THE DEVELOPMENT AND APPLICATION OF PRECONCENTRATION/ PREELUTION ION ...

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THE DEVELOPMENT AND APPLICATION OF PRECONCENTRATION/
PREELUTION ION CHROMATOGRAPHY METHODS FOR
THE DETECTION OF TRACE PERCHLORATE
IN DIFFICULT MATRICES
by
JACLYN ELAINE CAÑAS, B.S.
A DISSERTATION
IN
ENVIRONMENTAL TOXICOLOGY
Submitted to the Graduate Faculty
of Texas Tech University in
Partial Fulfillment of
the Requirements for
the Degree of
DOCTOR OF PHILOSOPHY
Approved
Todd Anderson
Chairperson of the Committee
Mike Hooper
Philip Smith
Kang Tian
Accepted
John Borrelli
Dean of the Graduate School
AUGUST, 2005

TABLE OF CONTENTS
FOREWORD........................................................................................................ii
ACKNOWLEDGMENTS......................................................................................iv
ABSTRACT..........................................................................................................x
LIST OF TABLES................................................................................................xii
LIST OF FIGURES.............................................................................................xiv
CHAPTER
I. INTRODUCTION.......................................................................................1
Perchlorate in the environment.........................................................1
Types of samples analyzed for perchlorate.......................................3
Non-ion chromatography methods for perchlorate
determination....................................................................................6
Early techniques..........................................................................8
Recent techniques.......................................................................9
Ion chromatography methods for perchlorate
determination..................................................................................21
Water samples..........................................................................21
Biological samples....................................................................24
Preconcentration in ion chromatography.........................................25
Preconcentration/preelution (PC/PE) ion chromatography
method............................................................................................27
Instrumentation........................................................................27
Preconcentration system operation..........................................28
Research objectives and hypotheses..............................................29
Research objectives.................................................................29
Research hypotheses and questions.......................................29
References.....................................................................................31
II. ION CHROMATOGRAPHY................................................................38
Instrument validation according to EPA Method 314.0....................38
Initial demonstration of accuracy and precision........................39
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Method detection limit..............................................................40
Matrix conductivity threshold....................................................40
Conclusion...............................................................................42
Preconcentration/preelution ion chromatography............................43
Optimization of operating conditions........................................43
References......................................................................................48
III. DEVELOPMENT AND APPLICATION OF A MODIFIED
ION CHROMATOGRAPHY METHOD FOR
PERCHLORATE DETERMINATION IN BIOLOGICAL
SAMPLES...........................................................................................49
Abstract.........................................................................................49
Introduction...................................................................................50
Materials and Methods..................................................................54
Reagents and standards..........................................................54
Sample preparation.................................................................54
Sample analysis.......................................................................57
Results and Discussion.................................................................59
GI tract.....................................................................................59
Quail eggs................................................................................61
Operating conditions................................................................63
Comparison to EPA Method 314.0..........................................74
Application of the methods......................................................78
Conclusions..................................................................................81
References....................................................................................82
IV. DEVELOPMENT AND APPLICATION OF A MODIFIED
ION CHROMATOGRAPHY METHOD FOR PERCHLORATE
DETERMINATION IN SAMPLES APPLICABLE TO HUMAN
HEALTH.............................................................................................85
Abstract.........................................................................................85
Introduction...................................................................................86
Materials and Methods..................................................................90
Reagents and standards..........................................................90
Sample preparation.................................................................91
Sample analysis.......................................................................94
Results and Discussion.................................................................95
Lettuce and urine.....................................................................95
Milk........................................................................................106
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Citrus.....................................................................................106
Comparison to EPA Method 314.0........................................110
Application of the methods.....................................................112
Conclusions................................................................................114
References..................................................................................116
V. DEVELOPMENT OF AN EXTRACTION METHOD
FOR PERCHLORATE IN SOILS........................................................119
Abstract.......................................................................................119
Introduction.................................................................................120
Materials and Methods................................................................123
Reagents and standards........................................................123
Soil collections.......................................................................123
Initial determination of perchlorate in EPA soils.....................124
Comparison of extraction and analysis techniques................124
Evaluation of soil extraction procedure parameters...............125
Effect of high ionic content on extraction efficiency...............127
Evaluation of matrix interferences..........................................127
Soil method detection limit and verification............................128
Results........................................................................................128
Initial determination of perchlorate in EPA soils.....................128
Comparison of extraction and analysis techniques................129
Evaluation of soil extraction procedure parameters...............134
Effect of high ionic content on extraction efficiency...............137
Evaluation of matrix interferences..........................................139
Soil method detection limit and verification............................144
Discussion...................................................................................145
References..................................................................................152
VI. CONCLUSION....................................................................................155
APPENDIX...............................................................................................158