGLXP DW DQG ZHUH LQYHVWLJDWHG IRU XVH LQ WKH PHDVXUHPHQW RI VRGLXP EORRG OHYHOV 7KH DQDO\WLFDO FXUYH IRU DTXHRXV VWDQGDUGV ILJXUH f ZDV OLQHDU XS WR D FRQFHQWUDWLRQ RI SSP 7KH FRUUHODWLRQ FRHIILFLHQW XVLQJ WKH UHVXOWV IRU VRGLXP FRQFHQWUDWLRQV XS WR SSP ZDV ZLWK D ORJORJ VORSH RI 7KH GHWHFWLRQ OLPLW ZDV SSE IRU DQ DWRPL]DWLRQ

PAGE 140

&RQFHQWUDWLRQ SSEf )LJXUH $TXHRXV DQDO\WLFDO FXUYH IRU PDQJDQHVH DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 141

&RQFHQWUDWLRQ SSEf )LJXUH 6WDQGDUG DGGLWLRQV IRU PDQJDQHVH LQ EORRG DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 142

6LJQDO &RQFHQWUDWLRQ SSPf )LJXUH $TXHRXV DQDO\WLFDO FXUYH IRU VRGLXP DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 143

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s SSP 34Wt66LZQ 7KH OHYHO RI SRWDVVLXP .f LQ EORRG ZDV PHDVXUHG XVLQJ WKH DWRPLF HPLVVLRQ OLQHV DW DQG 1HXWUDO GHQVLW\ ILOWHUV ZHUH XVHG WR UHGXFH WKH LQWHQVLW\ VR WKDW WKH GHWHFWRU ZDV DEOH WR PHDVXUH WKH SRWDVVLXP HPLVVLRQ /2'nV RI SSE IRU DQ DWRPL]DWLRQ SRZHU RI : DQG SSE IRU DQ DWRPL]DWLRQ SRZHU RI : ZHUH GHWHUPLQHG IRU DTXHRXV VWDQGDUGV 7KH /2' IRU SRWDVVLXP LQ EORRG ZDV SSP IRU DQ DWRPL]DWLRQ SRZHU RI : 7KH PHDVXUHG FRQFHQWUDWLRQ RI SRWDVVLXP LQ WKH KXPDQ EORRG VDPSOH ZDV SSP ILJXUH f

PAGE 144

,QWHQVLW\ )LJXUH 6SHFWUXP RI D S/ SSP VRGLXP EORRG VDPSOH DW DQ DWRPL]DWLRQ SRZHU RI :

PAGE 145

6LJQDO &RQFHQWUDWLRQ SSPf )LJXUH 6WDQGDUG DGGLWLRQV IRU VRGLXP LQ EORRG DW D ZDYHOHQJWK RI QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 146

6LJQDO &RQFHQWUDWLRQ SSPf )LJXUH 6WDQGDUG DGGLWLRQV IRU SRWDVVLXP LQ EORRG DW ZDYHOHQJWKV RI DQG QP DQG DQ DWRPL]DWLRQ SRZHU RI :

PAGE 147

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

PAGE 148

7DEOH &RPSDULVRQ RI PHDVXUHG HOHPHQWDO FRQFHQWUDWLRQV WR OLWHUDWXUH YDOXHV (OHPHQW &RQFHQWUDWLRQ UDQJH LQ EORRG SSPf >@ 0HDVXUHG FRQFHQWUDWLRQ SSPf 6RGLXP s 3RWDVVLXP s 0DJQHVLXP s /HDG s =LQF s 0DQJDQHVH /LWKLXP s

PAGE 149

&RQFOXVLRQ 7KH &03$(6 ZDV VXFFHVVIXOO\ DEOH WR PHDVXUH WKH OHYHOV RI VRGLXP SRWDVVLXP PDJQHVLXP OLWKLXP ]LQF DQG PDQJDQHVH LQ EORRG 7KH SUHFLVLRQ IRU PRVW FRQFHQWUDWLRQV ZDV EHWWHU WKDQ b DQG WKH OLQHDULW\ ZDV H[FHOOHQW RYHU WKH FRQFHQWUDWLRQ UDQJH RI LQWHUHVW 7KH GHWHFWLRQ OLPLWV IRU DOO WKH HOHPHQWV H[FHSW IRU PDQJDQHVH ZHUH EHORZ WKH UDQJH RI FRQFHQWUDWLRQV IRXQG LQ KXPDQ EORRG

PAGE 150

&+$37(5 &21&/86,216 $1' )8785( :25. &RQFOXVLRQV &03$(6 DV D /HDG LQ %ORRG 6FUHHQLQJ 0HWKRG 7KH &03$(6 FXUUHQWO\ VDWLVILHV PRVW RI WKH &HQWHUV IRU 'LVHDVH &RQWUROnV UHTXLUHPHQWV IRU D VFUHHQLQJ PHWKRG IRU OHDG LQ EORRG ,W LV FDSDEOH RI GHWHFWLQJ EORRG OHDG OHYHOV DFFXUDWHO\ EHORZ WKH FXUUHQW OHYHO RI FRQFHUQ 7KH OLPLW RI GHWHFWLRQ IRU OHDG LQ EORRG E\ WKH &03$(6 LV QHDU WKDW REWDLQHG E\ ,&3$(6 >@ 7KH &03$(6 KDV WKH DGYDQWDJH RYHU RWKHU PHWKRGV WKDW LW FDQ DQDO\]H ZKROH EORRG GLUHFWO\ ZLWKRXW DQ\ VDPSOH SUHWUHDWPHQW RU GLOXWLRQ /LPLWDWLRQV RI LWV XVH LQFOXGH WKH KLJK LQLWLDO FRVW IRU WKH LQVWUXPHQWDWLRQ GLIILFXOWLHV LQ WUDQVSRUWLQJ LW LH WR VFKRROVf DQG WKH UHTXLUHPHQW RI D FRPSUHVVHG JDV VRXUFH &03$(6 DV D 0XOWLHOHPHQW &OLQLFDO 7HFKQLTXH 7KH &03$(6 LV D WHFKQLTXH ZLWK VHQVLWLYLW\ WR DQDO\]H WUDFH HOHPHQWV DQG WKH OLQHDU G\QDPLF UDQJH WR PHDVXUH SULPDU\ HOHPHQWV 7KH LQVWUXPHQWDWLRQ LV LQH[SHQVLYH FRPSDUHG WR *)$$6 DQG ,&306 EXW LW LV H[SHQVLYH FRPSDUHG

PAGE 151

WR WKH HOHFWURFKHPLFDO PHWKRGV &03$(6 KDV WKH DGYDQWDJH RYHU HOHFWURFKHPLFDO PHWKRGV WKDW UHDJHQWV DUH QRW QHHGHG 7KH &03$(6 KDV VHYHUDO GLVDGYDQWDJHV IRU EORRG DQDO\VLV ,QWHUIHULQJ HPLVVLRQ OLQHV IURP WKH HOHFWURGH PDWHULDO FDQ PDNH WKH DQDO\VLV RI VRPH HOHPHQWV GLIILFXOW :KHQ WKH HOHFWURGH ZHDUV GRZQ LW PXVW EH UHSODFHG DQG WKHQ LW LV QHFHVVDU\ WR UHFDOLEUDWH WKH V\VWHP EHFDXVH WKH HOHFWURGHV DUH QRW UHSURGXFLEOH $OVR WKH HOHFWURGHV DUH GLIILFXOW WR PDNH EHFDXVH WKH WXQJVWHQ LV VRPHZKDW EULWWOH &XUUHQWO\ WKH RQO\ ZD\ WR DQDO\]H EORRG VDPSOHV LV E\ WKH PHWKRG RI VWDQGDUG DGGLWLRQV 7KLV DGGV WR WKH DQDO\VLV WLPH DQG LV D SRWHQWLDO VRXUFH RI FRQWDPLQDWLRQ ,I DTXHRXV VWDQGDUGV FRXOG EH XVHG IRU FDOLEUDWLRQ WKH PHWKRG ZRXOG EH FOLQLFDOO\ XVHIXO )XWXUH :RUN 7KH PHWKRG KDV SURYHQ WR EH FDSDEOH RI DQDO\]LQJ WKH HOHPHQWV VWXGLHG EXW IXUWKHU UHVHDUFK LV QHFHVVDU\ WR GHYHORS WKH PHWKRG LQWR VRPHWKLQJ WKDW FRXOG EH FRPPHUFLDOO\ PDGH IRU FOLQLFDO DQDO\VLV 7KH PHWKRG FRXOG DOVR EH XVHG LQ D QXPEHU RI RWKHU UHVHDUFK SURMHFWV

PAGE 152

$QDO\VLV RI 2WKHU +HDOWK 5HODWHG (OHPHQWV 2WKHU HVVHQWLDO WUDFH HOHPHQWV WKDW FRXOG EH VWXGLHG LQFOXGH LURQ FDOFLXP FKURPLXP FREDOW FRSSHU PRO\EGHQXP DQG VHOHQLXP >@ ,URQ )Hf GHILFLHQF\ LV RQH RI WKH PRVW ZLGHVSUHDG QXWULWLRQDO GHILFLHQFLHV ZRUOG ZLGH >@ 5HVHDUFKHUV DW WKH 1DWLRQDO &HQWHU IRU +HDOWK 6WDWLVWLFV +\DWWVYLOOH 0Gf HVWLPDWH WKDW LQIDQWV DQG PLOOLRQ ZRPHQ DUH LURQ GHILFLHQW > @ ,W LV HVWLPDWHG WKDW RYHU RQH WKLUG RI WKHVH FDVHV KDYH LURQ GHILFLHQF\ DQHPLD ,I RFFXUULQJ GXULQJ LQIDQF\ DQG HDUO\ FKLOGKRRG LURQ GHILFLHQF\ DQHPLD ,'$f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nV FHOOV $SSUR[LPDWHO\ WZR WKLUGV RI WKH ERG\nV LURQ LV WLHG XS LQ KHPRJORELQ LQ WKH

PAGE 153

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nV GLVHDVH > @ 0RQLWRULQJ

PAGE 154

WKH OHYHOV RI DOXPLQXP LQ WKH VHUXP DQG XULQH RI SDWLHQWV ZLWK UHQDO GLVHDVH LV DQ HIILFLHQW ZD\ WR PRQLWRU WKHLU SDWKRORJLFDO VWDWXV >@ &DGPLXP WR[LFLW\ LV D SDUWLFXODU ULVN WR VPRNHUV EHFDXVH FLJDUHWWHV \LHOG FDGPLXP LQ WKH VPRNHUnV OXQJV >@ &DGPLXP GLVSODFHV ]LQF IURP LPSRUWDQW HQ]\PHV PDNLQJ WKHP LQDFWLYH >@ 8VLQJ $TXHRXV 6WDQGDUGV IRU %ORRG $QDO\VLV 7KH XVH RI EORRG VDPSOHV DV VWDQGDUGV LV QRW YHU\ SUDFWLFDO $OWKRXJK WKH H[LVWHQFH RI OHDG LQ ERYLQH EORRG VWDQGDUGV IURP WKH &'&n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

PAGE 155

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

PAGE 156

7XQJVWHQ ILODPHQW 7XQJVWHQ OLJKWEXOE ILODPHQW )LJXUH 3URSRVHG PHWKRG RI XVLQJ D FRPPHUFLDO WXQJVWHQ OLJKWEXOE ILODPHQW DV WKH PHWKRG RI VDPSOH LQWURGXFWLRQ

PAGE 157

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

PAGE 158

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

PAGE 159

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

PAGE 160

0LQLDWXUL]H 6\VWHP 7KH HOHFWURQLFV RI WKH &03$(6 DUH FDSDEOH RI EHLQJ UHGXFHG GUDVWLFDOO\ LQ VL]H 7KH PLFURZDYH SODVPD SRUWLRQ RI WKH VHWXS VKRXOG EH DEOH WR EH UHGXFHG WR WKH VL]H RI D VPDOO PLFURZDYH RYHQ &XUUHQWO\ PLFURZDYH RYHQV FRQVLVW RI YHU\ VLPLODU SDUWV SURJUDPPDEOH SRZHU VXSSO\ KLJKPHGLXPORZf PDJQHWURQ DQG ZDYHJXLGH 7R IXOO\ PLQLDWXUL]H WKH V\VWHP D PHWKRG RI GHWHFWLRQ FRQVLVWLQJ RI VPDOOHU FRPSRQHQWV ZRXOG DOVR KDYH WR EH IRXQG $FRXVWRRSWLF WXQDEOH ILOWHU $Q DFRXVWRRSWLF WXQDEOH ILOWHU $27)f LV D FRPSDFW WXQDEOH QDUURZEDQG OLJKW ILOWHU >@ $Q $27) LV FRQVWUXFWHG E\ ERQGLQJ D SLH]RHOHFWULF WUDQVGXFHU WR D ELUHIULQJHQW FU\VWDO XVXDOO\ TXDUW] RU SDUDWHOOXULWH 7Hf $FRXVWLF ZDYHV DUH SURSDJDWHG WKURXJK WKH FU\VWDO E\ DSSO\LQJ D UDGLR IUHTXHQF\ UIf VLJQDO WR WKH WUDQVGXFHU 7KH DFRXVWLF ZDYHV SURGXFH JUDWLQJ LQ WKH FU\VWDO WKDW FDQ GLIIUDFW VHOHFW ZDYHOHQJWKV RI WKH LQFLGHQW EHDP 7KH SRVLWLRQ RI WKH EDQGSDVV FDQ EH FRQWUROOHG HOHFWURQLFDOO\ RYHU D ZLGH VSHFWUDO UDQJH E\ FKDQJLQJ WKH IUHTXHQF\ RI WKH UI VLJQDO >@ $27)nV KDYH EHHQ XVHG LQ IOXRUHVFHQFH HPLVVLRQ DQG VSHFWURVFRSLF LPDJLQJ H[SHULPHQWV >@ DQG WR WXQH DQG VWDELOL]H D ODVHU EHDP >@ +RUOLFN DQG )XOWRQ KDYH LQYHVWLJDWHG XVLQJ DQ $27) IRU DWRPLF VSHFWURPHWU\ >@ $Q LQGXFWLYHO\ FRXSOHG SODVPD D

PAGE 161

JORZ GLVFKDUJH DQG D KROORZ FDWKRGH ODPS ZHUH XVHG DV DWRPLF HPLVVLRQ VRXUFHV %\ XVLQJ WZR $27) FU\VWDOV WKH ZDYHOHQJWK UDQJH RI QP ZDV FRYHUHG ,Q RQH VHFRQG WKH HQWLUH VSHFWUXP ZDV VFDQQHG ZLWK D UHVROXWLRQ RI QP DW QP 8VLQJ DQ $27) ZLWK WKH &03$(6 LQVWHDG RI WKH FXUUHQWO\ XVHG VSHFWURPHWHU FRXOG KHOS PDNH LW PRUH VXLWDEOH DV D VFUHHQLQJ RU FOLQLFDO WHFKQLTXH 7KH DUUD\ W\SH GHWHFWRUV ZRXOG EH XQQHFHVVDU\ DQG D SKRWRPXOWLSOLHU WXEH 307f RU D SKRWRGLRGH FRXOG EH XVHG IRU WKH PHDVXUHPHQW RI WKH DQDO\WLFDO VLJQDO 7KLV ZRXOG JUHDWO\ UHGXFH WKH VL]H DQG H[SHQVH RI WKH &&03$(6 0LQLDWXUH GHWHFWRU 0LQLDWXUH ILEHU RSWLF VSHFWURPHWHUV DUH FRPPHUFLDOO\ DYDLODEOH IRU XQGHU 6 )LEHU 2SWLF 6SHFWURPHWHU 2FHDQ 2SWLFV ,QF 'XQHGLQ )/f 2QH VSHFWURPHWHU LV VR VPDOO WKDW LW FDQ ILW RQ D FRPSXWHU FDUG LQVLGH D QRWHERRN FRPSXWHU &XUUHQWO\ WKH VHQVLWLYLW\ DQG UHVROXWLRQ PD\ QRW EH VXIILFLHQW WR DQDO\]H HOHPHQWV LQ EORRG LQ WKH ORZ SSE UDQJH EXW LW PLJKW EH DEOH WR PHDVXUH WKH HPLVVLRQ VLJQDO DW WKH SSP OHYHO ,I WKLV V\VWHP FRXOG EH XVHG ZLWK D UHGXFHG VL]HG PLFURZDYH SODVPD VHWXS WKH V\VWHP ZRXOG EH SRUWDEOH WR VRPH H[WHQW ,W ZRXOG DOVR EH TXLWH LQH[SHQVLYH IRU DQ DWRPLF HPLVVLRQ LQVWUXPHQW

PAGE 162

$WRPL]DWLRQ 0HWKRG IRU 2WKHU 7HFKQLTXHV 7KH ILODPHQW VXSSRUWHG PLFURZDYH SODVPD LV D YHU\ HIILFLHQW DWRPL]DWLRQ VRXUFH 7KH DQDO\WLFDO YROXPH LV YHU\ FRPSDFW DQG FRXOG EH XVHG DV DQ DWRPL]DWLRQ VRXUFH IRU RWKHU DQDO\WLFDO PHWKRG /DVHU H[FLWHG DWRPLF IOXRUHVFHQFH VSHFWURPHWU\ /($)6f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

PAGE 163

/,67 2) 5()(5(1&(6 $+ $OL .& 1J DQG -' :LQHIRUGQHU -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ f : 5 / 0DVDPED % : 6PLWK DQG :LQHIRUGQHU $SSOLHG 6SHFWURVFRS\ f %0 6SHQFHU DQG -' :LQHIRUGQHU &DQDGLDQ -RXUQDO RI $SSOLHG 6SHFWURVFRS\ f 9HUVLHFN DQG 5 &RUQHOOV 7UDFH (OHPHQWV LQ +XPDQ 3ODVPD RU 6HUXP &5& 3UHVV %RFD 5DWRQ )/ f ,QJOH DQG 6 5 &URXFK 6SHFWURFKHPLFDO $QDO\VLV 3UHQWLFH+DOO ,QF 1HZ -HUVH\ f 0 'D[ 56' 0DJD]LQH f '& +DUULV 4XDQWLWDWLYH &KHPLFDO $QDO\VLV VHFRQG HG :+ )UHHPDQ DQG &RPSDQ\ 86$ f 76 /DYHUJKHWWD 3UDFWLFDO 0LFURZDYHV (QJOHZRRG &OLIIV 1HZ -HUVH\ 3UHQWLFH +DOO f $: 6FRWW 8QGHUVWDQGLQJ 0LFURZDYHV :LOH\ 1HZ
PAGE 164

: .HVVOHU DQG ) *HEKDUW *ODVWHFK %HU f 5 0DYURGLQHDQX DQG 5& +XJKHV 6SHFWURFKLPLFD $FWD f )DOOJDWWHU 9 6YRERGD DQG -' :LQHIRUGQHU $SSOLHG 6SHFWURVFRS\ f 4 -LQ < 'XDQ DQG -$ 2OLYDUHV 6SHFWURFKLPLFD $FWD 3DUW % f $7 =DQGHU DQG *0 +LHIWMH $SSOLHG 6SHFWURVFRS\ f 0DUVKDOO $ )LVKHU 6 &KHQHU\ DQG 67 6SDUNHV -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ f %HDXFKHPLQ -&< /H%ODQF *5 3HWHUV DQG -0 &UDLJ $QDO\WLFDO &KHPLVWU\ f -' :LQHIRUGQHU (3 :DJQHU DQG %: 6PLWK -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ f $ &URVO\Q %: 6PLWK DQG -' :LQHIRUGQHU &ULWLFDO 5HYLHZV LQ $QDO\WLFDO &KHPLVWU\ LQ SUHVV $+ $OL -' :LQHIRUGQHU $QDO\WLFV &KLPLFD $FWD f %0 6SHQFHU %: 6PLWK DQG -' :LQHIRUGQHU $SSOLHG 6SHFWURVFRS\ f % 0 3DWHO ( +HLWKPDU DQG :LQHIRUGQHU $QDO\WLFDO &KHPLVWU\ f 4 -LQ & =KX 0: %RUHU DQG *0 +LHIWMH 6SHFWURFKLPLFD $FWD % f 4 -LQ + =KDQJ < :DQJ ;
PAGE 165

< 'XDQ < /L 0 +RX = 'X DQG 4 -LQ $SSOLHG 6SHFWURVFRS\ f < 'XDQ ; 'X DQG 4 -LQ -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ f < 'XDQ ; 'X < /L DQG 4 -LQ $SSOLHG 6SHFWURVFRS\ f < 'XDQ < /L ; 7LDQ + =KDQJ DQG 4 -LQ $QDO\WLFV &KLPLFD $FWD f ./ 1XWWDOO :+ *RUGRQ DQG .2 $VK $QQDOV RI &OLQLFDO DQG ODERUDWRU\ 6FLHQFH f -: 2OHVLN $QDO\WLFDO &KHPLVWU\ $ f 0( 5HXVVHU DQG '$ 0F&DUURQ 1XWULWLRQ 5HYLHZV f $ 6WDQZD\ 7UDFH (OHPHQWV 0LUDFOH 0LFUR 1XWULHQWV 7KRUVRQV 3XEOLVKLQJ *URXS 5RFKHVWHU 97 f :RUOG +HDOWK 2UJDQL]DWLRQ 7UDFH (OHPHQWV LQ +XPDQ 1XWULWLRQ DQG +HDOWK 0DFPLOODQ %HOJLXP f ) /LFDVWUR 0 &KLULFROR 0& 0RULQL &DSUL /'DYLV 5 &RQWHF 5 0DQFLQL & 0HORWWL 5 3£UHQWH 5 6HUUD DQG ( &DUSHQH *HURQWRORJ\ f $6 3UDVDG HG (VVHQWLDO DQG 7R[LF 7UDFH (OHPHQWV LQ +XPDQ +HDOWK DQG 'LVHDVH $ODQ 5 /LVV ,QF 1HZ
PAGE 166

3/DQGULJDQ DQG $& 7RGG :HVWHUQ -RXUQDO RI 0HGLFLQH f -( )RXONH )'$ &RQVXPHU f 1REOH $QDO\WLFDO &KHPLVWU\ $ f -0 &KULVWHQVRQ 6FLHQFH RI WKH 7RWDO (QYLURQPHQW f &$ %XUWLV DQG (5 $VKZRRG HGV 7LHW] )XQGDPHQWDOV RI &OLQLFDO &KHPLVWU\ :% 6DXQGHUV &RPSDQ\ 3KLODGHOSKLD f -+ )UHHODQG*UDYHV DQG -5 7XUQODQG -RXUQDO RI 1XWULWLRQ 6 f 3*RRGQLFN DQG 55 )LHYH $PHULFDQ -RXUQDO RI 3V\FKLDWU\ f / 6KHQ 6 ;LDRTXDQ DQG 1 =KHPLQJ -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ f *' &KULVWLDQ -RXUQDO RI 3KDUPDFHXWLFDO DQG %LRPHGLFDO $QDO\VLV f -% +HQU\ HG &OLQLFDO 'LDJQRVLV DQG 0DQDJHPHQW E\ /DERUDWRU\ 0HWKRGV WK HG :% 6DXQGHUV &RPSDQ\ 3KLODGHOSKLD f 00 3OXKDWRU $% 7KRPVRQ DQG 51 )HGRUDN &DQ *DVWURHQWHURORJ\ f ++ 6DQGVWHDG DQG -& 6PLWK -RXUQDO RI 1XWULWLRQ 6 f %0 $OWXUD DQG %7 $OWXUD 6FDQG &OLQ /DE ,QYHVW f .DKQ &OLQLFDO /DERUDWRU\ 1HZV f 33DUVRQV $$ 5HLOO\ DQG $ +XVVDLQ &OLQLFDO &KHPLVWU\ f $$ /DPOD DQG 7
PAGE 167

19 6WDQWRQ (: *XQWHU 33DUVRQV DQG 3+ )LHOG &OLQLFDO &KHPLVWU\ f %)HOGPDQ $ 'n$OHVVDQGUR -' 2VWHUORK DQG %+ +DWD &OLQLFDO &KHPLVWU\ f 7= /LX /DL DQG -' 2VWHUORK $QDO\WLFDO &KHPLVWU\ f %)HOGPDQ -' 2VWHUORK %+ +DWD DQG $ 'n$OHVVDQGUR $QDO\WLFDO &KHPLVWU\ f 60 5RGD 5' *UHHQODQG 5/ %RUQVFKHLQ DQG 3% +DPPRQG &OLQLFDO &KHPLVWU\ f -' 2VWHUORK '6 6KDUS DQG % +DWD -RXUQDO RI $QDO\WLFDO 7R[LFRORJ\ f -DJQHU DQG < :DQJ (OHFWURDQDO\VLV f 3 2VWDSF]XN &OLQLFDO &KHPLVWU\ f -DJQHU 0 -RVHIVRQ 6 :HVWHUOXQG DQG $UHQ $QDO\WLFDO &KHPLVWU\ f 3%URFNPDQ DQG :) 'ULVODQH 3LWWVEXUJK &RQIHUHQFH $EVWUDFW &KLFDJR ,/ f &/ 6DQIRUG 6( 7KRPDV DQG %7 -RQHV $SSOLHG 6SHFWURVFRS\ f '& 3DVFKDO ./ &DOGZHOO DQG %* 7LQJ -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ f +<
PAGE 168

33DUVRQV DQG : 6ODYLQ 6SHFWURFKLPLFD $FWD % f %( -DFREVRQ /RFNLWFK DQG 4XLJOH\ &OLQLFDO &KHPLVWU\ f %DUDQRZVND 2FFXSDWLRQDO DQG (QYLURQPHQWDO 0HGLFLQH f 3& 'n+DHVH /9 /DPEHUWV / /LDQJ )/ 9DQ GH 9\HU DQG 0( 'H %URH &OLQLFDO &KHPLVWU\ f '7 0LOOHU '& 3DVFKDO (: *XQWHU 3( 6WURXG DQG -RVHSK 'n$QJHOR $QDO\VW f 33DUVRQV (QYLURQPHQWDO 5HVHDUFK f &'& 0DWHUQDO DQG &KLOG +HDOWK 5HVRXUFHV 'HYHORSPHQW 3URILFLHQF\ 7HVWLQJ 3URJUDP %ORRG /HDG -XO\ .6 6XEUDPDQLDQ 7KH 6FLHQFH RI WKH 7RWDO (QYLURQPHQW f -) 5RVHQ DQG ($ 7ULQLGDG /DE &OLQ 0HG f 66 4XH +HH 70F'RQDOG DQG 5/ %RUQVKHLP 0LFURFKHPLFDO -RXUQDO f .* %URGLH DQG 0: 5RXWK &OLQLFDO %LRFKHPLVWU\ f :1 $QGHUVRQ 30* %URXJKWRQ -: 'DZVRQ DQG *: )LVKHU &LQ &KLP $FWD f ,/ 6KXWWOHU DQG +7 'HOYHV $QDO\VW f '. (DWRQ DQG -$ +ROFRPEH $QDO\WLFDO &KHPLVWU\ f 93 *DUQ\V DQG /( 6P\WKH 7DODQWD f .6 6XEUDPDQLDQ $WRPLF 6SHFWURVFRS\ f .6 6XEUDPDQLDQ 3URJ $QDO 6SHFWURVF f

PAGE 169

.6 6XEUDPDQLDQ $WRPLF 6SHFWURVFRS\ f 9HUHEH\ <0 (QJ % 'DYLGRZ DQG $ 5DPRQ -RXUQDO RI $QDO\WLFDO 7R[LFRORJ\ f $OYDUDGR 3 &DYDOOL 1 2PHQHWWR 5RVVL -0 2WWDZD\ DQG /LWWOHMRKQ $QDO\WLFDO /HWWHUV f 5%RZLQV DQG 5+ 0F1XWW -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ f $ 6FKW] ,$ %HUJGDKO $ (NKROP DQG 6 6NHUIYLQJ 2FFXSDWLRQDO DQG (QYLURQPHQWDO 0HGLFLQH f 56 +RXN $QDO\WLFDO &KHPLVWU\ $ f / ;LOHL 9DQ 5HQWHUJKHLP 5 &RUQHOLV DQG / 0HHV $QDO\WLFD &KLPLFD $FWD f $ 7D\ORU 6 %UDQFK +0 &UHZV '+DOOV /0: 2ZHQ DQG 0 :KLWH -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ 5 f '$QGHUVRQ % *XR < ;X /0 1J /.ULFND .6NRJHUERH '6 +DJH / 6FKRHII :DQJ /6RNROO ': &KDQ .0 :DUG DQG .$ 'DYLV $QDO\WLFDO &KHPLVWU\ 5 f :.RU]XQ DQG :* 0LOOHU 6RGLXP DQG 3RWDVVLXP LQ 0HWKRGV LQ &OLQLFDO &KHPLVWU\ $3HVFH DQG /$ .DSODQ (GV 0RVE\ 6W /RXLV FKDS f 6 6KDQJ DQG : +RQJ )UHVHQLXV -RXUQDO RI $QDO\WLFDO &KHPLVWU\ f 5 &RUQHOLV % +HLQ]RZ 5)0 +HUEHU -0 &KULVWHQVHQ 20 3RXOVHQ ( 6DEELRQL '0 7HPSOHWRQ < 7KRPDVVHQ 0 9DKWHU DQG 9HVWHUEHUJ -RXUQDO RI 7UDFH (OHPHQWV LQ 0HGLFLQH DQG %LRORJ\ f )1 -RKQVRQ HG 'HSUHVVLRQ DQG 0DQLD 0RGHUQ /LWKLXP 7KHUDS\ ,5/ 3UHVV 2[IRUG 8. f *1 'RNX DQG 3< *DG]HNSR 7DODQWD f

PAGE 170

= 0LDQ]KL DQG 5 0 %DUQHV $SSOLHG 6SHFWURVFRS\ f + 8FKLGD < 1RMLUL + +DUDJXFKL DQG )XZD $QDO\WLFD &KLPLFD $FWD f 3 /HIORQ 5 3ODTXHW ) 5RVH +HQQRQ DQG 1 /HGHPH $QDO\WLFD &KLPLFD $FWD f + 9DQKRH 5 'DPV DQG 9HUVLHFN -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ f 0$ 9DXJKDQ $' %DLQHV DQG '0 7HPSOHWRQ &OLQLFDO &KHPLVWU\ f + 9DQKRH 9HUVLHFN / 0RHQV DQG 5 'DPV 7UDFH (OHPHQWV DQG (OHFWURO\WHV f + 9DQKRH & 9DQGHFDVWHHOH 9HUVLHFN DQG 5 'DPV $QDO\WLFD &KLPLFD $FWD f ( %DUDQ\ DQG ,$ %HUJGDKO &KDUDFWHUL]DWLRQ RI D 6LPSOH ,&306 0HWKRG IRU 0XOWLHOHPHQW 'HWHUPLQDWLRQ LQ :KROH %ORRG DQG 6HUXP 3RVWHU SUHVHQWHG DW WKH (XURSHDQ :LQWHU &RQIHUHQFH RQ 3ODVPD 6SHFWURFKHPLVWU\ -DQXDU\ *KHQW %HOJLXP $ 9LNVQD DQG ( 6HOLQ 7UDFH DQG 0LFURSUREH 7HFKQLTXHV f 5( $\DOD (0 $OYDUH] DQG 3 :REUDXVFKHN 6SHFWURFKLPLFD $FWD % f 17 +RQJ 19 +XQJ DQG %RPDQ -RXUQDO RI 7UDFH DQG 0LFURSUREH 7HFKQLTXHV f 1%LUFK $0 -RKQVRQ DQG & 3DGJKDP 7UDFH DQG 0LFURSUREH 7HFKQLTXHV f ( %DNNHU 5. 0HUXYD ( 3UHWVFK DQG 0( 0H\HUKRII $QDO\WLFDO &KHPLVWU\ f 2 'LQWHQ 8( 6SLFKLJHU 1 &KDQLRWDNLV 3 *HKULJ % 5XVWHUKR] :( 0RUI DQG : 6LPRQ $QDO\WLFDO &KHPLVWU\ f

PAGE 171

5/ %HUWKROI 0* 6DYRU\ .+ :LQERUQH -& +XQGOH\ *0 3OXPPHU DQG 6DYRU\ &OLQLFDO &KHPLVWU\ f / 5DPDOH\ 3:HGJH DQG 60 &UDLQ -RXUQDO RI &KHPLFDO (GXFDWLRQ f :5/ 0DVDPED $ + $OL DQG :LQHIRUGQHU 6SHFWURFKLPLFD $FWD % f 3:-0 %RXPDQV (G ,QGXFWLYHO\ &RXSOHG 3ODVPD (PLVVLRQ 6SHFWURVFRS\ 9RO -RKQ :LOH\ DQG 6RQV 1HZ
PAGE 172

%0 3DWHO -3 'HDYRU DQG -' :LQHIRUGQHU 7DODQWD f + 8FKLGD :5 0DVDPED 7 8FKLGD %: 6PLWK DQG -' :LQHIRUGQHU $SSOLHG 6SHFWURVFRS\ f -' +ZDQJ : 0DVDPED %: 6PLWK DQG -' :LQHIRUGQHU &DQDGLDQ -RXUQDO RI 6SHFWURVFRS\ f $+ $OL .& 1J DQG -' :LQHIRUGQHU 6SHFWURFKLPLFD $FWD % f $0 3OHVV %: 6PLWK 0$ %ROVKRY DQG -' :LQHIRUGQHU 6SHFWURFKLPLFD $FWD % f 6 +DQDDPXUD %: 6PLWK DQG -' :LQHIRUGQHU $QDO\WLFDO &KHPLVWU\ f $WVX\D DQG $NDWVXND 6SHFWURFKLPLFD $FWD % f + 8FKLGD 3$ -RKQVRQ DQG -' :LQHIRUGQHU -RXUQDO RI $QDO\WLFDO $WRPLF 6SHFWURPHWU\ f ./ 5LWHU 2, 0DWYHHY %: 6PLWK DQG -' :LQHIRUGQHU $QDO\WLFD &KLPLFD $FWD f *9 ,\HQJDU :( .ROOPDU DQG +%RZHQ 7KH (OHPHQWDO &RPSRVLWLRQ RI +XPDQ 7LVVXHV DQG %RG\ )OXLGV 9HUODJ &KHPLH :HLKHLP 1HZ
PAGE 173

%( :LOVRQ DQG $ *RQG\ 'LDEHWHV 5HV &OLQ 3UDFW f 30 &ODUNVRQ 6SRUWV 0HGLFLQH f 3 &RSHVWDNH )RRG &KHP 7R[LFRO f 1 9LRODQWH ) 3HWUXFFL 3' )HPLQLQH DQG 6 &DUROL 0LFURFKHPLFDO -RXUQDO f $( 2PX + 'DVKWL $7 0RKDPHG DQG $% 0DWWDSSDOOLO 1XWULWLRQ 6 f &' 7UDQ $QDO\WLFDO &KHPLVWU\ $ f )XOWRQ DQG +RUOLFN $SSOLHG 6SHFWURVFRS\ f &' 7UDQ DQG 5)XUODQ $QDO\WLFDO &KHPLVWU\ f 5 'ZHOOH DQG 3 .DW]ND 5HYLHZ RI 6FLHQWLILF ,QVWUXPHQWV f +DOOLNDLQHQ 3DUNNLQHQ DQG 7 -DDVNHODLQHQ 5HYLHZ RI 6FLHQWLILF ,QVWUXPHQWV f 37UHDGR ,: /HYLQ DQG (1 /HZLV $SSOLHG 6SHFWURVFRS\ f :6 6KLSS %LJJLQV DQG &: :DGH 5HYLHZ RI 6FLHQWLILF ,QVWUXPHQWV f ; :DQJ '( 9DXJKDQ 9 3HOHNKDW\ DQG &ULVS 5HYLHZ RI 6FLHQWLILF ,QVWUXPHQWV f &' 7UDQ DQG 0 %DUWHOW 5HYLHZ RI 6FLHQWLILF ,QVWUXPHQWV f 70 6SXGLFK %$ 3HO] DQG -: &DUQDKDQ $SSOLHG 6SHFWURVFRS\ f &' 7UDQ DQG 5)XUODQ $SSOLHG 6SHFWURVFRS\ f &' 7UDQ DQG 5)XUODQ 5HYLHZ RI 6FLHQWLILF ,QVWUXPHQWV f

PAGE 174

1 2PHQHWWR +*& +XPDQ 3 &DYDOOL DQG 5RVVL $QDO\VW f (3 :DJQHU %: 6PLWK DQG -' :LQHIRUGQHU $QDO\WLFDO &KHPLVWU\ f

PAGE 175

%,2*5$3+,&$/ 6.(7&+ $UWKXU 'DYLG %HVWHPDQ ZDV ERUQ LQ *UDQG 5DSLGV 0LFKLJDQ RQ -DQXDU\ 7KH VRQ RI 5HY $UWKXU DQG $XGUH\ +RQGHUGf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nV UHVHDUFK JURXS SXUVXLQJ KLV 3K' LQ DQDO\WLFDO FKHPLVWU\

PAGE 176

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n.HQQHG $VVRFLDWH 3URIHVVRU RI &KHPLVWU\ FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ /XLVn0 e /XLVO0 0XJD 3URIHVVRU RI &KHPLVWU\ DV FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ %HQMDPLQ $ n+RUHQVWHLQ $VVLVWDQW 3URIHVVRU RI &KHPLVWU\ FHUWLI\ WKDW KDYH UHDG WKLV VWXG\ DQG WKDW LQ P\ RSLQLRQ LW FRQIRUPV WR DFFHSWDEOH VWDQGDUGV RI VFKRODUO\ SUHVHQWDWLRQ DQG LV IXOO\ DGHTXDWH LQ VFRSH DQG TXDOLW\ DV D GLVVHUWDWLRQ IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ 3£XO ( (KUOLFK 3URIHVVRU RI 0DWKHPDWLFV

PAGE 177

7KLV GLVVHUWDWLRQ ZDV VXEPLWWHG WR WKH *UDGXDWH )DFXOW\ RI WKH 'HSDUWPHQW RI &KHPLVWU\ LQ WKH &ROOHJH RI /LEHUDO $UWV DQG 6FLHQFHV DQG WR WKH *UDGXDWH 6FKRRO DQG ZDV DFFHSWHG DV SDUWLDO IXOILOOPHQW RI WKH UHTXLUHPHQWV IRU WKH GHJUHH RI 'RFWRU RI 3KLORVRSK\ 'HFHPEHU 'HDQ *UDGXDWH 6FKRRO

PAGE 178

/' A 81,9(56,7< 2) )/25,'$


MULTIELEMENT ANALYSIS IN WHOLE BLOOD
USING A CAPACITIVELY COUPLED MICROWAVE
PLASMA ATOMIC EMISSION SPECTROMETER
By
ARTHUR DAVID BESTEMAN
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1997

I would like to dedicate this dissertation to my
parents, Arthur and Audrey Besteman. Their love and support
has meant so much to me. I am very blessed to have them as
my parents.

ACKNOWLEDGMENTS
I would like to thank Dr. Jim Winefordner for allowing
me to be a member of his group and for teaching me so much
about analytical chemistry. Working for him has truly been
a pleasure. I would also like to thank Dr. Ben Smith for
the great deal of help that he gave me in my research.
The whole Winefordner group has contributed to this
research, whether it be help with the project or help in
making working here a better experience. I would especially
like to thank Bryan Castle for all his help with the
computers and Dr. Kobus Visser for his help in making
modifications to my project. I must also thank Jeanne
Karably for her help with everything.
Over the course of this research project I was
fortunate enough to have three undergraduate assistants,
Don-Yuan Liu, Nancy Lau, and Gail Bryan. They all
contributed a great deal to this project and I appreciate
all their hard work.
I am grateful to the Chemistry Department Machine Shop
for their work in constructing the electrodes. I am also
iii

grateful to the University of Florida Infirmary for drawing
my blood without causing too much pain.
I must thank the Centers for Disease Control and
Prevention for the initial funding of this work. I also
thank Texaco Company and the University of Florida Division
of Sponsored Research for providing my support for the past
three years.
There are also several people I must thank for their
contributions before I entered graduate school. My high
school chemistry teacher, Mr. Roger Bratt, helped cultivate
my interest and appreciation for chemistry. During my
undergraduate education I worked for three summers with Drs.
Mark and Karen Muyskens. Through this experience I learned
much about doing research and how to work independently. I
am very grateful for all that they taught me.
Finally, I must thank my family and friends for all the
support they have given me while I have been so far from
home. I could not have done it without them.
IV

TABLE OF CONTENTS
ACKNOWLEDGMENTS iii
ABSTRACT viii
CHAPTERS
1 INTRODUCTION 1
2 BACKGROUND 4
Atomic Emission Spectrometry 4
Excitation Sources 7
Choice of Emission Lines 8
Microwave Plasmas in Atomic Emission 10
Capacitively Coupled Microwave Plasma 12
Microwave Induced Plasma 13
Microwave Plasma Torch 15
Comparison to the Inductively Coupled Plasma . 16
Conclusion 16
3 CLINICAL ELEMENTAL ANALYSIS IN BLOOD 19
Introduction 19
Medical Significance 20
Trace Elements 20
Lead 21
Manganese 24
Lithium 24
Zinc 25
Magnesium 26
Major Elements 27
Sodium 27
Potassium 27
Methods of Analysis 28
Lead 28
Screening methods 28
Clinical methods 32
Primary and Trace Elements 38
Atomic absorption spectrometry 39
Atomic emission spectrometry 40
Spectrophotometry 41
v

Inductively coupled plasma mass
spectrometry 42
X-ray fluorescence 44
Electrochemical techniques 44
Conclusion 4 7
4 EXPERIMENTAL SETUP AND MATERIALS 48
Setup 48
Microwave Plasma Electronics 48
Waveguide 50
Torch 50
Plasma Gases 52
Electrode 53
Lens Setup 54
Detector 56
Photodiode array 57
Charge coupled device 57
Computer Software 60
Materials 61
Aqueous Standards 61
Blood Standards 61
5 SAMPLE INTRODUCTION 65
Introduction 65
Methods of Sample Introduction into a CMP 65
Nebulization 66
Thermal Vaporization 68
Cup electrode 68
Filament electrode 72
Hydride Generation 74
Development of Electrode for Blood Analysis .... 75
Cup Holder Electrode 75
Platform Electrode 79
Suspension Method 87
Spiral Filament Electrode 89
Conclusion 93
6 ANALYSIS OF LEAD IN BLOOD 94
Introduction 94
Optimization of Parameters 94
Helium Flow Rate 94
Drying and Ashing Conditions 95
Cleaning 98
Sample Size 99
Sources of Noise 100
Analysis 100
Aqueous Standards 100
Bovine Blood Standards 101
NIST Standards 107
vi

Human Blood Standard 107
Blood and Aqueous Standards 109
Conclusion 114
7 MULTIELEMENT ANALYSIS IN BLOOD 115
Introduction 115
Trace Elements 117
Zinc 117
Lithium 118
Magnesium 125
Manganese 130
Primary Elements 130
Sodium 130
Potassium 134
Comparison to Literature Values 138
Conclusion 14 0
8 CONCLUSIONS AND FUTURE WORK 141
Conclusion 141
CMP-AES as a Lead in Blood Screening Method . 141
CMP-AES as a Multielement Clinical Technique 141
Future Work 142
Analysis of Other Health Related Elements . . 143
Using Aqueous Standards for Blood Analysis . 145
Commercially Made Filaments 146
Simultaneous Multielement Analysis 148
Other Biological Fluids 149
Plasma 149
Serum 150
Urine and spinal fluid 150
Miniaturize System 151
Acousto-optic tunable filter 151
Miniature detector 152
Atomization Method for Other Techniques . . . 153
LIST OF REFERENCES 154
BIOGRAPHICAL SKETCH 166
vii

Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
MULTIELEMENT ANALYSIS IN WHOLE BLOOD
USING A CAPACITIVELY COUPLED MICROWAVE PLASMA
ATOMIC EMISSION SPECTROMETER
By
Arthur David Besteman
December 1997
Chairperson: James D. Winefordner
Major Department: Chemistry
A capacitively coupled microwave plasma atomic emission
spectrometer (CMP-AES) has been evaluated as a clinical
method for the direct analysis of several of the primary and
trace elements in whole blood. A tungsten filament spiral
electrode was used with the CMP, and whole blood samples
were deposited on the electrode and subsequently dried,
ashed, and atomized. The emission was measured with a
spectrometer and either a photo diode array or a charge
coupled device detector. A sample size of only 2 ¿¡L was
required and the time for each sample run was under 4
minutes. This method has a wide dynamic range, allowing the
determination of both the primary elements in blood and the
elements present in trace quantities.

Much of the initial work focused on measuring the
levels of lead in blood. A detection limit of 30 ppb for
lead in whole blood was obtained and good accuracy was
obtained in the analysis of whole blood standards from the
National Institute of Standards and Technology.
The research then focused on applying the CMP-AES to
other elements in blood. The elements studied were
potassium, sodium, lithium, magnesium, manganese, and zinc.
Good linearity was obtained for these elements and the
concentration levels obtained for these elements were
consistent with literature values.
The primary advantages of this method are that no
sample pretreatment or dilution is required, it is easy to
run, has a low instrument cost, and is capable of doing
multielement analysis.
IX

CHAPTER 1
INTRODUCTION
The research project involved developing a capacitively
coupled microwave plasma atomic emission spectrometer (CMP-
AES) as a clinical method for multi-element analysis in
whole blood. Microwave supported plasmas are an excellent
source for atomic emission spectrometry. They produce a
high degree of excitation of atomic and polyatomic species,
have a relatively low cost, and are simple to operate.
CMP's have shown the ability to accomplish direct elemental
analysis in complex matrices [1-3]. Direct analysis is
desirable because it eliminates the use of hazardous
chemicals and the dilution of the sample in trying to
minimize matrix effects [1]. Direct analysis also
eliminates any contamination of the sample or interference
with the plasma that could be introduced by the solvent.
A sample introduction method has been developed that
enables the CMP-AES system to directly determine the
concentration of several elements in whole blood without any
sample dilution or pretreatment. A tungsten electrode is
1

2
used which has a spiral loop at the top. The samples of
blood are placed on this loop and dried by inductively
heating the electrode using microwave power. A flow of
helium gas is introduced through a quartz torch that
supports the electrode, and a low power plasma is formed at
the top of the electrode to ash the blood sample. The power
of the plasma is then increased for atomization and
excitation of the sample. The resulting emission is
measured using a spectrometer and either a photodiode array
or a charge coupled device detector. The peak area of the
atomic emission line of the analyte is then compared to an
analytical curve of standards to determine the concentration
of the analyte in the blood.
Initially this research focused on developing a
screening method for lead in whole blood. The design of the
filament was optimized, as well as the conditions for
drying, ashing, and atomizing the sample. All optimizations
were done using lead as the analyte. The method worked well
with whole blood, and gave excellent linearity and good
precision. The accuracy was tested by analyzing blood lead
Standard Reference Materials (SRM's). Good agreement was
obtained with SRM's with concentrations greater than 100
PPb.
The CMP-AES method was then used for the analysis of
several of the medically significant primary and trace

3
elements in blood. The following elements were chosen for
analysis: sodium, potassium, magnesium, manganese, lithium,
and zinc. For each element an atomic emission line was
chosen that was free from interference and that produced a
linear analytical curve over the concentration range of
interest. The operating conditions had to be modified to
some extent for several of the elements. Analysis was
performed on human blood standards for each element
sequentially by the method of standard additions. The CMP-
AES gave good linearity and precision for these elements.
The determined blood levels for most of the elements studied
were consistent with those found in literature.
In this dissertation, the development of the CMP-AES
for use as a method for elemental analysis in whole blood
will be discussed. A brief overview of atomic emission and
the microwave plasma as an analytical method will be given.
The clinical importance and the methods currently used to
analyze the elements studied will also be presented. The
main portion of the dissertation will discuss the
experimental setup used, the development of the sample
introduction system, and the results of the analysis of the
selected elements in whole blood. The last chapter of the
dissertation will discuss the conclusions made from the
research and the possibilities for future work.

CHAPTER 2
BACKGROUND
Atomic Emission Spectrometry
Atomic emission spectrometry is a useful method for
elemental analysis. It is very specific, has a wide dynamic
range, and has the capability of measuring many elements
simultaneously. Typically, its disadvantages include poor
sensitivities and serious matrix effects [4].
Atomic emission is the process of an atom being brought
to an excited state. The relaxation of the atom from the
excited state results in the emission of radiation. The
outer shell (valence) electrons are the components of the
atom that are excited. The electrons can be excited to a
number of different levels. The photons emitted from the
electrons as they relax from the different energy levels
have characteristic frequencies (v) giving rise to many
wavelengths for each element. The energy levels of each
element are different which results in a distinct emission
spectrum for each element. The energy (E) associated with
each emitted photon is determined by the product of Planck's
constant (h = 6.63 x 1CT34 Js) and the frequency,
4

5
E = hv = hc/X
where c = the speed of light (3.00 x 108 m/s in a vacuum) .
Figure 2.1 gives a simple example of the energies associated
with various transitions. The dotted lines represent the
excitation of electrons to two different energy levels, and
the solid lines indicate the various modes of relaxation
with their corresponding energies.
Not all transitions have the same probability of
occurrence. In general, the strongest emission is observed
from transitions which terminate at the ground electronic
level. This is called a resonance transition. If the
condition of thermal equilibrium is maintained, then the
number density (atoms per cm3) of analyte atoms in a given
excited state (n±) can be related to the total number
density of analyte atoms (nt) by the Boltzmann
distribution:
1 z (r)
The temperature (T) is the absolute temperature (K). Ej is
the excitation energy (J) relative to the ground state, and
g± is the statistical weight of state i. Z represents the
electronic partition function:
Z(T) = £".0 g1e'E1/kT

6
Figure 2-1. Energy diagram for excitation and emission [5],

7
The radiant power of emission (E) between two states (from
state i to state j) is given by the product of the
population density of the excited atoms (n3), the transition
probability (Ajl( s~3) that an excited atom will undergo the
transition from j to i, the energy of the emitted photon
(hv^) , and the volume element observed (V in cm3) :
<£>e = njhVji A31v
This value, as well as the number density of excited atoms,
is proportional to the analyte concentration in the sample.
This relationship is good only for low concentrations. By
measuring the intensity of emission from standards of
various concentrations of the analyte, the exact
relationship between analyte concentration and ®E can be
determined.
Excitation Sources
Many types of excitation sources are used for atomic
emission. Generally the excitation source is also the
atomization source. In atomic emission, the sample must
first be atomized. This is the process of forming free
atoms. When the free atoms are formed, they can then be
collisionally excited to produce the atomic emission lines.
For many years, flames were the most commonly used
atomic emission source because they are simple,
reproducible, and inexpensive. The flames used in atomic

8
emission are formed by the combustion of an oxidant gas and
a fuel gas. There are several disadvantages to using a
flame as an atomic emission source. The energy of the flame
is difficult to control, and it does not generate enough
energy to atomize all the elements or to populate high
excited states of some transitions.
The introduction of plasma sources for atomic emission
spectrometry has significantly improved the detection
limits, accuracy and precision for atomic emission
spectroscopy. A plasma is a partially ionized gas sustained
through an electrical discharge or through a microwave or
radiofrequency field [5-6]. Plasmas are advantageous
because they have a higher temperature and a less reactive
environment than flames. Plasmas also produce a higher
degree of excitation generating more atomic emission lines
for use in analysis. Inductively coupled plasmas (ICP) are
currently the most widely used. Microwave plasmas are also
effective atomic emission sources. Two types of microwave
plasmas are the microwave induced plasma (MIP) and the
capacitively coupled microwave plasma (CMP).
Choice of Emission-Lines
The atomic emission lines are spectrally separated by
using an optical dispersion device, typically a grating or a
prism. The emission lines must be chosen carefully for

9
optimum signal-to-noise (S/N). The most intense line for
the element of interest is not always the best line for
analysis. The spectral line chosen must be free from
spectral interferences. Interferences may come from the
emission of the inert gas used, impurities in the gas, other
concomitants in the sample, or the plasma support materials.
For analysis in complex matrices, concomitants in the sample
can be a significant problem. The resolution of the
spectrometer plays an important role in determining how well
the spectral line can be distinguished from nearby spectral
lines.
Another factor in choosing an emission line is self¬
absorption. As discussed previously, the emission intensity
is proportional to the number density of the excited atoms.
At high concentrations, the number density of atoms in the
various energy levels can be very high. The atoms present
in the lower energy levels can absorb the energy emitted
from the relaxing excited states. At high number densities
in the lower energy levels, a significant fraction of the
emitted energy can be absorbed instead of being detected as
emission signal. This is a significant problem if a
resonance line is used because the majority of the atoms are
present in the ground state. When self absorption begins to
occur, the slope of a log-log plot of emission intensity vs

10
concentration will deviate from the desired value of one and
approach a limiting value of one half [5]. In conventional
flames, the linear concentration range is often no more than
two orders of magnitude because of self absorption [7].
When analyzing samples of such a high concentration that
self absorption occurs, there are two basic strategies. The
first is to dilute the sample to a concentration where self
absorption does not occur. The second is to choose a weaker
spectral line that gives a linear response over the
concentration range of interest.
Microwave Plasmas in Atomic Emission Spectrometry
Microwaves are radio waves in the frequency range of
1.0 GHz and upward [8]. Microwaves have been very useful
for applications in radar and communications because of
their high frequency and short wavelength. The high
frequency of microwaves provides wide bandwidth capability.
The wavelength is long enough to penetrate materials, but
short enough to allow microwave energy to be concentrated in
a small area. This feature has been taken advantage of in
microwave ovens [9].
Two methods for transmitting microwave energy from one
point to another are the coaxial cable, and the waveguide.
The coaxial cable consists of two cylindrical conductors

11
separated by a continuous solid dielectric. The microwaves
travel through the dielectric [10]. Coaxial cables are
capable of a large bandwidth and are small in size, but have
the disadvantages of high attenuation and cannot handle high
powers. The waveguide can be either a circular or
rectangular hollow pipe. It is capable of handling high
powers with low loss, but is large in size and only has a
narrow bandwidth.
The first microwave discharge was observed in the
1940's by electrical engineers and physicists working on
radar equipment [11] . It was viewed as a nuisance instead
of a potential technological advancement. In 1951, Cobine
and Wilbur described some of the features of a microwave
plasma [12]. They described the plasma using helium, argon,
air, oxygen, and nitrogen as the support gases.
In 1958, Broida and Chapman used a microwave-induced plasma
(MIP) to analyze nitrogen isotopes [13]. Kessler and
Gebhardt used a capacitively coupled microwave plasma (CMP)
to analyze limestone in 1967 [14] . Mavrodineanu and Hughes
used a microwave plasma torch in 1967 to view the emission
spectra of several elements by introducing solutions into
the crater of a graphite discharge tip [15]. Fallgatter et
al., examined an argon microwave plasma as an excitation
source for atomic emission spectrometry in 1971 [16]. The

12
development of microwave plasmas has grown over the years
because of their high excitation efficiency for both
metallic and non-metallic elements, their low background
emission, and their low cost [17] . In recent years,
microwave plasmas have been applied to many different
analytical applications including analysis of solids,
biological fluids, and oil [1-3], Several authors have
written extensive reviews of the use of microwave plasmas in
spectrochemical analysis [17-22].
Caoacitivelv Coupled Microwave Plasma (CMP)
For a CMP, a magnetron (microwave power tube) generates
the microwaves which are conducted through a coaxial wave
guide. Within the waveguide, a standing wave is produced
which builds up microwave energy that is transferred to the
tip of a central single electrode. By oscillating in the
microwave field, the electrons gain enough kinetic energy to
collisionally ionize the support gas. This produces a
flame-like plasma at the tip of the electrode. The plasma
that is produced is capable of atomizing and exciting the
analyte in a sample. The signal is measured by focusing the
emission on the entrance slit of a spectrometer. The
multielement emission is usually measured with a photodiode
array (PDA) or a charge coupled device (CCD).

13
Several parameters must be optimized in order to obtain
satisfactory results with a CMP. These parameters include
the microwave power, the plasma gas flow rate, and the
position of the electrode with respect to the detector.
Optimum microwave powers differ depending on the type of
samples and the method of sample introduction. Helium is
used most often as the support gas with flow rates ranging
from 3 to 10 L/min [23].
Spencer et al. studied various parameters for a high flow
rate (>6 L/min) CMP [24] . The temperature measurements were
made with the following plasma conditions: 10 L/min helium,
150 cm3/min hydrogen and 700 W of applied power. The
following results were obtained for the analysis of aqueous
solutions: excitation temperature = 3430 K; and electron
number density = 4.4 x 1014 cm'3. They determined that the
values of Texc and ne are not statistically different for the
introduction of aqueous and organic solutions into the
plasma.
Microwave Induced Plasma (MIP)
Microwave induced plasmas (MIP) are created by using an
external resonant cavity or some other structure to couple
microwave energy to a stream of gas in a quartz tube. MIP's
are sustained at low powers (25 to 200 W) with argon or

14
helium as the support gas [18] . A microwave power supply is
attached to an antenna or circuit loop by a coaxial cable.
The energy goes through the antenna or loop and is
introduced into the resonant cavity generating a standing
wave. A quartz tube is placed in the cavity in such a way
that its axis is parallel to the line of electric field
oscillation. MIP's that use an electrothermal type of
atomizer have resulted in the best detection limits [18].
Microwave induced plasmas are more widely used than
capacitively coupled microwave plasmas because MIP's require
lower power and can be operated at atmospheric pressure. In
addition, CMP's involve the use of an electrode which can
cause spectroscopic contamination and memory effects if it
erodes [23]. However, CMP's do have several advantages over
MIP's. MIP's can only be operated at low powers while CMP's
are stable over a wide range of power levels (50-2000 W).
At higher powers, there are fewer matrix effects and more
intense signals. Also, a wide range of gases can be used to
sustain CMP's and CMP's are more tolerant to the
introduction of foreign materials than MIP's [25]. Sample
introduction problems have hindered the development of
commercial MIP instruments [5]. Memory effects are also a
problem in MIP atomic emission spectroscopy [18]. The
memory effects are probably a result of etching of the
quartz tube by the plasma providing a region where analyte

15
atoms can collect. An MIP is most useful as an excitation
source when it is combined with a separate sample atomizer.
Microwave Plasma Torch
Jin et al. developed a new type of microwave plasma
called the microwave plasma torch (MPT) [26-32]. A MPT
contains three concentric tubes, with the outer tube made of
brass and the inner tubes made of copper. The outer tube
serves as the microwave cavity which couples the microwave
energy to the torch forming a plasma at the top of the
torch. The carrier gas containing the sample aerosol enters
the inner tube and the plasma gas (helium or argon) flows
through the middle tube. This microwave plasma is very
stable and has a high tolerance to the introduction of
foreign materials [30]. The linear dynamic range for the
MPT was generally more than three orders of magnitude and
the detection limits for 15 rare earth elements were in the
part-per-billion (ppb) range [32]. This is a significant
advancement over the MIP because the MPT can withstand the
introduction of wet aerosols. Solutions are nebulized by an
ultrasonic nebulizer and the resulting aerosol is introduced
through a desolvation-dessicator system. The MPT does
however suffer from matrix effects and air entrainment in
the torch.

16
Comparison to the Inductively Coupled Plasma (TCP)
The inductively coupled plasma (ICP) is widely used in
industry and research. The ICP has a somewhat higher
temperature than the microwave plasma and produces a high
degree of excitation. The ICP consists of several
components. A gas, typically argon, flows through a torch
made out of three concentric quartz tubes. The top of the
torch is immersed in a high energy induction coil which
carries radiofrequency power (at 27 or 40 MHz) in the range
of one to three kilowatts. This causes the oscillation of
the argon atoms, and the high energy collisions that result
produce a plasma at the top of the torch with a temperature
more than 6000 K [6,33], The sample is generally introduced
by nebulization [34] . A fine mist of sample is generated by
pumping the sample through a pneumatic nebulizer and spray
chamber.
Conclusion
Atomic emission spectrometry is a very selective
analytical method that can be used for many types of
samples. Plasma sources have further increased the
usefulness of atomic emission spectrometry. Table 2-1 shows
a comparison of the plasma sources discussed. Although the
ICP and the MIP are currently in wider use than the CMP, the

17
CMP is better able to analyze complex matrices. This
feature of the CMP can be used for direct elemental analysis
in blood.

18
Table 2-1. Comparison of inductively coupled plasma (ICP),
capacitively coupled microwave plasma (CMP),
microwave induced plasma (ICP) and microwave
plasma torch (MPT) for atomic emission
spectrometry [21].
ICP
CMP
MIP
MPT
Gas
Argon
Helium
Argon
or
Helium
Argon
or
Helium
Power (W)
500-1500
70-1000
10-150
40-500
Gas
temperature
(K)
2000-6000
2000-3500
500-2000
1000-6000
Relative
standard
deviation
0.5-2%
2-10%
0.5-2%
1-5%
Linear
dynamic
range
~105
~104
~103
~104
Limit of
detection
(ppb)
0.1-100
0.1-1000
0.1-100
0.1-100

CHAPTER 3
CLINICAL ELEMENTAL ANALYSIS IN BLOOD
Introduction
The human body requires a delicate balance of the
levels of various elements. Too much or too little of a
particular element can have devastating physiological
effects. Some typical ailments are a result of an imbalance
of elements in the body. High levels of sodium and low
levels of potassium, magnesium, and calcium all lead to
hypertension (high blood pressure) [35]. Hypertension is
the most common disease in industrialized societies and
contributes to the development of cardiovascular disease,
stroke, and renal failure [35]. The reduction of the levels
of certain elements caused by medical treatment with some
drugs can also cause serious problems [36].
Elements are transported by the blood and taken up in
varying amounts by organs and tissues [4]. The significance
of the levels of various elements in health makes it
important to have readily available techniques to monitor
these elements. The biological importance of each element
19

20
studied during the course of this research and the methods
used to measure them will be discussed.
Medical Significance
Trace Elements
An element is classified as a trace element if the
concentration is below 250 ppm [37] . Trace elements can be
classified into two groups, essential and nonessential. An
element is considered essential if lack of that element
causes problems. Essential trace elements include
manganese, copper, zinc, tin, and nickel. Nonessential
elements are those that are present in biological organisms
but have not been determined to play an important role [4].
The role of trace elements in the body has received
much attention by the scientific community. Although they
are present in low concentrations, they can play essential
roles in biological functions, and can also be detrimental
to biological activity if present in too great an amount
[14]. Trace elements are very important in the structure of
enzymes and are needed in the production of proteins. Trace
elements are also essential for the normal growth and
development of the human skeleton [36].
The metabolism of certain trace elements is involved in
various diseases. Therefore, the measurement of the

21
concentration of trace elements in biological fluids can be
used as a test for certain diseases. Poor health can also
be caused by environmental exposure to some elements. The
proper levels of trace elements are especially important
during pregnancy to insure a healthy child [36], and in the
elderly for their immune response [38], Trace element
losses must be monitored closely in patients receiving
radiation therapy or chemotherapy. These patients may
require additional supplements of certain elements to
compensate for losses due to significant weight loss from
their illness or treatment [39].
Lead
Lead (Pb) poisoning is the leading environmental threat
to children in the United States [40-41]. The primary
sources of lead exposure are lead based paints and lead-
contaminated dust and soils. The Department of Housing and
Urban Development estimates that 4 million homes containing
young children have lead-based paint hazards [42] . Children
can also be exposed to lead though air, water, and food.
Lead poisoning affects virtually every system in the
body. It is especially harmful to the developing brain and
nervous system of unborn and young children [40, 43]. Lead
causes health problems because the body is unable to
distinguish between lead and calcium. When a person
consumes lead it is assimilated into the blood stream the

22
same way calcium is. Young children and pregnant women
absorb calcium more efficiently to meet their added
requirement so they are particularly at risk. Typically,
adults absorb 10 to 15 percent of the lead that reaches
their digestive tract. Pregnant women and young children
can absorb as much as 50% of the lead [44].
In blood, 94% of the lead is bound to the hemoglobin.
Within the past five years, it has been found that lead
concentrations as low as 100 ppb in the blood can be
detrimental to the health and intellectual development of a
child [40, 45]. Figure 3-1 shows the health effects of
various levels in the blood [40]. Acute lead poisoning can
result in anorexia, dyspepsia and constipation followed by
abdominal pain [46]. The detrimental effect of lead
poisoning on young children has led the Centers for Disease
Control and Prevention (CDC) to lower the acceptable level
of lead concentrations in the blood of children to 100 ppb,
compared to a level of 250 ppb considered acceptable from
1985 to 1991. The symptoms of lead poisoning are often
invisible at first, preventing the diagnosis and treatment
of most cases. The number of lead poisoning cases can be
greatly reduced if a large scale screening program is
implemented. This would require an inexpensive, easy-to-use
method to detect trace amounts of lead in blood.

23
Concentration
of lead in blood
(Ff±>)
1500
1000-
500
400
300
200
Health effect in
humans
Death (Children)
Brain and kidney damage (adults)
-Brain and kidney damage (children)
Increased blood pressure
(middle-aged men)
-Decreased IQ and growth in
young children
Pre-term birth, reduced birth weight,
-and decreased mental ability in
infants from mother's ej^nsure during
pregnancy
Figure 3-1. Health effects of lead poisoning (40).

24
Manganese
Manganese (Mn) is a important as a constituent of
metalloenzymes and as an enzyme activator [37, 47].
Research with animals has shown that Mn deficiency can lead
to impaired growth, skeletal abnormalities, disturbed
reproductive function, and problems with lipid and
carbohydrate metabolism. A deficiency of manganese leads to
a decreased level of blood clotting proteins and has also
been observed in several diseases including epilepsy [47-
48] .
Toxic levels of manganese can be the result of chronic
inhalation of airborne particulates containing high
concentrations of Mn from mines, steel mills, or some
chemical industries. Patients with liver disease are also
at risk from Mn toxicity because their liver may not
adequately clear the Mn absorbed from a normal diet. The
main signs of Mn toxicity include depressed growth and
appetite, impaired iron metabolism, and altered brain
function. Severe psychiatric abnormalities including
hyperirritability, violent acts, and hallucinations can be
caused by Mn toxicity [37].
Lithium
Lithium (Li) is used in the treatment of manic
depressive psychosis [49]. Lithium is administered in the
form of lithium carbonate or another lithium salt with as

25
much as 1800 mg taken daily [50]. Blood normally only
contains lithium at a level of low ppb, but for therapeutic
lithium levels, a range of 0.5-1.5 mM is maintained in the
blood [51]. This is close to the toxic level, and a level
of 5 mM can be lethal. This necessitates the monitoring of
lithium levels in patients receiving this type of treatment.
Zinc
Zinc (Zn) is the second most plentiful trace element in
the body. Zinc is important in the metabolic functions of
the body and is essential for the production and functioning
of over 40 enzymes that contain zinc [36]. Zinc is also
vital in the synthesis of DNA and RNA in every living cell.
Zinc plays a role in immune functions, in growth and
development, and in the synthesis and release of
testosterone. Zinc is especially important in expectant
mothers and in the growth of young children [52-53] .
Zinc plays a major role in fighting infections and in
the healing process [47] . Those at risk for zinc deficiency
include women of child bearing age, young children, and the
elderly [54]. If the zinc level is too low it can cause
congenital malformations, including spina bifida and central
nervous system abnormalities. It can also cause severe
growth retardation, arrested sexual maturity and a loss of
appetite [36]. The level of zinc is especially critical in
the elderly because of the deterioration of immune function

26
with age. Low zinc levels can indicate diabetes because
zinc is important in the storage and release of insulin. A
zinc imbalance may be involved in hypertension.
Most cases of zinc toxicity have been related to food
poisoning incidents and to industrial pollution [53] . Too
much zinc causes anemia (reduced hemoglobin production),
elevated white blood cell count, muscular problems,
exhaustion, diarrhea, nausea and dizziness [52-53]. Very
high levels of zinc can impair metabolic functions that are
dependent on other trace elements [54]. High levels of zinc
can also interfere with the absorption of copper which can
provoke iron deficiency and anemia [47].
Magnesium
Magnesium (Mg) is essential in the transfer, storage,
and utilization of energy. Mg regulates and catalyzes over
300 enzyme systems in mammals [55-56]. Mg also maintains
the cardiovascular system, regulates DNA and RNA synthesis
and structure, and is important in cell growth,
reproduction, and membrane structure. Mg controls many
processes in the body including neuronal activity,
neuromuscular transmission, cardiac excitability, muscular
contraction, blood pressure, and peripheral blood flow [47,
55] .
A deficiency of Mg promotes hyper coagulability of
blood, atherogenesis, vasoconstriction, cardiac arrhythmias

27
and also damage to the cardiac muscles. A Mg deficiency may
also be related to cardiovascular disease, hypertension,
diabetes, depression, and atherosclerosis [35, 52] .
Major Elements
Sodium
Sodium is the principal cation of the extracellular
fluid. It is essential in maintaining the pH balance of the
fluid and is also important in nerve transmissions and
muscle contraction. Sodium levels can be depleted by
vomiting, diarrhea, or heavy sweating. If depletion occurs
it is critical to take measures to bring the sodium level
back up to a healthy level. If the sodium level is too high
it can result in hypertension, kidney disease, or heart
disease [47].
Potassium
Potassium is important in the body in its maintenance
of fluid and electrolyte balance and cell integrity.
Diabetic acidosis, dehydration, or prolonged vomiting or
diarrhea can cause low potassium levels. Symptoms of low
potassium levels are muscular weakness, paralysis, and
mental confusion. Too much potassium can also cause
muscular weakness, confusion, as well as numbness, slowed
heart rate, vomiting, and eventually cardiac arrest [47].

28
Methods of Analysis
Lead
The Centers for Disease Control and Prevention has set
forth a number of desirable characteristics for an improved
blood lead measurement system. These characteristics
include an accuracy and precision of ±10 ppb at 100 ppb, a
detection limit of 10-20 ppb, a sample volume of less than
200 fiL, a low cost-per-test, an analysis time under five
minutes, portability, and minimal operator training required
to perform the method.
Screening methods
Currently used screening methods for lead in blood
which measure the level of either erythrocyte protoporphyrin
(EP) [57] or zinc protoporphyrin [45] in blood as an
indication of lead poisoning are not sensitive enough to
measure blood lead levels below 250 ppb. The EP test is
based on the increase in the amount of EP caused by an
increase in Pb. Porphyrins are the metabolic intermediates
in the biosynthetic process that produces heme [52] . Lead
impairs heme synthesis, preventing the incorporation of iron
into the protoporphyrin. This allows free protoporphyrin to
chelate cytosolic zinc. The amount of free protoporphyrin
can be measured because it fluoresces deep red [58] . The
whole blood is diluted and matrix modifiers are added. The

29
porphyrins are then separated from the blood and measured by
molecular fluorometry. This test has been recommended by
the CDC since 1978 [57]. Hematofluorometers have also been
used to screen children for lead [59]. These are portable
instruments that measure the zinc protoporphyrin directly in
a single drop of blood.
Two current methods being developed as portable
screening methods are anodic stripping voltammetry (ASV)
[60-65] and potentiometric stripping analysis (PSA)[66-67].
In anodic stripping voltammetry, a decomplexing agent is
added to the blood sample to free up the lead for
electrolysis. The Pb is reduced at a controlled potential
causing it to plate out on the surface of a mercury
electrode. A voltage sweep of the electrode releases the
lead and produces a current between the working and
reference electrode. By measuring this current, the amount
of lead can be determined [64]. This method has the
problems of instrument instability, slow speed, and
variations in response due to other elements present in the
blood. ASV also requires a plating solution. The use of
ASV with microelectrode arrays and indium as an internal
standard has improved the detection limit and precision for
the analysis of lead in blood [61].
In potentiometric stripping analysis, the lead analyte
is preconcentrated in a mercury film on a glassy carbon

30
electrode. This occurs by potentiostatic deposition where
electrons are added to the metal. The stripping step is
then achieved chemically by adding an oxidant. During the
stripping, the potential of the working electrode as a
function of time is closely monitored. This will produce a
well-defined stripping plateau which can be used for the
analysis of lead. Whole blood has to be diluted by a factor
of ten for analysis by the method of standard additions
[67]. The total time for analysis is about 5 minutes.
Both ASV and PSA possess the required accuracy and
precision to detect low blood lead levels. Electro-chemical
methods are advantageous as a screening method because they
are both portable and inexpensive; however, they have the
disadvantage that they require the use of reagents and
sample pretreatment when analyzing whole blood.
Exeter Analytical (North Chelmsford, MA) has developed
a commercial atomic absorption spectrometry (AAS) instrument
that can be used for blood lead screening [68]. The lead
absorption line at 283.31 nm is used with near line
background correction using the non-absorbing 287.33 nm lead
line. This instrument used a 150 W tungsten coil filament
in an enclosed chamber. Tungsten coils are excellent
atomization sources because of their high heating rate and
their commercial availability. Tungsten coils that are made
for halogen projector lamps can be used so they are

31
relatively inexpensive. One coil can last for approximately
70 runs. The blood samples were diluted by a factor of ten
with 0.2 % nitric acid, 0.5% Triton x-100, and 0.2% NH4H2P04.
Calibration is done with aqueous standards, and a detection
limit of 30 ppb with a RSD of 9.0% at 100 ppb is obtained.
This method produces results in less than 3 minutes, has a
low cost-per-test, and is easy to operate [68].
Recently, a portable, battery powered AAS was developed
by Jones and coworkers for lead in blood screening [69]. A
tungsten coil was used as the atomizer and a miniature fiber
optic spectrometer with a charge coupled device (CCD)
mounted on a input card of a personal computer was used as
the detector. The blood samples were digested in nitric
acid by microwave heating and then diluted with distilled
deionized water. A 20 sample was placed on the coil and
then dried for 2 minutes at 3.0 A and then atomized at a
current of 6.0 A. The absorption signal was collected using
a hollow cathode lamp and a fiber optic. The spectrometer
and multichannel detector allowed near-line background
correction technique to be used. The lead absorption line
at 283.3 nm was used for analysis and the average of the
nonabsorbing lead lines at 280.2 and 287.3 nm was used for
background correction. The total cost of this entire system
was below $6000. A detection limit of 1 ppb for lead was
determined. The linear dynamic range was 2 orders of

32
magnitude and the precision was 5%. The method was proven to
be accurate by analyzing NIST blood standards. The coil was
used in the analysis of up to 400 samples [69].
Clinical methods
Research is being done by many different government
agencies and universities to improve blood lead measurement.
Isotope dilution inductively coupled mass spectrometry (ID-
ICP-MS) [70] and graphite furnace atomic absorption
spectrometry (GFAAS) [71-72] are methods that are able to
detect trace amounts of lead in blood below the level of
concern (100 ppb). Both of these methods are very accurate
and precise, but have the disadvantages of requiring sample
pretreatment and expensive instrumentation. The expense of
testing is a major consideration since millions of children
would need to be tested in a large-scale public health
screening program.
Atomic absorption spectrometry (AAS) . Graphite furnace
atomic absorption spectrometry (GFAAS) is one of the most
popular methods for lead in blood analysis [71-90]. GFAAS
has excellent sensitivity and selectivity, large throughput,
and is capable of analyzing very small volumes. Many GFAAS
methods use a L'vov platform which is a small platform
placed in the graphite tube to hold the sample and ensure
that the tube and sample come to the same temperature at the
same time. In 1991, the Centers for Disease Control (CDC)

33
surveyed the methods being used by clinical laboratories for
blood lead analysis. Of the laboratories surveyed, 61% used
GFAAS, 5% of the labs used Delves cup AAS, 7% used
extraction AAS, 1% used carbon rod AAS, and 26% used ASV
[81] .
The methods used to analyze lead in blood by GFAAS
include: direct introduction of blood into the furnace;
dilution with either water, Triton X-100, or acid;
deproteinization with nitric acid; matrix modification;
solvent extraction; or a combination of several methods
[82]. The direct injection of blood samples into a graphite
furnace has many problems associated with it. The blood can
seep into the graphite and produce major memory effects [83-
84], and during drying and atomization, the blood residue
can cloud the viewing windows [85]. Also, a carbonaceous
residue from the proteins in the blood builds up in the
furnace and is unable to be vaporized even at high
temperatures [76, 83]. Diluting the blood samples with
water alone is not sufficient to reduce adequately the
amount of carbonaceous residue [86]. The presence of water
in the blood sample also gives rise to a slow precipitation
of the red cell membranes, reducing the homogeneity of the
sample [87]. Diluting the blood samples with a 0.5 to 2%
solution of Triton X-100, a surfactant, causes complete

34
lysis of the blood cells and produces a clear solution that
minimizes the negative effects of the blood matrix [88].
The problem of carbonaceous residue build up can be
virtually eliminated by deproteinization of the blood with
30-50% nitric acid. The supernatant of the resulting sample
can then be injected into the graphite tube. This procedure
destroys the bulk of the organic matter in the blood.
However, the use of nitric acid shortens the life of the
graphite tube because of the oxidation of the tube's
pyrolytic coating [89]. The blood could be deproteinized at
lower concentrations of acid, but the inorganic salts
present were removed, necessitating the use of standard
additions [90].
Adding matrix modifiers to the blood can help in
retaining the analyte while volatilizing away most of the
matrix. The most common matrix modifiers used in blood lead
analysis are diammonium hydrogen phosphate, ammonium
dihydrogenphosphate, and phosphoric acid [75, 82]. By
adding these matrix modifiers, higher furnace temperatures
can be used to ash away the matrix without significant loss
of the analyte. The method of solvent extraction can also
minimize matrix effects, but it is very tedious, prone to
contamination, and does not completely remove interferences
[91-92].

35
A GFAAS method has been developed which allows aqueous
standards to be used for blood lead analysis [71] . Prior to
analysis, the blood is deproteinized with a 5% nitric acid
solution containing 0.1% Triton X-100. The supernatant is
collected and the concentration of lead is measured using
Zeeman GFAAS. Parsons and coworkers have also developed a
method capable of calibrating with aqueous standards [45,
75]. A transversely heated graphite tube/platform called a
stabilized temperature platform furnace (STPF) was used.
This method produced a nearly isothermal system which
reduced the time of analysis, increased the precision, and
eliminated many of the chemical and matrix interferences.
Blood samples preserved in EDTA were diluted by a factor of
10 with a solution containing ammonium dihydrogen phosphate,
triton X-100 and nitric acid. The samples were directly
introduced into an autosampler where the mixing with the
solution occurs. Twelve micro-liter aliquots were injected
into the furnace and atomized. Each analysis took 90 s, and
the system was able to run approximately 100 samples per day
with duplicate injection. The precision was better than 5%.
While both of these methods are advantageous because aqueous
standards can be used for calibration, they have the
disadvantage of requiring appreciable sample treatment.
A flame AAS method has been developed that used 20 /¿L
of blood samples spotted on filter paper and then analyzed

36
in a Delves cup [93]. A Delves cup is a small nickel cup
that is positioned in the flame for analysis. The blood
sample must be allowed to dry on the filter paper and is
then ashed. The ashing step burned away the paper and then
the sample was introduced into the flame to be analyzed for
lead by measuring the absorption at a wavelength of 283.3
nm. The entire analysis time was 15 s per sample and a
limit of quantitation of 40 ppb was obtained. This method
gave excellent reproducibility and accuracy [93] . It has
the disadvantage that there was considerable variability in
the adsorptiveness of the papers which was detrimental to
the accuracy. Also, this method's requirement of allowing
the blood to dry on the filter paper resulted in the sample
being susceptible to contamination from airborne particles.
As a clinical method, flame AAS has the disadvantage that
the equipment is expensive and cumbersome and requires a
combustible gas source.
Inductively connled plasma atomic emission spectrometry
(ICP-AES1. A carbon rod atomizer has been used to analyze
blood samples with a ICP atomic emission spectrometer [94].
Blood samples were diluted by a factor of five with
distilled water. The samples were placed on the carbon rod
atomizer and then dried and volatilized. The resulting
vapor was carried into the plasma by the plasma gas. This
method of sample introduction was more efficient than

37
nebulization. An aqueous detection limit of 7 ppb was
reported for lead with a relative standard deviation (RSD)
of 0.2%.
Inductively coupled plasma mass spectrometry (ICP-MSI.
ICP mass spectrometry is a very sensitive method for the
measurement of lead in blood [70, 95-96]. The main method
of sample introduction in an ICP-MS is a nebulizer. Aqueous
samples are transferred to a nebulizer by a peristaltic
pump. The aerosol produced by the nebulizer is carried to
the plasma by a flow of gas, typically argon. The high
temperature of the plasma vaporizes and ionizes the sample
and the ions are then detected in a mass spectrometer
according to their mass to charge ratio [97]. ICP-MS with
isotope dilution, is the method with lowest bias for
determining lead in whole blood and serum [70, 95]. Isotope
dilution mass spectrometry involves measuring the change in
the relative abundance of two isotopes of an analyte after
adding a known amount of one of the isotopes to the sample.
The CDC uses isotope dilution (ID) ICP-MS for the analysis
of its certified reference material, lead in bovine blood,
from its Blood Lead Laboratory Reference System. An aliquot
of the whole blood sample is spiked with a radiogenic lead
isotopic standard. This aliquot along with an unspiked
aliquot is then digested with ultrapure nitric acid in a
microwave oven. After cooling, both samples are diluted and

38
then aspirated into an ICP-MS. The isotope ratios of lead
at mass 206 and mass 208 are then measured. While this
method is very accurate and precise for determining lead in
blood, it is more suitable for determining reference values
than being used as a clinical method because of it's high
cost and low throughput (10 samples per day) [70, 95].
Primary and Trace Elements
The main methods for trace elemental analysis in the
clinical laboratory are absorption or emission spectro¬
photometry. Typically, the blood is separated, and the
plasma or serum is used for analysis [4]. Methods capable
of performing trace elemental analysis include AAS, ICP-AES,
and ICP-MS. Other methods include electrochemical, neutron
activation, flame atomic fluorescence spectrometry,
molecular absorption spectrometry, X-ray fluorescence,
particle-induced X-ray emission and radiochemical techniques
[46]. However, many of these methods are not suitable for
routine use in a clinical setting. Neutron activation, for
example, is a very sensitive technique but requires the use
of a nuclear reactor and requires a very long time for
analysis [98]. Currently, AAS is the most widely used
method in clinical laboratories, usually employing
electrothermal sample introduction [46]. Recent reviews of
clinical methods of analysis have appeared in Analytical

39
Chemistry [99] and in the Journal of Analytical Atomic
Spectrometry [100] .
Atomic absorption spectrometry (AAS)
Sodium, potassium, zinc, magnesium, and iron blood
levels can be determined by flame atomic absorption
spectrophotometry (FAAS) [47, 101]. The samples are diluted
and introduced into the flame. The analysis of each element
requires a hollow cathode lamp that produces light at a
wavelength specific for that element. The fraction of
absorbed light is used to determine the concentration of the
element present. Shang and Hong have used a microvolume
injection technique to measure the levels of Cu, Zn, Ca, Mg,
and Fe by FAAS [102]. The blood samples were treated with
triton x-100 and then diluted with a mixture of 0.18 M HC1,
0.003 M La203, and 0.013 M KC1. The injection volume used
was 10 iiL. Atomic absorption has greater sensitivity than
either flame atomic emission spectrometry (FAES) or ion
selective electrodes (ISE), but it is less precise and not
as suitable for routine clinical analysis. It has a high
initial cost and the necessity for compressed gases and
flames are undesirable in the clinical laboratory.
GFAAS is a very popular method for elemental analysis
in blood. The various methods used for lead analysis are
also used for many other elements and have the same

40
advantages and disadvantages [90]. The levels of magnesium,
manganese, lithium and iron have all been determined by
GFAAS [47, 50, 52]. GFAAS has achieved a detection limit of
2 ppb for manganese in blood and is the most common method
for analysis of lithium in blood [50, 103]. The main
disadvantage of GFAAS as a clinical technique is its
limitation as a single element technique. Some researchers
have developed complex methods of determining two or three
elements simultaneously, but it is difficult and expensive,
requiring a complicated optical setup [74].
Atomic emission spectrometry (AES)
Sodium and potassium in serum are usually analyzed by
either flame atomic emission spectrometry (FAES) or by ion-
selective electrode potentiometry (ISE) [101] . FAES
requires a dilution of the sample by 100 to 200 times, often
adding lithium or cesium to the sample as an internal
standard and ionization suppressant. An air-propane flame
is used, and the sodium emission is monitored at 589 nm and
the potassium emission at 766 nm. Only 1 to 5% of the atoms
in the flame are excited to emission, but the concentration
of the elements is sufficient for accurate and precise
measurements [101]. Lithium levels can also be reliably
measured using flame emission spectrometry [104].
Flame photometric flow-injection analysis has been
successfully used to simultaneously measure the levels of

41
lithium, sodium and potassium in blood serum [105]. The
serum samples were diluted ten-fold with doubly-distilled
deionized water. The sample was then injected and split into
three portions so that each portion reached the detector at
a different time. Between the analysis of each sample
portion, the filter on the detector was changed to be
specific for each analyte. This method allowed the analysis
of 108 samples per hour [105].
ICP-AES has been used to measure the levels of Fe, K,
Mg, Na, Li and Zn in human serum and blood [106-108]. Serum
samples were digested in nitric acid or diluted with
deionized water. A microsampling system has been developed
for ICP-AES which uses <0.1 mL of sample [107], By
digesting the blood or serum sample with acid, aqueous
analytical curves could be used for calibration.
Spectrophotometry
Spectrophotometry involves selectively complexing and
separating an analyte using either an inorganic or organic
colorimetric reagent. Various organic reagents have been
used as spectrophotometric agents for the analysis of
lithium, magnesium, and iron in blood and serum [51-52].
Calmagite, methylthymol blue and formazam dye, are some
examples of chromophores that have been used for the
analysis of magnesium. The level of iron in blood is
analyzed by exposing the blood sample to strong acids to

42
dissociate the iron from its binding proteins. A chromogen
is then added to the sample to produce a iron chromogen
complex that has an absorbance maximum in the visible
region. The concentration of lithium in serum can be
measured by observing shifts in the spectrum of a reagent
caused by the presence of lithium. The reagents must be
very specific for lithium because sodium, which is present
at high concentrations in blood, is generally an
interferent. Crown ethers can be used for lithium analysis.
By using different cage sizes, conformational flexibility,
and various side groups, crown ethers can be made to form a
complex selectively with the several analytes of interest.
The complex formed can be extracted into an organic solvent
with an anionic reagent that is colored allowing
spectrophotometric analysis [51].
A major disadvantage of spectrophotometry is the
limited selectivity due to overlapping absorption bands. It
is, however, easy to use, rapid, and can be readily
automated [4].
inductively coupled plasma mass spectrometry (icp-ms)
ICP-MS has been used for the measurement of trace
elements in whole blood and serum [33, 109-112]. The
advantages of using ICP-MS include high throughput (40
samples/hour), possibility of simultaneous analysis, and
good detection limits. Over 50 elements have detection

43
limits in the range of 0.01 to 0.1 ppb [33]. Adding an
internal standard can often correct for matrix effects and
instrument drift.
Blood and serum samples for ICP-MS are usually digested
with acid or diluted. The sample pretreatment often
includes a separation step. The amount of time needed for
sample preparation has been reported as 25 minutes for 50
specimens [33]. Barany and Bergdahl reported on a method
for ICP-MS of trace analysis in blood where whole blood was
diluted 50 to 100 times with an alkaline solution. Each
analysis required only 75 seconds. Even with dilution, some
problems were encountered with the buildup of denatured
proteins from the blood so the torch required occasional
cleaning. This method was used for the determination of 7
trace elements in blood. It was not suitable however for
Mn, Se, Hg, or Cr [113].
The major disadvantage of using ICP-MS is the high cost
of the instrument and the operator expertise needed. Also,
the analysis of lighter elements is difficult because of
more interferences. Interferences arise from mass overlap
from either polyatomic ions, doubly charged ions, or
elements with the same isotopic masses. Currently, it is
not possible to analyze chromium, manganese, or iron by ICP-
MS in biological samples due to the presence of
interferences [33, 109-110, 113] .

44
X-rav fluorescence
X-ray spectrometry involves bombarding the sample with
radiation of distinct energy. This removes electrons from
the inner shells forming atoms in an excited state. The
electrons from the outer shells fall into the shells vacated
by the removed electrons according to specific transition
rules. The radiation emitted by this process is very
characteristic. The method of x-ray fluorescence can be
used for simultaneous multielement analysis on a very small
sample of blood (2-3 nh) without destroying the sample [114—
115]. The blood levels of potassium, calcium, chromium,
iron, nickel, zinc, selenium and lead can all be determined
in one measurement. Detection limits ranged from 21 ppm for
phosphorus to 30 ppb for lead in blood [114-116]. The
method of X-ray fluorescence has the disadvantage that it is
very difficult to match the composition of the calibration
standards to the matrix of the sample [4].
Electrochemical techniques
Voltammetry, an electrochemical method, is also capable
of measuring trace elements in blood. In voltammetry, the
measurements are based on the potential-current behavior of
a small electrode that is easily polarized [4]. Voltage is
applied to a microelectrode and the diffusion current is
measured as a function of the voltage. This allows both
quantitative and qualitative analysis of the trace element.

45
For this method, it is necessary to digest completely the
samples prior to analysis [4] .
Ion selective electrodes (ISE) are capable of
determining the level of potassium, sodium, magnesium and
lithium in blood or serum by measuring the potentiometric
charge as a function of ion concentration [51, 55, 117-120].
The membranes of ISE's are ideally sensitive to only one
ion. Most membranes, however, respond to ions other than
the one for which they are designed. Polymer-bound liquid
membranes use a membrane that contains a sensing material
dissolved in the polymer support matrix. If the sensing
material is neutral in charge, then it must complex with the
analyte in some way to transfer it across the membrane or it
must be able to facilitate ion exchange. Neutral sensing
materials are called ionophores and are often some type of
crown ether. Crown ethers can be made in such a way that
they can selectively complex a given ion. The polymer
matrix containing the sensing material is often polyvinyl
chloride (PVC) [121]. Bulky crown ethers used in a PVC
membrane ISE can exhibit a selectivity up to 2000:1 for
lithium [51]. A glass ion-exchange membrane is used for the
analysis of sodium, and a valinomycin neutral-carrier
membrane is used for potassium [101] .
The use of ISE's to analyze clinical samples involves
either the direct analysis of undiluted samples or the

46
indirect analysis of pre-diluted samples. Direct ISE
methods are subject to bias because of the difference in the
serum matrix and the aqueous samples used for calibration.
Indirect ISE is susceptible to error introduced by the
dilution.
ISE's to monitor Mg can yield rapid results on blood,
plasma, serum and aqueous solutions with sample sizes
ranging form 100 to 200 ¿¿L [55]. The Mg ISE's employ
ionophores using neutral carrier based membranes with
excellent precision reported at 2 to 4%. However, this
method does experience problems with very low levels of
magnesium because the analytical response is not linear at
these low concentrations [52].
ISE's compare favorably to the methods of atomic
absorption spectrometry and flame emission spectrometry for
the analysis of several elements. ISE's have the advantages
that they function in turbid solutions, have a wide dynamic
range, have a rapid response, are inexpensive, and are very
portable with current instruments weighing between 7 to 12
kg [117]. The rapid response is very beneficial in
monitoring dosages and compliance with medical treatment
such as lithium treatment in psychiatric patients. ISE's
have the disadvantages that they have limited sensitivity,
are subject to interferences from other ions and memory
effects, and require frequent calibration.

47
Conclusion
The analysis of the primary and trace elements in blood
is very important in maintaining and monitoring the health
of individuals. Although there are many methods capable of
doing multi-element analysis in blood, there is still much
room for improvement. The most accurate and precise methods
all require some sort of sample pretreatment. Sample
treatment requires time and is a possible source of
contamination. Ideally a clinical method for blood analysis
would be able to analyze whole blood directly, without
sample pretreatment, and would be able to use simple
standards (i.e. aqueous) for calibration.

CHAPTER 4
EXPERIMENTAL SETUP AND MATERIALS
Setup
The experimental setup is shown in figure 4-1. Each
component of the experimental setup will be described.
Microwave Plasma Electronics
The microwave plasma was generated by an 870 W
magnetron (Samsung 0M75A) at 2450 MHz. This type of
magnetron is commonly found in domestic microwave ovens.
Magnetrons are capable of high power with low cost and high
efficiency. Magnetrons produce microwaves through the
combination of an anode, cathode, and magnet. Electrons are
emitted from the cathode and are introduced into a
combination of electric and magnetic fields which cause the
electrons to move around the cathode. The electrons then
move toward the anode and exchange potential energy,
building up the microwave field. When the electrons hit the
anode, the power is coupled directly to the output. The
output allows the microwaves to be taken out via an external
48

High Voltage
Power Supply
AC-DC
Transformer
Electrode
Magnetron
T-iT-
Rectangular
Waveguide
Helium Flow in
Removable Quartz
Chimney
Teflon Tape
Figure 4-1. CMP-AES experimental setup.
Spectrometer
PDA or
CCD

50
transmission line [9]. A diagram of the magnetron is shown
in figure 4-2.
The magnetron was powered by a current regulated
analog-programmable power supply (Model 106-05R, Bertrán
High Voltage, Hicksville, NY, USA). An A.C. power
transformer (Magnetek Triad, model F-28U, Newark
Electronics, Chicago, IL) was used to provide a high
current, low AC voltage for the magnetron filament.
Waveguide
The rectangular waveguide was made out of aluminum and
constructed in the laboratory. The waveguide had the
following dimensions: height = 47 mm, width = 98 mm, length
= 277 mm. The waveguide had a hole near one end on the top
allowing the output of the magnetron to be inserted, and
holes on the top and bottom near the other end allowing the
torch to be suspended within the waveguide. The hole
diameter for the torch was 44 mm, and the center of the hole
was 58 mm from the end.
Torch
The torch consisted of four concentric quartz tubes:
an outer quartz tube (outer diameter (o.d.) =19 mm)
directed the flow of helium; a removable quartz tube (o.d. =
15 mm) reduced the dead volume of the torch; and an inner

51
Heater leads
and cathode
leads
Figure 4-2
Magnetron

52
quartz tube (o.d. = 5 mm) that supports a short piece of
quartz tubing (o.d. = 2 mm) in which the filament rests.
The inner quartz tube is used to decrease the volume of the
torch in order to reduce the amount of helium gas required.
The inner quartz tube is a separate piece of quartz tubing
held in place in the torch with teflon tape. In some
experiments, the inner tube is brought up around the plasma
so that it shields the plasma. The inner tube as a shield
is better than using the torch itself because the inner
quartz tube is easily replaced if the plasma attacks it and
makes it optically unclear. A quartz chimney surrounds the
top of the torch to reduce instabilities caused by air
currents.
Plasma Gases
Helium (BOC Gases, The BOC Group, Inc., Murray Hill,
N.J.) was used as the plasma gas. Helium was an excellent
plasma gas for atomic emission spectroscopy because of its
high ionization energy [122]. The ionization energy of
helium is 24.6 eV compared to 15.8 eV for argon [123], The
high ionization energy enhanced the possibility of energy
transfer to the analyte. A helium plasma is able to excite
efficiently elements introduced into the plasma, and has low
background characteristics. Hydrogen (BOC Gases, The BOC
Group, Inc., Murray Hill, N.J.) was introduced into the

53
plasma at a flow rate of 250 cmVmin for the cleaning step.
The presence of hydrogen in the plasma helped to create a
reducing environment and increased the temperature of the
plasma [124] . The higher temperature and reducing
environment helped in the removal of the carbonaceous
residue left over from the blood sample.
Electrode
The graphite cup holder electrodes were made out of
spectroscopic grade carbon (Union Carbide, Carbon Products
Division, Cleveland, OH). The metals used for the cups and
the electrodes were obtained from Alfa Aesar/Johnson
Matthey, Ward Hill MA. The following metals were obtained
as rods and machined to make the various electrodes: nickel
(99.5% pure), titanium (99.99% pure), and tungsten (99.95%
pure). The tungsten screen used was obtained from Newark
Wire Cloth Co., Newark, NJ.
The tungsten wire (99.95% pure) used was also obtained
»
from Alfa Aesar/Johnson Matthey, Ward Hill, MA. Three
diameters of wire were used: 0.25 mm, 0.5 mm, and 0.75 mm.
The final filament used was made out of the 0.5 mm tungsten
wire. The top of the filament was a tight 2.5 turn spiral
with a diameter of 3 mm. The total length of the filament
was 6.5 cm.

54
Lens Setup
The initial lens setup (figure 4-3a) used two
planoconvex lenses. The first lens (diameter = 50.8 mm,
focal length = 125 mm) was placed 125 mm from the plasma to
collimate the emission from the plasma. The second lens
(diameter = 25.4 mm, focal length = 50.8 mm) was placed so
that the emission was focused onto the entrance slit of the
spectrometer.
In an attempt to improve the precision of the CCMP-AES,
the lens setup was changed after the lead-in-blood work was
completed. The lenses (figure 4-3b) were set up so that the
emission from the plasma filled the collimating mirror of
the spectrometer. Two lenses had to be used because a
single lens could not be placed close enough to the plasma
for the desired focusing. A first lens (focal length = 38.1
mm, diameter = 38.1 mm, Esco Products/Precision, Oak Ridge,
New Jersey) was used to form a one-to-one image of the
plasma at a proper distance away from the plasma. It is
placed 76 mm from the plasma. The second lens (focal length
= 25.4 mm, diameter = 25.4 mm, Esco Products/Precision, Oak
Ridge, New Jersey) was then used to magnify the image in
such a way that the collimating mirror of the spectrometer
was completely filled with emission. The second lens was
placed 102.78 mm from the first lens. The distance for each

Plasma
O
a)
Plasma
0
b)
Collimating Focusing
Lens Lens
Lens 1
\ Len
L /
• «
s 2
\
P. . 1 / \
/ 1:1 Image
/ of Plasma
s
)
¿
Figure 4-3. Lens setup (not to scale): a) lead in
blood work, b) multielement work.
Spectrometer
Spectrometer
To collimating
mirror of
spectrometer
»
<_n
<_n

56
lens was calculated from the equations:
1/f = 1/s + 1/s' and m = s'/s
where f is the focal length of the final lens, s is the
distance between the emission source and the final lens, s'
is the distance between the lens and the mirror, and m is
the resulting magnification of the image. In the
modification of this lens setup, s became the distance from
the second lens to the one-to-one image formed by the first
lens. This lens setup resulted in a magnification of the
plasma image of approximately 25 times.
Detector
The detector consisted of a 0.5 m spectrometer (Spex
1870, Edison, NJ, USA) and either a photodiode array (PDA)
or a charge coupled device (CCD). The spectrometer grating
contained 1200 grooves/mm with a blaze wavelength of 300 nm.
The preliminary work and the lead in blood research was done
using the PDA. The multielement work was done with the CCD.
The spectrometer slit width was adjusted for each
element. If greater sensitivity was needed, the slit width
was opened to as much as 40 ¿¿m. For elements requiring less
sensitivity and higher resolution, a slit width as small as
10 /¿m was used. The slit height was kept constant at 2 cm.
Both the PDA and the CCD gave a spectral window of 40 nm.

57
Photodiode array
The intensified photodiode array (Tracor Northern TN-
6122A, Middleton, WI, USA) consisted of 1024 silicon
photodiodes arranged linearly, each spaced 25.4 apart.
Each photodiode consisted of a layer of silicon doped with
atoms containing extra electrons (p-type semiconductors) on
top of a layer of silicon doped with atoms with one valence
electron less than silicon (n-type semiconductor). This
allows the current to flow in only one direction. A reverse
biased potential is applied across the diode so that when
exposed to light, electron hole pairs are created producing
a current that is proportional to the amount of light [125-
126] .
Charge coupled device
The detector was changed from the photodiode array
(PDA) that was used for much of the lead-in-blood work, to a
charge coupled device (CCD) for all of the multielement
work. This change was necessary because of problems that
developed with the hardware and software that controlled the
PDA. The CCD detector has the advantage that it was two
dimensional and was cryogenically cooled to reduce the dark
current.
The CCD contained 296 x 1152 picture elements (pixels).
Each pixel was 20 ¡j.m square and consisted of a metal-oxide-
silicon (MOS) capacitor. The pixels were made out of an

58
insulating silicon dioxide layer over a p-type silicon
substrate. This was topped by a thin metal electrode [125,
127-128], When a photon struck a pixel, it penetrated the
lattice breaking the covalent bonds between adjacent silicon
atoms. This created electron-hole pairs which were measured
as an electric charge. The radiation striking each pixel
was proportional to the resulting charge and was measured by
transferring the charge to a single point. The covalent
bonds could also be broken by thermal agitation. The
thermal generation of charge was reduced by cooling the CCD.
Figure 4-4 shows the effect of cooling on the CCD background
counts. The temperature was maintained constant by a
heating element in the CCD dewar. The temperature was
maintained at -110 °C even though there was not much change
in the dark counts below a temperature of -40 °C. At
temperatures higher than -90 °C the liquid nitrogen
evaporates too quickly. At temperatures lower than -140 °C,
the charge transfer efficiency from pixel to pixel may be
lowered, degrading the CCD performance [126].
If the light levels reaching the CCD were too high,
blooming could occur. Blooming is the spillage of charge
from an over-illuminated pixel to an adjacent pixel [126,
128]. The signal to noise ratio and the dynamic range could
be improved by the process of binning. Binning combines the
charge from adjacent pixels during readout. The charge read

Background Count Values
59
Figure 4-4. CCD background dependence on temperature.

60
will increase by the number of pixels binned, but the noise
will stay the same. Binning has the disadvantage of
reducing the spatial resolution [126],
Originally, the CCD detector was not sensitive to
emission below 400 nm. The camera was sent to Spectral
Instruments (Tucson, Arizona) so that a UV enhancement
coating could be applied to the CCD element. The coating
was lumogen yellow, an organic phosphor. The phosphor
absorbs light in the UV range and re-emits it in the visible
range.
Computer Software
The programmable power supply and the triggering of the
detector were controlled by a computer (PC's Limited, model
28608L, PC's Limited, Austin, TX) and a computer interface
(Model SR 245, Stanford Research Systems, Palo Alto, CA,
USA) using a program written in Microsoft QuikBasic 4.50
(Copyright Microsoft Corporation, 1985).
The emission spectra were collected using CCD9000â„¢
spectral acquisition software, version 2.2.2 (copyright
1990-1992, Photometries, Ltd.). The peak areas were
determined using the program LabCalcâ„¢ (copyright 1987-1992,
Galactic Industries Corporation). Analytical curves were
constructed using Originâ„¢ version 4.0 (copyright 1995,
Microcalâ„¢ Software, Inc.).

61
Materials
Aqueous Standards
Aqueous standards were prepared by sequentially
diluting 1000 ppm reference standards for each element
(Fisher Chemical, Fisher Scientific, Fair Lawn, New Jersey).
The standards used in the standard additions of the blood
analysis were prepared from the salts of the elements being
analyzed. This was necessary because the standards needed
to be non-acidic to prevent denaturing of the blood. Also,
the concentrations required for some of the elements were
larger than the available aqueous standards. All the
aqueous standards were prepared using deionized water
(specific resistivity 18 MQ/cm) from a Milli-Q Plus water
system (Millipore Corporation, Bedford, MA). The aqueous
standards were introduced for analysis using a 2 ¡xh air
displacement pipetter (Eppendorf, Brinkman Instruments Inc.,
Westbury, NY).
Blood Standards
The lead bovine blood standards used were Quality
Control Materials (QCM) produced and distributed by the CDC
Blood Lead Laboratory Reference System (BLLRS). The samples
were collected by the CDC from two cows kept at the CDC
livestock facility (Lawrenceville, GA) that were given

62
dosages of lead nitrate in gelatin capsules. The blood was
collected from the cows and the initial concentration was
determined using atomic absorption spectrometry. Varying
amounts of the two blood samples were then blended to give a
range of lead concentrations. The final concentrations of
the samples were determined using ID-ICP-MS [70].
Human whole blood was collected by venipuncture into a
Vacutainer (Becton Dickinson Vacutainer Systems, Franklin
Lakes, NJ, USA) coated with KEDTA as an anticoagulant. The
standard addition samples were made by adding varying
amounts of an aqueous standard to a 0.75 mL portion of whole
blood. Deionized water was added to the sample to produce a
final volume of 1.0 mL. This resulted in a sample that was
75% whole blood. The samples were gently rolled and then
sonicated for 5 minutes to thoroughly mix the aqueous
standard and the blood.
A lead-in-blood Standard Reference Material (SRM 955a)
was purchased from the National Institute of Standards and
Technology (NIST) (Gaithersburg, MD). This SRM consisted of
four vials of frozen bovine blood each containing a
different concentration of lead. The concentration of lead
in each SRM was determined by NIST using ID-ICP-MS and
confirmed using GFAAS and laser-excited atomic fluorescence
spectrometry. The concentrations are shown in Table 4-1.
The uncertainty reflects a confidence level of 95%.

63
It was necessary to keep the blood samples frozen when
not in use. By freezing the blood, the bacterial and
chemical interaction of the blood sample were greatly
reduced. If not frozen, the various elements can bind to
proteins in the blood and settle out. Although the content
of the element in the vial remains the same, the
concentration in the liquid portion will be less than the
target value for the standard. The proteins could also
denature leading to a change in the homogeneity of the blood
[129]. Prior to use, the blood samples were allowed to thaw
to room temperature, homogenized by gently rolling, and then
sonicated for 10 minutes.
The blood samples were introduced for analysis by a
positive displacement micropipetter (Drummond® model 525,
Drummond Scientific Co., Broomall, PA). Before depositing
the sample, the outside of the glass capillary tip was wiped
with a Kimwipeâ„¢ to remove any blood that had adhered to the
tip. The pipetter was cleaned between sample runs by
repeatedly depressing the plunger first in a solution of 5%
nitric acid solution and then in deionized water.

64
Table 4-1. Concentration of lead in SRM 955a at 22°C.
Vial Number
Concentration (ppb)
955a-l
50.1 ± 0.90
955a-2
135.3 ± 1.3
955a-3
306.3 ± 3.2
955a-4
544.3 ± 3.8

CHAPTER 5
SAMPLE INTRODUCTION
Introduction
Capacitively coupled microwave plasma atomic emission
spectrometry (CMP-AES) has been used to analyze various
types of samples directly. Discrete sample introduction in
a CMP is easier than in a microwave induced plasma or an
inductively coupled plasma because a CMP is the only one
that uses an electrode to support the plasma.
Investigations have involved the analysis of various
matrices including dry tomato leaf samples, coal fly ash,
steel, oil, and biological materials [1-3, 130-132] . A
variety of methods have been used for sample introduction
into a CMP. They have included nebulization, thermal
vaporization, and hydride generation.
Methods of Sample Introduction into a CMP
In the earliest work with a CMP as an atomic emission
source, solid electrodes were used to support the plasma.
The analyte solution was vaporized and carried into the
plasma by premixing the analyte carrier gas and the plasma
65

66
gas. Hanamura et al. used a platinum clad tungsten
electrode with this method of sample introduction [133] .
The platinum coating was used because the platinum is
thermally stable, chemically inert, and has a low thermionic
emission rate. These properties of platinum increased the
electrode lifetime and reduced the contamination of the
plasma by elements present in the electrode. Interfering
emission lines from the electrode is one of the major
drawbacks of the single electrode CMP. Hanamura and
coworkers use this type of electrode to analyze hydrogen and
oxygen in metals and also mercury in water [133-134] .
Nebulization
Several researchers have used a nebulizer to introduce
aqueous samples into a CMP [124, 135-137]. A nebulizer is
an easy and inexpensive way to introduce a solution into a
plasma. Nebulization is a process where the sample to be
analyzed is transferred by a peristaltic pump to a nebulizer
which converts the sample into an aerosol in a spray
chamber. The aerosol is then swept by a carrier gas through
the center of the electrode into the plasma. A disadvantage
of nebulization is that much of the sample is lost in the
spray chamber.

67
Patel et al. used pneumatic nebulization with a CMP to
analyze aqueous samples for 15 elements [135]. Sample
solutions were nebulized with a Meinhard nebulizer and a
laboratory-constructed spray chamber and desolvation system.
A tubular electrode made out of tantalum was used to support
the plasma. The analyte carrier gas passed through the
center of the hollow electrode and entered into the plasma
at the top of the electrode [25] . By introducing the sample
directly into the core of the plasma, the interactions
between the sample and plasma were improved. Also, the
concentration of the analyte in the plasma viewing region is
increased, improving the detection limits, signal to noise,
and signal to background. It was determined that this
method gave low detection limits with a wide linear dynamic
range for a number of different elements. Several other
tube materials and forms of electrodes were evaluated. The
electrode types included a platinum tube, a copper tube, a
platinum coated tungsten wire (0.5 mm o.d.) a molybdenum
rod, and a tungsten rod with platinum cladding [135].
Hwang et al. used graphite as the electrode material
[137] . This electrode had a lower emission background and
did not significantly contaminate the plasma in comparison
to the metal rod electrode. Excellent detection limits for
several elements in aqueous solutions were obtained [137] .

68
Thermal Vaporization
Two previous methods of sample introduction by thermal
vaporization (TV) include a tungsten filament electrode
(figure 5-la) [23, 131-132] and a cup holder electrode
(figure 5-lb) [1-3, 130, 138-139]. The sample was
introduced into the CMP by directly depositing it on the
filament or in the cup held by the electrode. Thermal
vaporization is advantageous over nebulization in that a
greater percentage of the sample is introduced into the
plasma. TV has the disadvantages of poorer precision,
greater interference effects, and a lower throughput of
samples.
Hanamura et al. used a another method of thermal
vaporization with a CMP to measure carbon, hydrogen,
nitrogen, oxygen and mercury in orchard leaves and tuna fish
[140]. A separate furnace vaporizer was used. The sample
was held in a quartz crucible which was heated. The carrier
gas was flown through the sample chamber to carry the
volatile constituents through the center tube of the torch
and into the plasma for analysis.
Cup electrode
A cup can be used to introduce both liquid and solid
samples into a CMP. In order to use a cup electrode, an
electrode must be fabricated such that the top of the

69
!â– â– â– #
a) b) c)
f
M
d)
rui
Figure 5-1. Electrode designs: a) filament electrode,
b) cup holder electrode, c) platform electrode,
d) titanium electrode with nickel cap,
e) titanium electrode with titanium cap.

70
electrode has a hollowed out portion that will snugly hold
the cup. The electrode must be made out of a material that
is conductive and has a higher melting point than the
thermal temperature of the plasma. Materials that can be
used for the electrode are graphite or various metals.
Graphite electrodes are cheaper and more resistive than
metal electrodes, and emission from the metal electrode can
also cause interference in analysis. Electrodes made out of
metal have several advantages over those made out of
graphite. Metal electrodes are more durable and last longer
than graphite electrodes. Also, graphite electrodes form
refractory carbides and produce gaseous molecular carbon
species which cause interference in emission measurements.
Cups made out of both graphite and tungsten have been
used to hold the sample. The cup was placed on the top of
the electrode and the electrode containing the cup was
placed into the central tube of the torch. The plasma was
ignited at a low power (around 100 W) to ash the sample and
was then raised to 400 - 700 W to atomize and excite the
analyte, enabling the measurement of the emission [1]. By
using a cup instead of a wire filament, higher powers could
be used so that there were fewer matrix effects and the
signal was larger. The disadvantage of using a cup was that
the atoms were dispersed over a wider volume so the number
density of excited atoms was smaller.

71
Ali et al. used CMP-AES with a cup electrode with both
the electrode and the cup made out of graphite. Detection
limits ranging between 10 and 210 pg were obtained for 12
elements with a precision better than 12% [138] . A sample
volume of only 5 («L was used. The graphite cup was coated
with tantalum carbide to reduce memory effects. Because
graphite was quite porous, memory effects were observed for
all the elements analyzed. The cups lasted 30-40 firings
and then had to be replaced due to etching of the cup rim by
the plasma. Multielement analysis with this system was
performed on coal fly ash and tomato leaves [1]. Spencer et
al. used a tungsten cup to analyze silicon in oils [3].
Tungsten was found to be an excellent cup material because
of its tolerance to high temperatures, long lifetime, low
emission background, and low memory effects.
More recently Pless et al. used a tungsten cup in a
graphite electrode for multielement analysis [139] . The
cup had a total volume of 30 /¿L. Detection limits in the
low picogram range were obtained for 10 ¿íL samples of
cadmium, magnesium, and zinc in aqueous solutions. Cadmium
in solids was also analyzed obtaining a detection limit in
the picogram range [130]. Various matrices were analyzed by
this system including coal fly ash, tomato leaves, soil,
bovine liver, and oyster tissue. The results achieved good

72
agreement with the certified values of the reference
materials.
Filament electrode
Ali and Winefordner evaluated a tungsten filament
electrode for multielement analysis in aqueous solutions
[23]. Filaments have the advantage that they are simple and
inexpensive. The sample was introduced into the plasma by
placing a few microliters of sample in a loop in the
filament. The sample was then dried at low microwave
power. The filament heated up rapidly creating a high rate
of volatilization. After the sample was dry, the plasma was
ignited and the sample was ashed if necessary by a low power
(30 W) microwave plasma . The power of the plasma was
increased until the sample was atomized and excited so that
the emission could be measured. It was found that adding a
low flow rate (100 mL/min) of hydrogen gas with the plasma
gas reduced the background emission from the tungsten
filament. The absolute detection limits of 12 elements were
in the range of 1 to 100 pg and this compared favorably to
the method of graphite furnace atomic absorption
spectrometry (GFAAS). A linear dynamic range of 3 to 4
orders of magnitude was obtained and the precision was
better than 10%. Reported lifetimes for the filaments were
500-1000 runs [23].

73
Wensing et al. evaluated a CMP-AES for a lead blood
screening method using a tungsten loop (figure 5-la) as the
electrode [131-132], A tungsten wire of 0.25 mm thickness
was tied in a knot, leaving a small loop in the center, and
the remaining ends of the wire were bent so that they could
be inserted into a piece of quartz tubing which was then
inserted into the plasma torch. The blood samples were held
in the loop by adhesion to the wire.
A 5 pL blood sample was placed in the filament loop and
subsequently dried, ashed, and atomized. Drying was
accomplished using microwave power to inductively heat the
electrode for 90 seconds. After drying, the helium gas flow
was turned on and a small plasma was ignited, ashing the
sample at a power of 55 W for two minutes. The sample was
then atomized in a helium plasma at a power of 170 W. The
lead emission at 405.8 nm was measured using a photodiode
array (PDA). A cleaning step was necessary in order to
remove the carbonaceous residue from the left over blood
sample. Cleaning was performed by increasing the power to
200 W and adding a flow of hydrogen gas to the helium
plasma. The cleaning procedure lasted for one minute and
effectively removed all blood residue from the filament.
The filament electrode CMP-AES method was able to meet
two of the criteria set forth by the Centers for Disease

74
Control (CDC) for a lead in blood screening method. The
detection limit for lead in blood was 7 ppb and the analysis
time was under five minutes. However, the filament
electrode was not accurate for blood lead concentrations
unless matrix effects were reduced by diluting the blood
with deionized water by a factor of approximately one half.
Even with dilution, the method was not sufficiently accurate
for blood lead concentrations below approximately 200 ppb
and the precision did not meet the requirements set forth by
the CDC for lead in blood screening methods.
Using the filament as the electrode had several drawbacks.
The filaments were handmade and so were difficult to make
reproducibly. It was also difficult to deposit the sample
in the filament loop with adhesion to the wire as the only
source of support for the sample. Finally, the lifetime of
the filament electrode was greatly shortened if the
microwave plasma power was raised above a certain point.
Hydride Generation
Hydride generation involved introducing the elemental
analytes to the CMP as a gas. An acidified aqueous solution
of the sample was added to a small volume of 1% sodium
borohydride in a reaction cell. After a certain amount of
time had passed, the resulting hydride of the element was
carried to the CMP by a flow of the plasma gas. Akatsuka

75
and Atsuya used a CMP with hydride generation to analyze
arsenic in sewage sludge, and iron in steels. They obtained
a detection limit of 0.25 ppb for arsenic in solution [141].
Uchida et al. used the method of hydride generation with a
CMP to analyze inorganic tin [142].
Development of Electrode for Blood Analysis
Cup Holder Electrode
A cup holder electrode (figure 5-lb) was investigated
for the analysis of lead in blood. A cup holder electrode
had several advantages over the filament electrode used by
Wensing et al. for lead blood analysis. Using a cup holder
electrode allowed the introduction of larger sample volumes
and made sample deposition easier and more reproducible.
Also, a cup holder electrode is a more robust electrode
allowing the atomization power to be increased, which could
lead to increased emission intensity.
Initially the electrode material chosen was graphite.
Graphite is a good material because it can sustain very high
temperatures, it is inexpensive, and it is easy to machine
to make modifications to the electrode. The easy
machinability of graphite allowed various parameters of the
electrode (length and penetration) to be optimized before

76
switching to a metal cup holder. The metal holder would be
more durable but not as easy to machine as graphite.
The graphite electrode contained a hole in the top
which held a nickel cup. A graphite cup would not be
suitable for blood analysis because the graphite could form
refractory compounds which would interfere with the lead
signal. Also, the blood could seep into the graphite
causing memory effects. A cup made out of metal would be a
better choice because there would be less of a chance of
interfering species and memory effects. Initially, nickel
was chosen as the cup material because it did not oxidize
easily, making it very durable. The cup had a sample
capacity of 20 ¡iL.
Several parameters for the cup electrode were studied.
The change in electrode from the filament to the cup
electrode required reoptimizing the conditions of the
plasma. The coupling of the microwave energy and the
stability of the plasma were affected by the length of the
electrode, and the electrode's penetration into the
waveguide. The optimum coupling position of the electrode
was determined by varying the electrode length penetration
into the microwave field to find the parameters where the
minimum microwave power was needed to sustain the plasma.
The first parameter studied was the length of the
electrode. Initially the height of the electrode above the

77
waveguide was kept constant at 8 mm. This was the height
used in the work with the tungsten filament electrode.
Different lengths of the electrode were then used
determining the range of powers over which a stable plasma
would form. The power supplied to the magnetron was
gradually increased until a plasma would form. The power
was increased until the plasma was no longer stable and then
decreased until the plasma could no longer be sustained.
The lengths of the electrodes ranged from 3.5 cm to 7.0 cm
which corresponded to a depth of penetration into the
waveguide of 2.7 cm to 5.7 cm. This experiment was repeated
keeping the penetration depth of the electrode into the
waveguide constant at 3.2 cm and evaluating different
lengths of the electrodes. As the penetration depth was
increased, the plasma could be maintained at higher powers.
For some positions of the electrode, the maximum power of
700 W could not be achieved because the plasma started to
make a very loud whining noise. The length and penetration
that produced a stable plasma over the widest range of
powers was chosen as the optimum. Figure 5-2 shows some
examples of the data collected for the optimization of
electrode length and penetration.
Using the optimum conditions found for the electrode,
the analysis of aqueous lead solutions was studied. At an
atomization power of 370 W, the lead emission took

78
Figure 5-2
Optimization of electrode length and
penetration depth of graphite electrode

79
approximately 20 seconds to appear and then remained for 90
seconds for a 10 jiL sample of a 50 ppm lead standard. At
such a high concentration and power, the signal should have
been much greater. Tungsten and titanium cups were
evaluated with the graphite cup holder, but these cups also
gave poor results.
The next electrode evaluated was a cup holder made out
of titanium with a nickel cup. Titanium metal instead of
graphite could improve the coupling of the microwaves to the
electrode, improving the efficiency of atomization and
excitation. After atomization with this system, the cup
remained very hot and required a long time to cool down. If
an aqueous sample was deposited in the cup before it was
sufficiently cooled, the sample would vaporize. No
improvement of the lead signal intensity was observed.
Platform Electrode
A cup holder electrode made out of titanium that had
not been drilled to hold a cup was then studied as the
method of sample introduction. This type of electrode was
labelled the platform electrode because the sample was
placed on the flat top portion of the electrode. The top
portion was approximatly 6.5 mm long and 6 mm in diameter
and the post was ~ 3 mm in diameter. A 10 iiL aqueous lead
sample was placed on the flat top of the electrode, dried

80
for 90 seconds at approximately 150 W and then atomized with
a plasma power of 300 W. The titanium platform electrode
gave a larger signal than had previously been obtained. The
signal still lasted a long time (figure 5-3a) but not as
long as with the graphite electrode and the nickel cup. The
signal increased (figure 5-3b) when the bulky top part of
the electrode (that was intended to hold the cup) was
removed, yielding a thin metal rod (Figure 5-2c). With this
electrode design, the plasma formed on the same surface that
the sample was on, increasing the interaction of the sample
and the plasma, yielding more efficient atomization and
excitation.
A significant problem was experienced with the titanium
electrode. After several runs, the lead signal would begin
to decrease in intensity and take longer to appear. It was
necessary to sand off the top of the electrode to regain the
larger signals. Each time the electrode was sanded, a
titanium atomic emission line appeared that interfered with
the lead line being used for measurement. The electrode had
to be tempered by igniting a plasma and then slowly taking
it to higher powers to eliminate the interference before
conducting another run after cleaning. The more the
electrode was used, the sooner in between runs it had to be
cleaned off. The interfering titanium line also limited the
amount of power that could be applied to the plasma. At

slgnal Signal
81
Figure 5-3. Temporal profiles for lead signal for the
platform electrodes: a) platform with cup
holder portion, b) thin titanium rod platform.

82
powers above 400 W, the interfering line appeared. It is
desirable to have an electrode that could last for an
indefinite period of time and would not have any emission
lines which would limit the powers used. For these reasons,
several other materials were tried for the platform
electrode.
Tungsten, which had been used for the filament
electrode, has a higher melting point and lower background
emission than titanium and so it was evaluated as the
electrode material. A 10 ¿¿L aqueous sample on the tungsten
electrode took approximately 5 minutes to dry at a microwave
power of 150 W. The lead signal, upon atomization, took
several seconds to appear and then lasted for about 30
seconds. The signal was small compared to the signal
obtained using the titanium electrode, even at higher
powers. Nickel was studied next, but it also produced
results similar to those obtained with the tungsten
electrode.
A titanium electrode with a nickel cap which screwed
into the top was then evaluated (figure 5-2d). This design
was used in an attempt to obtain a similar signal as that
obtained with the titanium electrode, but with a longer
lifetime because of the nickel cap. The signal obtained for
this electrode was similar to that obtained when the whole

83
electrode was nickel; a low intensity signal was delayed in
appearing and had a long temporal profile.
From the results obtained, the electrode made out of
pure titanium was the best platform electrode even though it
would have to be changed on a regular basis. The titanium
platform electrode lasted approximately 130 firings for
aqueous samples. The titanium platform gave good results
for aqueous lead samples (figure 5-4) achieving a detection
limit of 30 ppb for a 5 pL sample volume. However, the
precision was poor for concentrations of 100 ppb and below.
Analysis of lead in whole blood was performed using
whole blood quality control materials (QCMs). The
analytical curve for these standards (figure 5-5) was linear
(R = 0.997) and produced a detection limit of 50 ppb. After
running an individual analysis, it was necessary to clean
the electrode by scraping off the remaining blood residue.
This was not difficult, but added approximately one minute
to the analysis time. Occasionally, the blood sample would
interfere with the plasma yielding poor precision. The
interference of the blood samples with the plasma might be
due to a problem in depositing the sample. Since the
surface of the electrode was flat, it was difficult to
deposit the sample in the same way each time. The maximum

84
Concentration (ppb)
Figure 5-4. Analytical curve for aqueous lead standards on
the titanium platform electrode.

85
Figure 5-5. Analytical curve for whole blood lead standards
on titanium platform electrode.

86
capacity of the titanium rod platform was 5 pL, and the
sample would sometimes run over the side.
In order to achieve reproducible sample deposition,
electrodes containing a depression in the top were used. It
was found that the size and shape of the depression was very
important in measuring the lead signal. If the depression
was too deep, the signal was small. If the volume of the
blood sample was too large, the blood would interfere with
the formation of the plasma. When blood samples were run
with the depression electrode, the inside of the depression
became dirty and was difficult to clean. Even for shallow
depressions, the lead signal was approximately one half of
the signal obtained by the electrode without the depression.
The electrode with the depression had a short lifetime of
only 30 firings for blood samples.
To reduce the amount of time required to clean the
electrode, a titanium electrode with a cap was used (figure
5-2e). This electrode design allowed one cap to be cleaned
while another cap was being used for analysis. Samples
could also be dried separately, and then placed on the cap
holder to use the microwave plasma for the ashing and
analysis. This shortened the analysis time by ninety
seconds and could be beneficial for the storage and
transport of the blood samples in the clinical setting.
Caps with various diameters and various sized depressions

87
were used. Some problems were experienced with the
uniformity of the plasma on the titanium cap electrode. At
lower microwave powers, the plasma would sometimes form on
one side of the cap and either stay at that side or flicker
around the edge of the cap. At higher microwave powers,
some of the caps yielded good signal, but it was difficult
to clean them when analyzing blood samples. The caps were
also difficult to reproducibly construct. Caps with the
same design did not produce the same signal.
â– Suspension Method
The results with the platform electrode demonstrated
that it is necessary for the plasma to interact directly
with the blood sample. Anytime the blood sample was below
the plasma in some sort of depression, the signal was
drastically reduced. However, when the blood sample was on
the surface of the electrode where the plasma formed, the
blood would often interfere with the stability of the
plasma. A method for which the sample was suspended above
the electrode was used to try to account for keeping the
sample in the plasma without being on the surface where the
plasma forms. A titanium rod electrode was used to support
the plasma and a macor holder was used to support a screen
or a wire mesh above the electrode (figure 5-6). Initially
stainless steel screens (10-20 and 40 mesh) were used.

88
Figure 5-6. Suspension method of sample introduction.

89
Platinum screens (40 mesh), tungsten screens (20 and 40
mesh), and a four-squared cross made out of tungsten wire
were also tried.
The sample would not dry with microwave power alone, so
a very low power plasma was ignited below the screen. For
blood samples, the drying caused some problems because if
the plasma was too close to the sample or too high in power,
it would cause the sample to bubble and spatter. The
titanium electrode was changed to a pointed tungsten
electrode which could sustain a very low power plasma which
dried the blood more effectively. The power of the plasma
was increased for ashing, and then further increased for
atomization. This method worked well for aqueous standards
and greatly decreased the background during atomization
because the macor holder shielded most of the emission from
the plasma. However, this method of sample introduction did
not work well for blood samples. The mesh became very
brittle at higher plasma powers and broke very easily.
Spiral Filament Electrode
Each method of sample introduction tried had various
advantages to it. The cup holder electrode held the sample
the best, the filament electrode was easiest to clean, the
platform electrode gave the best signal, and the macor
holder resulted in the lowest background. Various features

90
of several of these methods were combined to design an
improved filament electrode. A thicker (0.5 mm in diameter)
tungsten wire was used which was more durable and could
sustain higher powers than the original filament (0.25 mm in
diameter) could. Initially a single loop was made at the
top of the wire to hold the sample, but it was difficult to
deposit the sample in the loop. A two and a half turn
spiral was then made at the top of the electrode The spiral
served as sort of a platform and held a 2 ^1 blood sample
very well. The spiral filament electrode (figure 5-7)
performed well for both aqueous and blood samples (chapter
6) and was easy to clean. The filament was, however,
difficult to make because the tungsten wire was very brittle
and would often split during the construction of the spiral.
An attempt was made to use commercial tungsten light
bulb filaments to hold the sample. A 20 turn, rectangular
light bulb filament was placed over the loop of a filament
electrode. This method would remove the necessity of having
the spiral at the top of the electrode and could also help
make the electrodes more reproducible. The method worked
well for aqueous samples (figure 5-8) giving a detection
limit of 44 ppb, but was very hard to clean after the
analysis of blood samples. It also eroded quickly under the
high plasma powers used to clean the blood from the
electrode.

91
~ 3 mm
*
65 mm
Wire Diameter = 0.5 mm
Â¥
Figure 5-7. Tungsten spiral filament.

Concentration (ppb)
Figure 5-8. Analytical curve for aqueous lead standards
the commercial tungsten filament.

93
Conclusion
The best method of sample introduction was the spiral
filament electrode. The spiral provided a surface which
could hold the sample and support the plasma so that the
sample was directly in the plasma. The sample could easily
be deposited on the spiral reproducibly. The filament was
also simple to clean after each analysis.

CHAPTER 6
ANALYSIS OF LEAD IN BLOOD
Introduction
The initial goal of the research was to develop the
CMP-AES as a screening method for lead in whole blood. The
guidelines set forth by the Centers for Disease Control
(CDC) for an improved blood lead measuring system were used
to evaluate if the CMP-AES was an appropriate screening
method. Once the electrode design was decided, a number of
other operating parameters had to be optimized.
Optimization of Parameters
Helium Flow Rate
Wensing et al. used a helium flow rate of 10 L/min for
their work on lead in blood [131-132]. Lower gas flow rates
generally increased the residence time of the analyte in the
plasma, which increased the efficiency of atomization and
the intensity of emission. It also reduced the amount of
gas consumed. Therefore, the effect of flow rate on lead
emission intensity was investigated. The emission signal
gradually increased with decreasing flow rate. At flow
94

95
rates below 6 L/min, the plasma no longer appeared stable.
A flow rate of 8 L/min was chosen because this flow rate
produced a stable plasma and reproducible results.
Drying and Ashing Conditions
Drying and ashing steps are essential in the direct
analysis of whole blood. The drying step removes the
moisture content of the blood allowing a plasma to be formed
on the top of the electrode. A low power was applied to the
magnetron which generates microwaves in the waveguide,
inductively heating the tungsten electrode. The electrode
got sufficiently hot to vaporize most of the moisture in the
blood. A sufficient power had to be applied to remove the
moisture without causing the blood to spatter. For use as a
screening method, the amount of time per analysis is very
important so the drying time must not take too long.
A low power plasma was used to ash the sample. The
ashing step removed much of the carbonaceous material in the
blood preventing it from interfering with the emission from
the analyte. Without ashing, a very high background was
produced that saturated the detector. Also, the high power
plasma used for atomization and emission was not stable if
there was a significant amount of blood material left on the
electrode.

96
The power of the plasma and the time used for ashing
were very important. If the power was too low or the time
was too short, not enough of the blood material was removed
causing the problems just discussed. If the ashing power
was too high or the time was too long, the analyte could be
volatilized and lost, decreasing the signal. Various ashing
powers (figure 6-1) and times were investigated.
The best method of ashing the blood samples involved
using a number of steps, gradually increasing the ashing
power. With inductive heating of the electrode, the blood
sample on the electrode would never fully dry. A very low
microwave power was applied and the plasma was ignited by
touching a tungsten wire to the tungsten electrode. The
friction from the two wires was sufficient to spark the
plasma. The plasma power was then increased by a small
amount causing the blood to bubble, but not spatter, until
all the moisture was removed. When the blood sample was
completely dry, the power of the plasma was further
increased to remove much of the blood material. Two steps
were used for the actual ashing of the sample, and a third
step was used to ensure that the plasma formed for
atomization was stable. If the plasma power jump from the
ashing steps to the atomization step was too large, the
resulting plasma was initially unstable.

Signal
97
Figure 6-1. Effect of ashing power on blood lead signal.

98
Cleaning
The cleaning step is essential for reproducible
analysis. If blood residue was left on the electrode prior
to another measurement it could cause memory effects or
interfere with the atomization and emission of the sample.
The cleaning step must be sufficient to remove all remaining
carbonaceous material without significantly reducing the
lifetime of the electrode. If the cleaning conditions were
too harsh, the tungsten filament became very brittle and
wore away.
The cleaning procedure used involved increasing the
power to 200 W with a reduction in helium flow rate to 2
L/min for 10 seconds and then a return to 8 L/min for
another 10 seconds. Hydrogen gas was introduced for the
cleaning step at a flow rate of 350 cmVmin. The addition
of hydrogen helped to clean the electrode by increasing the
gas temperature of the plasma [124] . The decreased flow
rate of helium increased the amount of oxygen in the plasma
improving the oxidization and removal of the carbonaceous
blood residue. After cleaning, the electrode had a very
shiny appearance and was free from any carbon residue. The
cleaning step reduced the lifetime of the electrode;
however, it was still possible to use the electrode for
close to 100 samples.

99
Sample Size
The sample size was very important for screening
methods. One method of collecting blood samples for lead
screening was the finger stick method. This involved
piercing an individuals finger and then collecting blood
using a capillary tube, which collected only microliter
volumes; therefore, the method used must not require a
sample larger than the amount collected. Larger samples
are beneficial because they contain more analyte and are
easier to handle and to introduce reproducibly than are
smaller samples. Various sized blood samples were analyzed
for lead using the CMP-AES. These results indicated that
there was not a large increase in signal with sample size.
The precision, however, degraded significantly with
increased sample size. For very large samples, the spiral
filament appeared to be overloaded, with blood hanging below
the spiral top and adhering to the stem of the filament just
below the spiral. Filaments with larger spirals which were
able to accommodate larger sample sizes were tried, but did
not give improved results. Increased ashing times were also
tried to account for the larger amount of blood but were
unsuccessful. A sample size of 2 ¡j.L was chosen because this
volume gave good precision and was not difficult to
reproducibly deposit on the electrode.

100
Sources of Noise
The largest source of noise for the CMP-AES was
investigated. Sample runs were performed 10 times each for
aqueous samples, blood samples, and an empty filament. The
noise from the dark current and from fluctuations in the
plasma with it continually running were also investigated.
The dark current was the smallest source of noise. The
noise from runs with an empty filament and with aqueous
blanks was three times that of the dark current. Blood
samples produced a level of noise ten times greater than the
dark current. The results demonstrate that the instability
of the emission background from the blood was the greatest
source of noise in the blood analysis.
Analysis
Aqueous Standards
Aqueous analytical curves were constructed using 2 pL
samples. The sample was dried for 60 s at 55 W. The power
was decreased to 30 W and a flow of 8 L/min of helium was
introduced. The plasma was ignited and immediately the
power was increased to 165 W for atomization and emission.
The lead emission was integrated over ten 0.18 second time
intervals. The peak area of the lead signal at a wavelength
of 405.8 nm was calculated for each time interval and the

101
peak areas were added over the lifetime of the lead signal
to obtain a peak volume. The signal was then plotted vs.
the concentration. The resulting analytical curve is shown
in figure 6-2. A detection limit of 45 ppb was obtained.
The correlation coefficient of the analytical curve was
0.9997 and the log-log slope was 1.04. The precision was 2%
for concentrations greater than 100 ppb and 10% for
concentrations lower than 100 ppb.
Bovine Blood Standards
A 2 pL blood sample was deposited onto the top of the
electrode. The blood sample was dried by inductively
heating the electrode using microwave power. After the
blood sample was dry, a low power plasma was ignited and the
sample was ashed in stages. The power was then increased
for atomization. When atomization was complete, the power
was further increased for cleaning. The steps for drying,
ashing, atomization and cleaning are shown in table 6-1.
The signal (figure 6-3) was analyzed by the method used for
aqueous standards. Figure 6-4 shows the temporal profile
for a 2 nh 411 ppb lead blood standard. Each blood standard
was analyzed six times. The analytical curve obtained by
running the CDC bovine blood standards is shown in figure 6-
5. The error bars represent a 90% confidence interval. The
relative standard deviation (RSD) for blood lead

102
Figure 6-2. Analytical curve for aqueous lead standards on
spiral electrode.

103
Table 6-1. Microwave plasma power settings for blood lead
determination
Step
Time (s)
Power (W)
Helium Gas
Flow Rate
(L/min)
Drying 1
20
33
0
Drying 2
20
40
0
Drying 3
20
53
0
Ashing 1
5
30
8
Ashing 2
30
35
8
Ashing 3
30
40
8
Ashing 4
1
45
8
Atomization
9
130
8
Cleaning 1
10
250
2
Cleaning 2
10
250
8

Signal
60000
50000
40000
30000
400 402 404 406 408 410
Wavelength (nm)
Figure 6-3.
Emission spectrum (400-410 nm) for a 2 |iL whole blood sample
containing 411 ppb lead.

Signal
105
5000
4000
3000
2000
1000
0
0
Time (s)
Figure 6-4.
Temporal profile for lead emission signal in
blood.

106
Figure 6-5. Analytical curve for bovine blood lead
standards.

107
concentrations of i 100 ppb is less than 10%. The RSD for
blood lead concentrations of 20 ppb to 100 ppb is less than
20%. The analytical curve is linear with a correlation
coefficient of 0.998 and a log-log slope of 0.999.
nisi Standards
The Standard Reference Materials were analyzed and
compared to the analytical curve obtained from the CDC blood
standards. The measured concentrations are shown next to
the certified concentration values in table 6-2. The
measured values agree with the certified values with 90%
confidence for all the SRM's except for the lowest
concentration. The accuracy at this concentration is
reasonable considering that 50.1 ppb is very near the
detection limit of 30 ppb.
Human Blood Standard
A human blood standard of unknown lead concentration
was also analyzed using the results from the lead bovine
blood standards as the analytical curve. A value of 90 ± 17
ppb was determined. The method of electrothermal
vaporization-laser enhanced ionization spectrometry (ETV-
LEIS) was also used to analyze the same human blood standard
[143] . A lead concentration of 87 ± 3 ppb was determined by
this method.

108
Table 6-2. Measurement of NIST lead in whole blood
standard reference material.
Vial Number
Certified
Concentration
(ppb)
Measured
Concentration
(PPb)
%Bias
955a-l
50.1 ± 0.9
67 ± 20
+ 33.7
955a-2
135.3 + 1.3
147 ± 30
+ 8.6
955a-3
306.3 ± 3.2
298 + 24
-2.7
955a-4
544.3 ± 3.8
563 ± 20
+ 3.4

109
Blood and Aqueous Standards
A desirable characteristic of the method would be the
capability of using aqueous standards for the analytical
curve. The dependence of the lead signal on plasma power
differed for aqueous and blood lead standards. As the
atomization power for an aqueous standard was increased, the
signal increased until it reached a plateau. For blood
standards, however, the signal initially increased with
increasing power but then reached a maximum and started to
slowly decrease. At an atomization power of 130 W, the
signal for both types of standards was the same as shown in
figure 6-6. This would allow the use of aqueous standards
for the determination of the lead levels in whole blood
standards. Figure 6-7 shows an analytical curve in which
both blood and aqueous standards were used. This curve
shows good agreement (R=0.994) for both types of standards.
The power at which the blood and aqueous signals were equal
was reproducible from day to day for the same electrode, but
was not reproducible for different electrodes. The spiral
electrodes were made by hand, and it was difficult to make
each electrode exactly the same. If they could be made
commercially, the reproducibility would greatly increase,
and the use of aqueous standards would be plausible.
The effect of the blood matrix on the lead signal
intensity was investigated. A blood standard and an aqueous

Signal
no
3000 -
2500 -
2000 -
1500 -
1000 -
500-
0- —
118
' 1 1 1 ' 1 ' 1 ' 1 ' 1 ' 1 '
120 122 124 126 128 130 132
Atomization Power (W)
Figure 6-7.
Power comparison for blood and aqueous lead
standards.

Ill
Concentration (ppb)
Figure 6-8. Analytical curve for blood and aqueous
lead standards.

112
standard of the same concentration of lead were mixed in
various amounts to produce blood samples that were 25, 50,
and 75% whole blood. Although the sample composition was
different for each standard, the concentration of lead
remained the same. The intensity of lead signal for these
samples and for pure blood and aqueous samples was measured
at several atomization powers ranging from 131 to 250 W.
The temporal profiles for the whole blood, the 50% blood,
and the aqueous sample at atomization powers of 131 and 250
W are shown in figure 6-9. At all the atomization powers
used, the signal for the samples containing blood appeared
quicker and lasted a shorter time than the aqueous sample.
This could be due to species in the blood that increase the
volatilization rate of the lead present. This could explain
how at the lower atomization powers, the samples containing
some blood in them have greater signals than the
corresponding aqueous standard. By making the lead more
volatile, the processes of atomization and excitation are
more efficient. As the atomization power was increased,
this effect was minimized. The amount of lead signal
reached a maximum because the maximum amount of lead analyte
was atomized. Increasing the power did not increase the
number density of lead atoms in the plasma. Also, if
something in the blood was increasing the rate of
volatilization of the lead, a significant portion of the

113
b)
Figure 6-
Time (s)
9. Temporal profiles for the lead signal in
samples of varying blood composition at
atomization powers of a) 131 w and b) 250 W.

114
lead analyte could be lost during the ashing step. This
would explain why the signal for aqueous samples increased
beyond that of the blood samples for high atomization
powers.
Conclusion
The current system satisfies or approaches many of the
requirements of the CDC. The accuracy and precision
approach ± 10 ppb at 100 ppb with a lower detection limit
approaching 20 ppb. The required blood specimen volume is
only 2 /¿L, and the analysis time is under 4 minutes. The
system can easily be automated so that operator training
will be minimal and the instrument has low operating costs.
The two characteristics that the instrument does not fully
meet are portability and cost. The requirement of helium
tanks and the size of all the instrument components limits
the portability. The microwave electronics are very
inexpensive because of the commercial production of the
microwave oven; however, the PDA or CCD currently used as
the detector makes the system expensive. This type of
detector is not necessary for detecting only one element, so
less expensive detection systems could be used.

CHAPTER 7
MULTIELEMENT ANALYSIS IN BLOOD
Introduction
Although the CMP-AES did not meet all the requirements
for a screening method, it may still be useful as a clinical
method. The method of atomic emission allows the
measurement of many elements. Figure 7-1 shows an atomic
emission spectrum of whole blood. There are many atomic
emission lines available to analyze the various elements in
blood. The CMP-AES was used to analyze the levels of
sodium, potassium, magnesium, manganese, zinc and lithium in
blood. The level of sodium and potassium is very high in
blood, so it was necessary to determine which atomic
emission lines will give linear responses in the
concentration range of interest. The primary advantage of
this method is that no dilution or sample pretreatment of
whole blood is necessary for analysis, so it is not
practical for us to dilute the blood samples in order to be
able to use the strongest atomic emission lines. The
initial work for each element was accomplished using aqueous
standards.
115

Signal
800
Figure 7-1. Emission spectrum of whole blood
116

117
The method of standard additions was used because
currently there is no suitable blood standard for elements
other than lead. Statistically, the useful concentration
range of standards added to the sample should result in a
final concentration of sample between 1.5 to 3 times the
original concentration of analyte [7]. For standard
additions analysis it is sufficient to analyze two samples,
a sample without any standard added and a spiked sample. To
insure linearity for the elements studied, a minimum of
three samples were analyzed.
Trace Elements
Zinc
The first atomic emission line used for zinc was 636.2
nm. A limit of detection (LOD) of 140 ppb for aqueous
samples at an atomization power of 170 W was determined
using this wavelength. The analytical curve lost its
linearity above a concentration of 2 ppm. Lower atomization
powers of 130 W and 90 W were tried, but the analytical
curve still was not linear at higher concentrations. Zinc
was present in blood at concentrations greater than 2 ppm,
and so a weaker atomic emission line had to be found. The
line at 472.2 was used and was linear over the concentration
range of interest. A LOD of 70 ppb was determined for

118
aqueous standards (figure 7-2) at an atomization power of
150 W. Figure 7-3 shows the analytical signal for zinc in
blood. The LOD for zinc in blood was 2 ppm at an
atomization power of 70 W. The detection limit remained
approximately the same (1 ppm) for an atomization power of
165 W. The measured concentration of zinc in human blood
was 8.5 ± 1.4 ppm at an atomization power of 70 W (figure 7-
4) and 8.8 ± 3.2 ppm at an atomization power of 165 W.
Lithium
The atomic emission line at 670.8 nm was used for the
analysis of lithium in blood. The analytical curve for
aqueous standards is shown in figure 7-5. The data point
from the 500 ppb lithium standard was not used for the
linear fit because it is not in the linear region of the
analytical curve. A LOD of 10 ppb was determined for
lithium in aqueous standards at an atomization power of 70
W. When the blood standards were analyzed, a significant
background appeared surrounding the lithium peak (figure 7-
6a). A red glass filter was placed in front of the
spectrometer and this greatly reduced the background (figure
7-6b). The measured concentration of lithium in blood was
2.6 ± .2 ppb with a detection limit of 0.6 ppb (figure 7-7).
The measured concentration of lithium in blood
corresponds with reference values. However, the amount of

Signal
119
Concentration (ppm)
Figure 7-2. Analytical curve for aqueous zinc standards at
a wavelength of 472.2 nm and an atomization
power of 150 W.

Intensity
Figure 7-3. Spectrum of a 2 pL, 10 ppm, zinc blood sample at an atomization
power of 70 W.

Signal
121
Concentration (ppm)
Figure 7-4. Standard additions for zinc in blood at a
wavelength of 472.2 nm and an atomization power
of 70 W.

122
Concentration (ppb)
Figure 7-5. Analytical curve for aqueous lithium standards
at a wavelength of 670.8 nm and an atomization
power of 70 W.

Intensity Intensity
123
Wavelength
b)
Wavelength (nm)
Figure 7-6. Spectra of a 2¿íL, 5 ppb lithium blood sample
at an atomization power of 70 W before (a) and
after (b) addition of red glass filter.

124
40000 -
35000 -
/
30000 -
A
25000 -
/
Signal
-»• ro
cn o
o o
o o
o o
1 1 1 L
/
10000-
/
5000-
/
0-
—i—i—i—i—i—i—i—i—i—i
0 20 40 60 80
Concentration (ppb)
Figure 7-7.
Standard additions for lithium in blood at a
wavelength of 670.8 nm and an atomization power
of 70 W.

125
lithium in the blood of patients receiving lithium treatment
is usually several ppm. A weaker lithium line at 610.4 ran
was used to investigate the linearity of analysis in this
higher concentration range. Aqueous standards were first
analyzed using an atomization power of 115 W. Figure 7-8
shows that the linear dynamic includes the region of
interest with a detection limit of 10 ppb and a correlation
coefficient of 0.9999. Blood samples containing higher
lithium concentrations were also analyzed (figure 7-9). A
detection limit of 30 ppb with a correlation coefficient of
0.998 was obtained. The relative standard deviation was
better than 7% for all concentrations measured for both
blood and aqueous standards.
Magnesium
The 518.4 nm atomic emission line was used for the
analysis of magnesium (figure 7-10). The low power used for
atomization of the other elements was not sufficient for the
magnesium. An atomization power of 130 W was used. The
LOD's were 5 ppm for aqueous standards and 6 ppm for blood.
The measured level of Mg in the human blood sample was
28.7 ± .1 ppm (figure 7-11).

126
Concentration (ppm)
Figure 7-8. Analytical curve for aqueous lithium standards
at a wavelength of 610.4 nm and an atomization
power of 115 W.

127
Concentration (ppm)
Figure 7-9. Analytical curve for blood lithium standards at
a wavelength of 610.4 nm and an atomization
power of 115 W.

Intensity
Figure 7-10.
Spectrum of a 2 pL, 50 ppm, magnesium blood
sample at an atomization power of 130 W.
to
CD

129
Concentration (ppm)
Figure 7-11. Standard additions for magnesium in blood at a
wavelength of 518.4 nm and an atomization
power of 130 W.

130
Manganese
Manganese (Mn) has three closely spaced atomic emission
lines at 403.08, 403.31, and 403.45 nm. The spectrometer
was not able to fully resolve these lines, so the combined
area of all three peaks was used for analysis. An
interfering peak appeared very close to the Mn peak and was
accounted for by blank subtraction. The integration time
was reduced from two seconds to one second and this reduced
the amount of background without reducing the amount of Mn
signal. The analysis of manganese required an atomization
power of 230 W. The LOD's for Mn were 90 ppb for aqueous
standards (figure 7-12) and 30 ppb for blood standards
(figure 7-13). A concentration of 62 ± 8 ppb was measured
in the human blood sample.
Primary Elements
Sodium
The resonance lines of sodium at 589.59 and 589.0 were
investigated for use in the measurement of sodium blood
levels. The analytical curve for aqueous standards (figure
7-14) was linear up to a concentration of 1 ppm. The
correlation coefficient using the results for sodium
concentrations up to 1 ppm was 0.999 with a log-log slope of
1.01. The detection limit was 10 ppb for an atomization

131
Concentration (ppb)
Figure 7-12. Aqueous analytical curve for manganese at a
wavelength of 403 nm and an atomization power
of 230 W.

132
Concentration (ppb)
Figure 7-13. Standard additions for manganese in blood at a
wavelength of 403 nm and an atomization power
of 230 W.

Signal
133
Concentration (ppm)
Figure 7-14. Aqueous analytical curve for sodium at a
wavelength of 589 nm and an atomization power
of 70 W.

134
power of 70 W. The concentration of sodium in blood is well
above 1 ppm so other atomic lines were investigated. Sodium
lines at both 568.8 and 819.5 nm were tried, but
theanalytical curve for these lines was not linear at higher
concentrations. The atomic emission at 498.3 nm gave linear
results over the concentration range of interest so it was
used for blood analysis. The sodium peaks in blood are
shown in figure 7-15. Neutral density filters had to be
used because the emission intensity from the sodium was too
high for the detector. An LOD of 60 ppm was determined
using the 498.3 nm line and atomizing at 110 mA. The
concentration of sodium measured in the human blood sample
was 1240 ± 60 ppm.
PQt&SSiwn
The level of potassium (K) in blood was measured using
the atomic emission lines at 766.49 and 769.90. Neutral
density filters were used to reduce the intensity so that
the detector was able to measure the potassium emission.
LOD's of 30 ppb for an atomization power of 150 W and 140
ppb for an atomization power of 70 W were determined for
aqueous standards. The LOD for potassium in blood was 250
ppm for an atomization power of 70 W. The measured
concentration of potassium in the human blood sample was
1660 + 120 ppm (figure 7-17).

Intensity
Figure 7-15. Spectrum of a 2 p.L, 1900 ppm, sodium blood
sample at an atomization power of 110 W.
135

Signal
136
Concentration (ppm)
Figure 7-16. Standard additions for sodium in blood at a
wavelength of 498 nm and an atomization power
of 110 W.

Signal
137
Concentration (ppm)
Figure 7-17. Standard additions for potassium in blood at
wavelengths of 766.5 and 769.9 nm and an
atomization power of 70 W.

138
Comparison to Literature Values
The values obtained for the different elements using
the CCMP-AES were compared to literature values. The
comparison is shown in table 7-1. All the values determined
fall in the reference range except for sodium and lithium,
which are both lower than the reference range. The level of
lithium is not much lower than the reference range, and the
level of sodium is of the same order of magnitude as the
reference range. The source used [144] for the reference
range did not claim that the values were normal, it only
pooled values obtained by various researchers for elemental
analysis in blood. Therefore, the elemental levels below
the lowest concentration of the reference range does not
indicate a deficiency, nor does a value above the highest
concentration indicate an excess. Unless the determined
value is significantly outside the reference range, it could
still be within the range for good health. Reference ranges
can be very dependent on the population studied, the
techniques used for sample collection, and the analytical
method used [33, 145].

139
Table 7-1. Comparison of measured elemental concentrations
to literature values.
Element
Concentration
range in blood
(ppm) [144]
Measured
concentration
(ppm)
Sodium
1710 - 2050
1240 ± 60
Potassium
1450 - 1920
1660 ± 120
Magnesium
27.1 - 45.5
28.7 ± .1
Lead
0.088 - 0.40
0.090 ± .017
Zinc
4.8 - 9.3
8.5 ±1.4
Manganese
0.0016 - 0.075
0.062 ± .008
Lithium
0.003 - 0.038
0.0026 ± .0002

140
The CMP-AES was successfully able to measure the levels
of sodium, potassium, magnesium, lithium, zinc, and
manganese in blood. The precision for most concentrations
was better than 10% and the linearity was excellent over the
concentration range of interest. The detection limits for
all the elements except for manganese were below the range
of concentrations found in human blood.

CHAPTER 8
CONCLUSIONS AND FUTURE WORK
Conclusions
CMP-AES as a Lead in Blood Screening Method
The CMP-AES currently satisfies most of the Centers for
Disease Control's requirements for a screening method for
lead in blood. It is capable of detecting blood lead levels
accurately below the current level of concern. The limit of
detection for lead in blood by the CMP-AES is near that
obtained by ICP-AES [146]. The CMP-AES has the advantage
over other methods that it can analyze whole blood directly,
without any sample pretreatment or dilution. Limitations of
its use include the high initial cost for the
instrumentation, difficulties in transporting it (i.e. to
schools), and the requirement of a compressed gas source.
CMP-AES as a Multielement Clinical Technique
The CMP-AES is a technique with sensitivity to analyze
trace elements and the linear dynamic range to measure
primary elements. The instrumentation is inexpensive
compared to GFAAS and ICP-MS, but it is expensive compared
141

142
to the electrochemical methods. CMP-AES has the advantage
over electrochemical methods that reagents are not needed.
The CMP-AES has several disadvantages for blood analysis.
Interfering emission lines from the electrode material can
make the analysis of some elements difficult. When the
electrode wears down, it must be replaced and then it is
necessary to recalibrate the system because the electrodes
are not reproducible. Also, the electrodes are difficult to
make because the tungsten is somewhat brittle. Currently,
the only way to analyze blood samples is by the method of
standard additions. This adds to the analysis time and is a
potential source of contamination. If aqueous standards
could be used for calibration, the method would be
clinically useful.
Future Work
The method has proven to be capable of analyzing the
elements studied, but further research is necessary to
develop the method into something that could be commercially
made for clinical analysis. The method could also be used
in a number of other research projects.

143
Analysis of Other Health Related Elements
Other essential trace elements that could be studied
include iron, calcium, chromium, cobalt, copper, molybdenum,
and selenium [36].
Iron (Fe) deficiency is one of the most widespread
nutritional deficiencies world wide [36]. Researchers at
the National Center for Health Statistics (Hyattsville, Md.)
estimate that 700,000 infants and 7.8 million women are iron
deficient [56, 147] . It is estimated that over one third of
these cases have iron deficiency anemia. If occurring
during infancy and early childhood, iron deficiency anemia
(IDA) can impair psychomotor development [148] . IDA also
causes a lack of energy, low birth weight, prematurity,
impaired immune response, and abnormalities of the skin,
nails, and mucous membrane [148] . Any time a person loses a
significant amount of blood, he or she must make up for the
blood lost and will require iron. Vegetarianism can lead to
iron deficiency because meat and fish are better sources of
iron than vegetables and help in the absorption of iron from
other foods [53].
Iron metabolism is intimately tied up with the
metabolism of other trace elements. Its main role is in the
structure of red blood cells, which provide the oxygen
supply to the rest of the body's cells. Approximately two
thirds of the body's iron is tied up in hemoglobin in the

144
red blood cells. Iron is also found in transport proteins
such as transferrin and ferritin.
Abnormally high levels of iron can cause damage to
several organs including the liver, heart, pancreas, and
pituitary gland. High levels may also cause ischemic heart
disease and cancer [148] .
Calcium is important in the prevention of osteoporosis
and hypertension. Calcium is also very important for the
growth of children, and expectant mothers need to have a
sufficient supply for their unborn baby.
Chromium is essential for normal carbohydrate
metabolism [149-151]. Chromium is also a potentiator for
insulin action. A deficiency of chromium could lead to
insulin resistance [47].
Copper is involved in the immune and anti-oxidative
defense mechanisms and in tissue repair. Irregular levels
of copper have also been associated with several diseases
[47] .
Elements that exhibit toxicity at high levels include
aluminum and cadmium. Aluminum can be toxic if the levels
are too high. Aluminum can permeate food cooked in aluminum
cook ware and it is also found in table salt, antacids, and
deodorants [36]. An aluminum overload contributes to anemia
and can cause nervous system toxicity. Aluminum has also
been linked to Alzheimer's disease [47, 152]. Monitoring

145
the levels of aluminum in the serum and urine of patients
with renal disease is an efficient way to monitor their
pathological status [153].
Cadmium toxicity is a particular risk to smokers
because cigarettes yield cadmium in the smoker's lungs
[154]. Cadmium displaces zinc from important enzymes making
them inactive [36].
Using Aqueous Standards for Blood Analysis
The use of blood samples as standards is not very
practical. Although the existence of lead in bovine blood
standards from the CDC's BLLRS makes it convenient to use
these standards for lead, the availability is limited to
research and quality control purposes. Also, there is not
such a program for other elements in blood. The standard
additions method works for elemental analysis, but the
sample preparation is time consuming and the addition of
standards can be a source of contamination. Also, it is
difficult to do simultaneous multielement analysis using
standard additions.
The work done comparing aqueous and blood lead
standards is promising. At the determined atomization
power, good agreement was obtained for the two types of
standards indicating that the method could be used for blood
lead screening using aqueous standards. It is possible that

146
a similar relationship for atomization power could be found
for other elements.
Another possibility for standards is trying
synthetically prepared standards that approximate the matrix
of blood. However, there are no such standards currently
available.
Commercially Mads Filaments
The lack of reproducibility between filaments makes
finding a commercially made filament worth investigating.
Tungsten filaments of various shapes and sizes are used in
light bulbs. These filaments can be investigated to see if
they will work with the CMP-AES system. It may be necessary
to design a support made out of tungsten or titanium rod as
part of the electrode. The support electrode would be
immersed in the waveguide and the filament would be attached
to the top of the electrode. Figure 8-1 shows a possible
design for using a commercial filament. The filament is
made out of tungsten and has a rectangular shape with a
hollow center. The two ends of the filament could be bent
at a ninety degree angle and inserted into two holes in the
top of a titanium support electrode. The rectangular
portion of the tungsten filament would provide a platform
for the placement of the sample. The microwave energy would

147
Tungsten
filament
Tungsten
lightbulb
filament
Figure 8-1. Proposed method of using a commercial tungsten
lightbulb filament as the method of sample
introduction.

148
be coupled to the filament through the support. The plasma
would form either at the top of the filament or at the top
of the support electrode, engulfing the filament, providing
efficient atomization and excitation. If successful it
could be possible to use the filaments interchangeably. The
blood could then even be collected on the filament and dried
and ashed using a furnace, and then stored prior to
analysis. This would greatly increase the throughput of the
method.
Simultaneous Multielement Analysis
An echelle spectrometer coupled with a two dimensional
charge transfer device makes it possible to collect a
spectral range of 500 nm. This would allow simultaneous
multielement analysis using a CMP-AES. Pless et al. used
such a system to do multielement analysis in solid samples
[130]. For multielement analysis in blood samples, a
compromise would be needed for the conditions of each
element so that all elements could be measured
simultaneously. If such a compromise could be found without
a significant sacrifice of sensitivity, precision, and
accuracy, then a direct elemental analysis could be
performed on a single microliter blood sample. Simultaneous
multielement analysis of blood would be very useful for many

149
reasons. It would provide much information without
requiring a large amount of blood sample, which is
especially important in maternal and paediatric studies. If
a trace element profile could be easily obtained, the trace
element interactions in a wider range of diseases could be
determined Also, unsuspected elemental deficiencies or
overload could easily be detected during routine testing.
Simultaneous multielement analysis also reduces the
possibility of contamination from the handling of the sample
which is required in sequential elemental analysis [39].
Other Biological Fluids
Whole blood is one of the most complex matrices of
biological fluids. Both serum and plasma are constituents
of whole blood, so the CMP-AES system should perform as well
or better for these fluids. In some cases, the levels of
elements in serum or plasma is a better indicator of health
than the measurement of the levels in whole blood. Other
biological fluids could also be analyzed.
Plasma
Blood plasma is the portion of blood remaining after
the red and white blood cells and the platelets are removed.
Blood plasma serves as the transport medium that delivers
nutrients to the cells. It also removes the metabolites of

150
the cells and is involved in the regulation of physiological
processes [4].
Serum
Serum is different from plasma in that it contains no
fibrinogen. The absence of fibrinogen gives serum the
advantage over plasma that no anticoagulants are needed,
reducing the chance of contaminating the sample. However,
the serum needs to be obtained by centrifugation, and not as
much can be collected for a given amount of blood [4]. The
measurement of iron in serum is more useful than the
measurement of iron in whole blood. The levels of iron in
whole blood does not provide adequate information on iron
status because the amount of iron it its various forms may
vary independently. The level of iron in serum, however,
correlates well with serum transferrin which is a better
indicator of iron status [56].
Urine and spinal fluid
The analysis of urine for primary and trace elements is
important to determine how the body loses important
nutrients. It can also be used as an indication of a recent
occupational exposure, particularly for elements such as
arsenic, chromium, lead, mercury, and nickel [37]. A
decrease in the urinary excretion of an element can indicate
a deficiency of that element [47] . The levels of elements
in spinal fluid can be indicative of various diseases [37].

151
Miniaturize System
The electronics of the CMP-AES are capable of being
reduced drastically in size. The microwave plasma portion
of the setup should be able to be reduced to the size of a
small microwave oven. Currently, microwave ovens consist of
very similar parts: programmable power supply
(high/medium/low), magnetron, and waveguide. To fully
miniaturize the system, a method of detection consisting of
smaller components would also have to be found.
Acousto-optic tunable filter
An acousto-optic tunable filter (AOTF) is a compact,
tunable, narrow-band light filter [155]. An AOTF is
constructed by bonding a piezoelectric transducer to a
birefringent crystal, usually quartz or paratellurite
(Te02) . Acoustic waves are propagated through the crystal
by applying a radio frequency (rf) signal to the transducer.
The acoustic waves produce grating in the crystal that can
diffract select wavelengths of the incident beam. The
position of the bandpass can be controlled electronically
over a wide spectral range by changing the frequency of the
rf signal [155]. AOTF's have been used in fluorescence,
emission, and spectroscopic imaging experiments [155-164]
and to tune and stabilize a laser beam [165-166].
Horlick and Fulton have investigated using an AOTF for
atomic spectrometry [156]. An inductively coupled plasma, a

152
glow discharge, and a hollow cathode lamp were used as
atomic emission sources. By using two AOTF crystals, the
wavelength range of 350-600 nm was covered. In one second,
the entire spectrum was scanned with a resolution of 0.22 nm
at 361 nm. Using an AOTF with the CMP-AES instead of the
currently used spectrometer could help make it more suitable
as a screening or clinical technique. The array type
detectors would be unnecessary and a photomultiplier tube
(PMT) or a photodiode could be used for the measurement of
the analytical signal. This would greatly reduce the size
and expense of the CCMP-AES.
Miniature detector
Miniature fiber optic spectrometers are commercially
available for under $3000 (S2000 Fiber Optic Spectrometer,
Ocean Optics, Inc., Dunedin, FL). One spectrometer is so
small that it can fit on a computer card inside a notebook
computer. Currently, the sensitivity and resolution may not
be sufficient to analyze elements in blood in the low ppb
range, but it might be able to measure the emission signal
at the ppm level. If this system could be used with a
reduced sized microwave plasma setup, the system would be
portable to some extent. It would also be quite inexpensive
for an atomic emission instrument.

153
Atomization Method for Other Techniques
The filament supported microwave plasma is a very
efficient atomization source. The analytical volume is very
compact and could be used as an atomization source for other
analytical method. Laser excited atomic fluorescence
spectrometry (LEAFS) using a both a flame [167] and a
graphite furnace [168] has been used as a method to
determine the levels of lead in blood. A detection limit of
4 ppb was determined using a flame and 10 ppt using a
graphite furnace. As a source for atomic fluorescence, the
plasma would not have to excite the sample, only atomize and
excite it. This would allow a lower power to be used so
that the analyte would have a longer residence time in the
plasma and would be more completely dissociated [17] . The
excellent performance of the CMP and the advantages it has
over a flame and a graphite furnace might be able to lower
the detection limits and improve the accuracy for LEAFS.

LIST OF REFERENCES
1. A.H. Ali, K.C. Ng, and J.D. Winefordner, Journal of
Analytical Atomic Spectrometry 6, 211 (1991).
2. W. R. L. Masamba, B. W. Smith, and J. D. Winefordner
Applied Spectroscopy 46, 1741 (1992).
3. B.M. Spencer and J.D. Winefordner, Canadian Journal of
Applied Spectroscopy 39, 43 (1994).
4. J. Versieck and R. Cornells, Trace Elements in Human
Plasma or Serum, CRC Press, Boca Raton, FL (1989).
5. J. D. Ingle and S. R. Crouch, Spectrochemical Analysis.
Prentice-Hall, Inc., New Jersey (1988).
6. M. Dax, RSD Magazine 39, 28 (1997).
7. D.C. Harris, Quantitative Chemical Analysis, second ed.
W.H. Freeman and Company, USA (1987).
8. T.S. Laverghetta, Practical Microwaves. Englewood
Cliffs, New Jersey, Prentice Hall (1996).
9. A.W Scott, Understanding Microwaves. Wiley, New York
(1993) .
10. J.J. Carr, Elements of Microwave Electronics
Technology. Harcourt Brace Jovanovich, Publishers, San
Diego (1989) .
11. Y. Asami and T. Hori, Nature 144, 981 (1939).
12. J.D. Cobine and D.A. Wilbur, Journal of Applied Physics
22, 835 (1951).
13. H.P. Broida and M.W. Chapman, Analytical Chemistry 30,
2049 (1958).
154

14.
155
W. Kessler and F. Gebhart, Glastech. Ber. 40, 194
(1967) .
15. R. Mavrodineanu and R.C. Hughes, Spectrochimica Acta
23, 13 (1967).
16. K. Fallgatter, V. Svoboda, and J.D. Winefordner,
Applied Spectroscopy 25, 347 (1971).
17. Q. Jin, Y. Duan, and J.A. Olivares, Spectrochimica Acta
Part B 52, 131 (1997).
18. A.T. Zander and G.M. Hieftje, Applied Spectroscopy 35,
357 (1981).
19. J. Marshall, A. Fisher, S. Chenery, and S.T. Sparkes,
Journal of Analytical Atomic Spectrometry 11, 213
(1996) .
20. D. Beauchemin, J.C.Y. LeBlanc, G.R. Peters, and J.M.
Craig, Analytical Chemistry 64, 442 (1992).
21. J.D. Winefordner, E.P. Wagner, and B.W. Smith, Journal
of Analytical Atomic Spectrometry 11, 689 (1996).
22. A. Croslyn, B.W. Smith, and J.D. Winefordner, Critical
Reviews in Analytical Chemistry, in press.
23. A.H. Ali, J.D. Winefordner, Analytics Chimica Acta 264,
327 (1992).
24. B.M. Spencer, B.W. Smith, and J.D. Winefordner, Applied
Spectroscopy 48, 289 (1994).
25. B. M. Patel, E. Heithmar, and J. D. Winefordner,
Analytical Chemistry 59, 2374 (1987).
26. Q. Jin, C. Zhu, M.W. Borer, and G.M. Hieftje,
Spectrochimica Acta 46B, 417 (1991).
27. Q. Jin, H. Zhang, Y. Wang, X. Yuan, and W. Yan.
Journal of Analytical Atomic Spectrometry 9, 851
(1994) .
28. Y. Duan, Y. Li, and Q. Jin, Journal of Analytical
Atomic Spectrometry 8, 1091 (1993).

156
29. Y. Duan, Y. Li, M. Hou, Z. Du, and Q. Jin, Applied
Spectroscopy 47, 1871 (1993).
30. Y. Duan, X. Du, and Q. Jin, Journal of Analytical Atomic
Spectrometry 9, 629 (1994).
31. Y. Duan, X. Du, Y. Li, and Q. Jin, Applied Spectroscopy
49, 1079 (1995) .
32. Y. Duan, Y. Li, X. Tian, H. Zhang, and Q. Jin,
Analytics Chimica Acta 295, 315 (1994).
33. K.L. Nuttall, W.H. Gordon, and K.O. Ash, Annals of
Clinical and laboratory Science 25, 264 (1995).
34. J.W. Olesik, Analytical Chemistry 68, 469A (1996).
35. M.E. Reusser and D.A. McCarron, Nutrition Reviews 52,
367 (1994).
36. A. Stanway, Trace Elements: Miracle Micro Nutrients.
Thorsons Publishing Group, Rochester, VT (1987).
37. World Health Organization, Trace Elements in Human
Nutrition and Health. Macmillan, Belgium (1996).
38. F. Licastro, M. Chiricolo, M.C. Morini, I. Capri, L.J.
Davis, R. Contec, R. Mancini, C. Melotti, R. Párente,
R. Serra, and E. Carpene, Gerontology 41, 235 (1995).
39. A.S. Prasad, ed. Essential and Toxic Trace Elements in
Human Health and Disease. Alan R. Liss, Inc., New York
(1988) .
40. W.L. Roper, V.H. Houk, H. Falk, S. Binder, Preventing
Lead Poisoning in Young Children: a Statement by the
Centers for Disease Control and Prevention, U.S.
Department of Health and Human Services, Public Health
Service, Centers for Disease Control and Prevention,
Atlanta, GA (1991).
41. R.L. Boeckx, Analytical Chemistry 58, 274A (1986).
42. "Blood Lead Levels Keep Dropping; New guidelines
Proposed for Those Most Vulnerable", HHS News, 2/21/97.

43.
157
P.J. Landrigan and A.C. Todd, Western Journal of
Medicine 161, 153 (1994).
44. J.E. Foulke, FDA Consumer 8, 1 (1993).
45. D. Noble, Analytical Chemistry 65, 265A (1993).
46. J.M. Christenson, Science of the Total Environment 166,
89 (1995) .
47. C.A. Burtis and E.R. Ashwood, eds., Tietz Fundamentals
of Clinical Chemistry, W.B. Saunders Company,
Philadelphia (1996).
48. J.H. Freeland-Graves and J.R. Turnland, Journal of
Nutrition 126, 2345S (1996) .
49. P.J. Goodnick and R.R. Fieve, American Journal of
Psychiatry 142, 761 (1985).
50. L. Shen, S. Xiao-quan, and N. Zhe-ming, Journal of
Analytical Atomic Spectrometry 3, 989 (1988) .
51. G.D. Christian, Journal of Pharmaceutical and
Biomedical Analysis 14, 899 (1996) .
52. J.B. Henry, ed., Clinical Diagnosis and Management by
Laboratory Methods, 19th ed., W.B. Saunders Company,
Philadelphia (1996).
53. M.M. Pluhator, A.B. Thomson, and R.N. Fedorak, Can. J.
Gastroenterology 10, 97 (1996).
54. H.H. Sandstead and J.C. Smith, Journal of Nutrition
126, 2410S (1996) .
55. B.M. Altura and B.T. Altura, Scand. J. Clin. Lab.
Invest. 56, 211 (1996) .
56. J. Kahn, Clinical Laboratory News 23, 1 (1997).
57. P.J. Parsons, A.A. Reilly, and A. Hussain, Clinical
Chemistry 37, 216 (1991).
58. A.A. Lamóla and T. Yamane, Science 186, 936 (1974).

158
59. N.V. Stanton, E.W. Gunter, P.J. Parsons, and P.H.
Field, Clinical Chemistry 35, 2104 (1989).
60. B.J. Feldman, A. D'Alessandro, J.D. Osterloh, and B.H.
Hata, Clinical Chemistry 41, 557 (1995) .
61. T.Z. Liu, D. Lai, and J.D. Osterloh, Analytical
Chemistry 69, 3539 (1997).
62. B.J. Feldman, J.D. Osterloh, B.H. Hata, and A.
D'Alessandro, Analytical Chemistry 66, 1983 (1994).
63. S.M. Roda, R.D. Greenland, R.L. Bornschein, and P.B.
Hammond, Clinical Chemistry 34, 563 (1988).
64. J.D. Osterloh, D.S. Sharp, and B. Hata, Journal of
Analytical Toxicology 14, 8 (1990).
65. D. Jagner and Y. Wang, Electroanalysis 7, 614 (1995) .
66. P. Ostapczuk, Clinical Chemistry 38, 1995 (1992).
67. D. Jagner, M. Josefson, S. Westerlund, and K. Aren,
Analytical Chemistry 53, 1406 (1981).
68. P.J. Brockman and W.F. Drislane, 1996 Pittsburgh
Conference, Abstract 1038, Chicago, IL (1996).
69. C.L. Sanford, S.E. Thomas, and B.T. Jones, Applied
Spectroscopy 50, 174 (1996).
70. D.C. Paschal, K.L. Caldwell, and B.G Ting, Journal of
Analytical Atomic Spectrometry 10, 367 (1995).
71. H.Y. Yee, J.D. Nelson, and B. Jackson, Journal of
Analytical Toxicology 18, 415 (1994) .
72. D.I. Bannon, C. Murashchik, C.R. Zapf, M.R. Farfel, and
J.J. Chisolm, Jr., Clinical Chemistry 40, 1730 (1994).
73. J. M. Christensen, O.M. Poulsen, and T. Anglov, Journal
of Analytical Atomic Spectrometry 7, 329 (1992).
74. A. Deval and J. Sneddon, Microchemical Journal 52, 96
(1995) .

159
75. P.J. Parsons and W. Slavin, Spectrochimica Acta 48B,
925 (1993).
76. B.E. Jacobson, G. Lockitch, and G. Quigley, Clinical
Chemistry 37, 515 (1991).
77. I. Baranowska, Occupational and Environmental Medicine
52, 229-232 (1995).
78. P.C. D'Haese, L.V. Lamberts, L. Liang, F.L. Van de
Vyer, and M.E. De Broe, Clinical Chemistry 37, 1583
(1991).
79. D.T. Miller, D.C. Paschal, E.W. Gunter, P.E. Stroud,
and Joseph D'Angelo, Analyst 112, 1701 (1987) .
80. P.J. Parsons, Environmental Research 57, 149 (1992).
81. CDC Maternal and Child Health Resources Development
Proficiency Testing Program - Blood Lead - July 1991.
82. K.S. Subramanian, The Science of the Total Environment
89, 237 (1989) .
83. J.F. Rosen and E.A. Trinidad, J. Lab. Clin. Med. 80,
567 (1972) .
84. S.S. Que Hee, T.J. McDonald, and R.L. Bornsheim,
Microchemical Journal 32, (1985).
85. K.G. Brodie and M.W. Routh, Clinical Biochemistry 17,
19 (1984) .
86. W.N. Anderson, P.M.G. Broughton, J.W. Dawson, and G.W.
Fisher, Cin. Chim. Acta. 50, 129 (1974).
87. I.L. Shuttler and H.T. Delves, Analyst 111, 651 (1986).
88. D.K. Eaton and J.A. Holcombe, Analytical Chemistry 55,
946 (1983).
89. V.P. Garnys and L.E. Smythe, Talanta 22, 881 (1975).
90. K.S. Subramanian, Atomic Spectroscopy 8, 7 (1987).
91. K.S. Subramanian, Prog. Anal. Spectrosc. 9, 237 (1986).

160
92. K.S. Subramanian, Atomic Spectroscopy 9, 169 (1988).
93. K. Verebey, Y.M. Eng, B. Davidow, and A. Ramon, Journal
of Analytical Toxicology 15, 237 (1991).
94. J. Alvarado, P. Cavalli, N. Omenetto, G. Rossi, J.M.
Ottaway, and D. Littlejohn, Analytical Letters 22, 2975
(1989) .
95. R.J. Bowins and R.H. McNutt, Journal of Analytical
Atomic Spectrometry 9, 1233 (1994) .
96. A. Schütz, I.A. Bergdahl, A. Ekholm, and S. Skerfving,
Occupational and Environmental Medicine 53, 736 (1996).
97. R.S. Houk, Analytical Chemistry 58, 97A (1986).
98. L. Xilei, D. Van Rentergheim, R. Cornelis, and L. Mees,
Analytica Chimica Acta 211, 231 (1988) .
99. A. Taylor, S. Branch, H.M. Crews, D.J. Halls, L.M.W.
Owen, and M. White, Journal of Analytical Atomic
Spectrometry 12, 119R (1997).
100. D.J. Anderson, B. Guo, Y. Xu, L.M. Ng, L.J. Kricka,
K.J. Skogerboe, D.S. Hage, L. Schoeff, J. Wang, L.J.
Sokoll, D.W. Chan, K.M. Ward, and K.A. Davis,
Analytical Chemistry 69, 165R (1997).
101. W.J. Korzun and W.G. Miller, "Sodium and Potassium" in
Methods in Clinical Chemistry; A.J. Pesce and L.A.
Kaplan Eds.; Mosby, St. Louis, chap. 13 (1987).
102. S. Shang and W. Hong, Fresenius Journal of Analytical
Chemistry 357, 997 (1997).
103. R. Cornelis, B. Heinzow, R.F.M. Herber, J.M.
Christensen, O.M. Poulsen, E. Sabbioni, D.M. Templeton,
Y. Thomassen, M. Vahter, and 0. Vesterberg, Journal of
Trace Elements in Medicine and Biology 10, 103 (1996).
104. F.N. Johnson, ed., Depression and Mania, Modern
Lithium Therapy, IRL Press, Oxford, UK (1987) .
105. G.N. Doku and P.Y. Gadzekpo, Talanta 43, 735 (1996).

161
106. Z. Mianzhi and R. M. Barnes, Applied Spectroscopy 39,
793 (1985).
107. H. Uchida, Y. Nojiri, H. Haraguchi, and K. Fuwa,
Analytica Chimica Acta 123, 57 (1981).
108. P. Leflon, R. Plaquet, F. Rose, G. Hennon, and N.
Ledeme, Analytica Chimica Acta 327, 301 (1996).
109. H. Vanhoe, R. Dams, and J. Versieck, Journal of
Analytical Atomic Spectrometry 9, 23 (1994).
110. M.A. Vaughan, A.D. Baines, and D.M. Templeton,
Clinical Chemistry 37, 210 (1991).
111. H. Vanhoe, J. Versieck, L. Moens, and R. Dams, Trace
Elements and Electrolytes 12, 81 (1995).
112. H. Vanhoe, C. Vandecasteele, J. Versieck, and R. Dams,
Analytica Chimica Acta 244, 259 (1991).
113. E. Barany and I.A. Bergdahl, Characterization of a
Simple ICP-MS Method for Multielement Determination in
Whole Blood and Serum, Poster presented at the 1997
European Winter Conference on Plasma Spectrochemistry,
January 14, 1997, Ghent Belgium.
114. A. Viksna and E. Selin, J. Trace and Microprobe
Techniques 14, 763 (1996).
115. R.E. Ayala, E.M. Alvarez, and P. Wobrauschek,
Spectrochimica Acta 46B, 1429 (1991).
116. N.T. Hong, N.V. Hung, and J. Boman, Journal of Trace
and Microprobe Techniques 14, 153 (1996).
117. N.J. Birch, A.M. Johnson, and C. Padgham, J. Trace and
Microprobe Techniques 14, 439 (1996).
118. E. Bakker, R.K. Meruva, E. Pretsch, and M.E.
Meyerhoff, Analytical Chemistry 66, 3021 (1994).
119. O. Dinten, U.E. Spichiger, N. Chaniotakis, P. Gehrig,
B. Rusterhoz, W.E. Morf, and W. Simon, Analytical
Chemistry 63, 596 (1991).

120.R.L. Bertholf, M.G. Savory, K.H. Winborne, J.C.
Hundley, G.M. Plummer, and J. Savory, Clinical
Chemistry 34, 1500 (1988).
162
121. L. Ramaley, P.J. Wedge, and S.M. Crain, Journal of
Chemical Education 71, 164 (1994).
122. W.R.L. Masamba, A. H. Ali, and J. D. Winefordner
Spectrochimica Acta 47B, 481 (1992).
123. P.W.J.M. Boumans, Ed., Inductively Coupled Plasma
Emission Spectroscopy, Vol. 2. John Wiley and Sons,
New York, (1987) .
124. W.R.L. Masamba and J.D. Winefordner, Spectrochimica
Acta 48B, 521 (1993) .
125. E.J. Lerner, Laser Focus World 32/5, 93 (1996).
126. J.M. Harnly and R.E. Fields, Applied Spectroscopy 51,
334A (1997).
127. E.J. Lerner, Laser Focus World 32/8, 103 (1996).
128. AT200 CCD Camera System Hardware Reference Manual,
Photometries, Ltd., Tucson, AZ (1992).
129. K.S. Subramanian, Biological Trace Element Research
49, 187 (1995).
130. A.M. Pless, A. Croslyn, M.J. Gordon, B.W. Smith, and
J.D. Winefordner, Talanta 44, 39(1997).
131. M.W. Wensing, B.W. Smith, and J.D. Winefordner,
Analytical Chemistry 66, 531 (1994) .
132. M.W. Wensing, D.Y. Liu, B.W. Smith, and J.D.
Winefordner, Analytics Chimica Acta, 1994, 299, 1.
133. S. Hanaamura, B.W. Smith, and J.D. Winefordner,
Canadian Journal of Spectroscopy 29, 13 (1984) .
134. S. Hanaamura, W.J. Wang, and J.D. Winefordner,
Canadian Journal of Spectroscopy 30, 46 (1985).

163
135. B.M. Patel, J.P. Deavor, and J.D. Winefordner, Talanta
35, 641 (1988).
136. H. Uchida, W.R. Masamba, T. Uchida, B.W. Smith, and
J.D. Winefordner, Applied Spectroscopy 43, 425 (1989).
137. J.D. Hwang, W. Masamba, B.W. Smith, and J.D.
Winefordner, Canadian Journal of Spectroscopy 33, 156
(1988) .
138. A.H. Ali, K.C. Ng, and J.D. Winefordner,
Spectrochimica Acta 46B, 1207 (1991).
139. A.M. Pless, B.W. Smith, M.A. Bolshov, and J.D.
Winefordner, Spectrochimica Acta 51B, 55 (1996).
140. S. Hanaamura, B.W. Smith, and J.D. Winefordner,
Analytical Chemistry 55, 2026 (1983) .
141. I. Atsuya and K. Akatsuka, Spectrochimica Acta 36B,
747 (1981).
142. H. Uchida, P.A. Johnson, and J.D. Winefordner, Journal
of Analytical Atomic Spectrometry 5, 81 (1990).
143. K.L. Riter, O.I. Matveev, B.W. Smith, and J.D.
Winefordner, Analytics Chimica Acta 333, 187 (1996).
144. G.V. Iyengar, W.E. Kollmar, and H.J. Bowen, The
Elemental Composition of Human Tissues and Body Fluids,
Verlag Chemie, Weiheim, New York (1978).
145. O. Vesterberg, G. Nordberg, and D. Bruñe, Fresenius
Journal of Analytical Chemistry 332, 556 (1988).
146. Correspondence with Jobin Yvon, Edison, New Jersey.
147. A.C. Looker, P.R. Dallman, M.D. Carroll, E.W. Gunter,
and C.L. Johnson, Journal of the American Medical
Association 277, 973 (1997).
148. S.R. Lynch and R.D. Baynes, Journal of Nutrition 126,
2405S (1996) .
149. V. Senft and J. Kohout, Cas Lek Cesk 135, 150 (1996).

164
150. B.E. Wilson and A. Gondy, Diabetes Res. Clin. Pract.
28, 179 (1995).
151. P.M. Clarkson, Sports Medicine 23, 341 (1997).
152. P. Copestake, Food Chem. Toxicol. 31, 679 (1993).
153. N. Violante, F. Petrucci, P.D. Feminine, and S. Caroli,
Microchemical Journal 46, 199 (1992).
154. A.E. Omu, H. Dashti, A.T. Mohamed, and A.B.
Mattappallil, Nutrition US, 502 (1995) .
155. C.D. Tran, Analytical Chemistry 64, 971A (1992).
156. G. Fulton and G. Horlick, Applied Spectroscopy 50, 885
(1992).
157. C.D. Tran and R.J. Furlan, Analytical Chemistry 65,
1675 (1993).
158. R. Dwelle and P. Katzka, Review of Scientific
Instruments 58, 1996 (1987).
159. J. Hallikainen, J. Parkkinen, and T. Jaaskelainen,
Review of Scientific Instruments 59, 81 (1988) .
160. P.J. Treado, I.W. Levin, and E.N. Lewis, Applied
Spectroscopy 46, 553 (1992).
161. W.S. Shipp, J. Biggins, and C.W. Wade, Review of
Scientific Instruments 47, 565 (1976) .
162. X. Wang, D.E. Vaughan, V. Pelekhaty, and J. Crisp,
Review of Scientific Instruments 65, 3653 (1994) .
163. C.D. Tran and M. Bartelt, Review of Scientific
Instruments 63, 2932 (1992) .
164. T.M. Spudich, B.A. Pelz, and J.W. Carnahan, Applied
Spectroscopy 51, 765 (1997).
165. C.D. Tran and R.J. Furlan, Applied Spectroscopy 46,
1092 (1992).
166. C.D. Tran and R.J. Furlan, Review of Scientific
Instruments 65, 309 (1994).

165
167. N. Omenetto, H.G.C Human, P. Cavalli, and G. Rossi,
Analyst 109, 1067 (1984).
168. E.P. Wagner, B.W. Smith, and J.D. Winefordner,
Analytical Chemistry 68, 3199 (1996).

BIOGRAPHICAL SKETCH
Arthur David Besteman was born in Grand Rapids,
Michigan, on January 12, 1971. The son of Rev. Arthur and
Audrey (Honderd) Besteman, Arthur has two older sisters,
Debra and Diane. From the age of one to fifteen, Arthur
grew up in Zeeland, Michigan. He moved to Wyoming,
Michigan, where he attended Calvin Christian High School and
graduated in June of 1989. He then enrolled at Calvin
College and received his Bachelor of Science degree in May
of 1993 majoring in chemistry. While at Calvin College,
Arthur worked with Drs. Mark and Karen Muyskens, two
physical chemists, studying the multiphoton ionization and
fragmentation of methyl aniline. Arthur entered the
graduate program at the University of Florida in August of
1993 and became a member of Dr. James Winefordner's research
group, pursuing his Ph.D. in analytical chemistry.
166

I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
parnés D. Win/fordner, Chair
Graduate Research Professor
of Chemistry
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
Robert T.'Kenned
Associate Professor of
Chemistry
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality,
a dissertation for the degree of Doctor of Philosophy.
Luis'-M.
/u
£
LuislM. Muga
Professor of Chemistry
as
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
Benjamin A. 'Horenstein
Assistant Professor of
Chemistry
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
Pául E. Ehrlich
Professor of Mathematics

This dissertation was submitted to the Graduate Faculty
of the Department of Chemistry in the College of Liberal
Arts and Sciences and to the Graduate School and was
accepted as partial fulfillment of the requirements for the
degree of Doctor of Philosophy.
December, 1997
Dean, Graduate School

LD
1780
199 7
. 6^ /
UNIVERSITY OF FLORIDA
3 1262 08556 5975