Trace Analysis. Volume 4

310 Pages·1985·4.013 MB·English

by  James F. Lawrence (Eds.)

Contributors to This Volume
TERRY F. BIDLEMAN
LES EBDON
JOHN R. GARBARINO
R. E. JERVIS
BEVERLEY ANN KING
J. J. LABRECQUE
S. LANDSBERGER
S. MONARO
HOWARD E. TAYLOR
R. E. VAN GRIEKEN
TRACE ANALYSIS
Volume 4
Edited by
James F. Lawrence
Food Research Division
Health Protection Branch
Health and Welfare Canada
Ottawa, Ontario, Canada
1985
ACADEMIC PRESS, INC.
(Harcourt Brace Jovanovich, Publishers)
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COPYRIGHT © 1985, BY ACADEMIC PRESS, INC.
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United Kingdom Edition published by
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ISBN 0-12 682104-6
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PRINTED IN THE UNITED STATES OF AMERICA
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CONTRIBUTORS
Numbers in parentheses indicate the pages on which the authors' contributions begin.
Terry F. Bidleman (51), Department of Chemistry, Marine Science Pro-
gram, and Belle W. Baruch Institute for Marine Biology and Coastal
Research, University of South Carolina, Columbia, South Carolina
29208
Les Ebdon (1), Department of Environmental Sciences, Plymouth Poly-
technic, Plymouth PL4 8AA, England
John R. Garbarino (185), U.S. Geological Survey, Denver Federal Cen-
ter, Lake wood, Colorado 80225
R. E. Jervis (237), Department of Chemical Engineering, University of
Toronto, Toronto M5S 1A4, Ontario, Canada
Beverley Ann King (1), Department of Chemistry, Sheffield City Poly-
technic, Sheffield SI 1WB, England
J. J. LaBrecque (101), Instituto Venezolano de Investigaciones Cientifi-
cas, Caracas, Venezuela
S. Landsberger (237), Nuclear Reactor, McMaster University, Hamilton
L8S 4K1, Ontario, Canada
S. Monaro (237), Laboratoire de Physique Nucleaire, Universite de Mon-
treal, Montreal H3C 3J7, Quebec, Canada
Howard E. Taylor (185), U.S. Geological Survey, Denver Federal Center,
Lakewood, Colorado 80225
R. E. Van Grieken (101), Department of Chemistry, University of Ant-
werp (U.I.A), B-2610 Antwerp-Wilrijk, Belgium
vii
PREFACE
This fourth volume of Trace Analysis continues along the lines of the
previous volumes in presenting state-of-the-art reviews of selected topics
in the area of trace analysis. Volumes 1 and 2 dealt with various applica-
tions of high-performance liquid chromatography for the determination of
trace substances. Volume 3 and the present volume have been directed
toward topics in both organic and inorganic trace analysis of biological
materials and environmental samples.
The first article in volume 4 presents recent developments and applica-
tions of ion-selective polymeric membrane electrodes for biological tis-
sues and fluids. Included are applications to important ions, gas-sensing
probes, enzyme electrodes and biosensors, drug detection, immunoelec-
trodes, and the measurement of membrane potentials of biological sys-
tems. The second article discusses recent developments in the use of solid
adsorbents for preconcentrating trace organic substances, mainly pollu-
tants, from air. Types of adsorbents, collection efficiencies, comparative
sampling with different adsorbents, chromatographic approaches, and va-
por-particle partitioning applications are presented in detail. The third
article provides a detailed evaluation of X-ray emission spectroscopy for
trace analysis, including the principles of the technique, descriptions of
excitation and detection modes, and applications to pollutants in air, wa-
ter, and other environmental substances. The fourth article follows with a
similar treatment of inductively coupled plasma emission spectroscopy
and its application to the determination of trace elements in surface and
groundwater samples. This includes instrumentation, sampling, precon-
centration, and coupling the technique with chromatography for element
speciation. The final article is devoted to a comparison of neutron activa-
tion analysis and proton-induced X-ray emission spectroscopy for the
determination of trace elements in rain and snow. Theoretical aspects,
sample preparation, intermethod comparisons, and interpretation of
results are considered. This analysis complements that in the third article,
resulting in the extensive coverage of X-ray spectroscopy as an analytical
technique for a variety of environmental samples.
These five contributions should provide the reader with much insight
into the use of the various techniques described for a variety of trace
analytical problems. Together they make an extremely informative and
ix
X Preface
useful addition to this series. I would like to thank L. Ebdon, B. A. King,
T. F. Bidleman, R. E. Van Grieken, J. J. LaBrecque, J. R. Garbarino,
H. E. Taylor, S. Landsberger, R. E. Jervis, and S. Monaro for their hard
work in providing material for this volume.
JAMES F. LAWRENCE
CONTENTS OF PREVIOUS VOLUMES
VOLUME 1
Determination of Trace Organic Compounds in Aqueous Environmental Samples by High-
Performance Liquid Chromatography
Jeffrey A. Graham
Electrochemical Detectors for High-Performance Liquid Chromatography and Flow Analy-
sis Systems
K. Brunt
The Separation and Determination of Metal Species by Modern Liquid Chromatography
R. M. Cassidy
Liquid Chromatography in the Analysis of Mycotoxins
Peter M. Scott
Applications of Ion Chromatography in Trace Analysis
Hamish Small
Index
VOLUME 2
Trace Analysis of Vitamins by Liquid Chromatography
J. N. Thompson
Combining Liquid Chromatography with Mass Spectrometry
R. C. Willoughby and R. F. Browner
Applications of Steric Exclusion Chromatography in Trace Analysis
Ronald E. Majors and Thomas V. Alfredson
Trace-Enrichment Techniques for Organic Trace Analysis
W. A. Saner
HPLC Analysis of Polar Substances on Unmodified Silica
J. B. Green and P. L. Grizzle
Index
xi
xii Contents of Previous Volumes
VOLUME 3
Section 1. Biological Fluids and Tissues
Recent Developments in the Determination of Carbonyl Compounds in Biological Fluids
and Tissues
James H. Raymer and Milos V. Novotny
Recent Developments in Enzymatic Methods for Clinical Analysis
George G. Guilbault
Chlorinated Hydrocarbon Residues in Primate Tissues and Fluids
Jos Mes
Analysis of Ascorbic Acid and Related Compounds in Fluids and Tissues
Landis W. Doner
Recent Developments in Therapeutic Drug Monitoring of Antiepileptic Drugs
George K. Szabo and Thomas R. Browne
Section 2. Environmental Analysis
Determination of Environmental Pollutants by Direct Fluorescence Spectroscopy
Kjetill 0stgaard
Analysis of Polycyclic Aromatic Compounds in Combustion Emissions
A. G. Howard and G. A. Mills
Index
RECENT DEVELOPMENTS AND
APPLICATIONS OF ION-SELECTIVE
POLYMERIC MEMBRANE
ELECTRODES FOR BIOLOGICAL
TISSUES AND FLUIDS
Les Ebdon
Department of Environmental Sciences
Plymouth Polytechnic
Plymouth, England
and
Beverley Ann King
Department of Chemistry
Sheffield City Polytechnic
Sheffield, England
I. Introduction 2
II. Electrodes for the Determination of Ions 3
A. Hydrogen Ions 3
B. Sodium Ions 5
C. Potassium Ions 6
D. Lithium Ions 17
E. Calcium Ions 18
F. Magnesium Ions 29
G. Chloride Ions 29
H. Nitrate Ions 29
III. Gas-Sensing Probes 30
A. Introduction 30
B. Ammonia 31
C. Carbon Dioxide 31
IV. Enzyme Electrodes and Biosensors 33
A. Measurement of Urea 35
B. Measurement of Creatinine 37
1
Copyright © 1985 by Academic Press, Inc.
TRACE ANALYSIS, VOLUME 4 All rights of reproduction in any form reserved.
ISBN 0-12-682104-6
2 Les Ebdon and Beverley Ann King
C. Measurement of Amino Acids 37
D. Measurement of Glucose 38
E. Measurement of Nitrate 38
V. Drug Detection 40
VI. Immunoelectrodes 41
VII. Measurement of Membrane Potentials of Biological
Systems 43
References 44
I. INTRODUCTION
Ion-selective electrodes (ISE) are devices which enable the activity of a
given ion in a solution to be determined potentiometrically. They consist
of a selective membrane, an internal reference electrolyte (filling solu-
tion), and an internal reference electrode, which form a half-cell. An
external reference electrode completes the circuit. When the ion-selective
electrode is in contact with a solution of ions a potential difference is
generated between the internal filling solution and the sample solution
across the membrane. The potential (E) varies with ion activity according
to the Nernst equation
E = E° log a>
e
in which is0 is the standard potential, R is the gas constant, T is the
absolute temperature, z is the charge on the ion, and a is the activity.
x
When, as is customary, the relationship is expressed as millivolts per
decade change in ion activity, E is close to 60 mV at 25°C for monovalent
ions.
The membrane components of ISE vary greatly and may be used to
define the class of ISE. An early form of ISE consisted of a liquid ion
exchanger supported by a porous membrane. Moody and Thomas pio-
neered a new type of ISE by incorporating the liquid ion exchanger in a
nonporous polymer membrane. The new electrodes showed superior
physical properties. Miniaturization of these sensors was investigated by
Freiser, who introduced coated-wire ISE by coating metal wires with
polymer membranes. Simon and co-workers have produced many new
and highly selective electroactive materials of the neutral ligand type.
Guilbault prepared new types of ISE by prefacing the selective mem-
branes with enzymes and bacteria. These electrodes are capable of ana-
lyzing substrates such as urea and amino acids by detection of the prod-
ucts of enzyme-catalyzed reactions.
The introduction of ISE to clinical medicine has been relatively slow