Table Of ContentLiquid Chromatography
in Environmental Analysis
Contemporary Instrumentation and Analysis
Gary M. Hieftje, Editor
Editorial Board
Bernard J. Bulkin Gary Horlick
R. Graham Cooks Gordon F. Kirkhright
Leo de Galan Bruce R. Kowalski
Merle A. Evenson Milos V. Novotny
Tomas Hirschfield Earl L. Wehry
Liquid Chromatography in Environmental Analysis, edited by
James F. Lawrence, 1984
Lasers in Chemical Analysis, edited by Gary M. Hieftje, John C.
Travis, and Fred E. Lytle, 1981
Introduction to Bioinstrumentation, with Biological, Medical, and
Environmental Applications, Clifford D. Ferris, 1979
Liquid Chromatography
in Environmental Analysis
Edited by
James F. Lawrence
Health and Welfare Canada, Ottawa, Canada
Humana Press • Clifton, New Jersey
Library of Congress Cataloging in Publication Data
Main entry under title:
Liquid chromatography in environment.al analysis.
(Contemporary instrumentaion and analysis)
Bibliography: p.
Includes irKIex.
I. Liquid chromatography. 2. Envrionmental
chemistry. I. Lawrence, James F. II. Series.
QD79.C454LS535 1983 543'.0894 83-10711
ISBN·13: 978·1·4612·9778.9 e·ISBN·13: 978·14612·53()6.8
DOl: IO.IOO7/978-1-4612-53()6.8
~1984 The Humana Press Inc.
SoftoovcrrtprU.ofthe Il<Ylb:Jvcr Istedition 1984
Crescent Manor
PO Box 2148
Clifton, NJ 07015
All rights reserved
No part of this book may be reproduced, stored in a retrieval syStem,
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Preface
Since the 1960s there has evolved a great interest in and concern for the
types and quantity of chemicals that find their way into the general envi
ronment. One result of this has been an increased activity in the analysis
of such compounds, particularly those that pose even a remote threat to
our well-being. In the past ten years or so, high-pressure liquid chroma
tography (HPLC) has developed to the point where in many instances it is
the method of choice for environmental analysis. This volume attempts to
demonstrate to the reader the utility of HPLC in environmental analytical
chemistry and includes not only analysis, but special techniques
involving sample preparation, concentration, and cleanup for other deter
minative methods. Applications to compounds over a wide range of
polarity-from nonpolar polycyclic aromatic hydrocarbons, through
moderately polar substances such as many pesticides, to polar substances
such as ionic and nonionic surfactants, organometallics, and inorganic
ions-are presented.
The volume starts off with a chapter on quality assurance in environ
mental trace analysis and is concerned with all activities that have an im
portant effect on the quality of the environmental measurements. Quality
assurance is becoming more important, especially in regulatory or com
mercial service laboratories in which the quality of the generated data
may be challenged. The second chapter provides an in-depth discussion
of methodology for the determination of polycyclic aromatic hydrocar
bons (PAH). These nonpolar compounds are important environmental
pollutants and HPLC has been shown to be particularly effective in their
analysis. The chapter details methodology for many PAH in a variety of
environmental samples.
Following this are two chapters that describe HPLC methodology
and sample preparation for moderately polar compounds such as pes-
v
vi PREFACE
ticides, and polar ionic and nonionic surface active substances such as
emulsifying, dispersing, wetting, and foam-producing agents. The latter
group consist of chemicals composed of a hydrocarbon chain containing
highly polar functional groups. Application to water, soil, and plant and
animal tissues is included.
The chapter on trace metals is particularly comprehensive and in
cludes discussions of state-of-the-art HPLC techniques applied to inor
ganics. Chromatography and detection systems are compared that include
coupling of HPLC with absorbance, fluorescence, atomic absorption,
plasma emission, and electrochemical detection and the various modes of
liquid chromatography. The sixth chapter details recent developments in
anion analysis by ion chromatography. This technique has enjoyed con
siderable growth since the mid-1970s and has been proven to be ex
tremely useful for environmental applications.
The last two chapters present the advantages of using HPLC in a spe
cialized way to improve analysis even if the final determination is made
by some other analytical technique. Column switching and trace enrich
ment are both of much interest at present, especially to environmental an
alysts, where sample collection and concentration can be simplified or
where separation selectivity can be altered by simply switching from one
column to the next, on-line. Also, HPLC is ideally suited to the isolation
of precise chromatographic fractions, resulting in relatively pure extracts
for analysis. A good example of this is the integral role played by HPLC
in the purification of dioxins at parts per trillion levels in fish samples for
quantitation by gas chromatography-mass spectrometry.
This volume, although not comprehensive in the sense that it does
not present extensive applications of HPLC in the area of environmental
analysis, does contain selected topics that present ideas and approaches
that may be applied to the development of a quality assurance program,
the analysis of compounds over a large polarity range, including organ
ics, inorganics, and ionic substances in a wide variety of sample materi
als, and the use of novel arrangements and applications of HPLC systems
to improve or simplify analysis. This information should provide the ana
lyst with valuable ideas that will help solve many diverse environmental
analytical problems.
I wish to express my sincere thanks to J.R. Hall, B. J. Das, P.
Jandera, E. G. Cotterill, T. H. Byast, I. S. Krull, E. L. Johnson, K. K.
Haak, M. C. Harvey, S. D. Steams, and J. J. Ryan for their excellent
contributions to this volume.
J. F. Lawrence
Contributors
T. H. BYAST • Agricultural Research Council, Begbroke Hill, Yarnton,
Oxford, UK
E. G. COTTERILL • Agricultural Research Council, Begbroke Hill,
Yarnton, Oxford, UK
BEJOY S. DAS • Ontario Research Foundation, Sheridan Park,
Mississauga, Ontario, Canada
K. K. HAAK • Dionex Corporation, Sunnyvale, California
JACK R. HALL • IT Enviroscience, Knoxville, Tennessee
MACK C. HARVEY • Valco Instruments, Houston, Texas
PAVEL J ANDERA • Department of Analytical Chemistry
E. L. JOHNSON • Dionex Corporation, Sunnyvale, California
I. S. KRULL • Institute of Chemical Analysis, Boston, Massachusetts
JOHN J. RYAN • Health Protection Branch, Ottawa, Ontario, Canada
STANLEY D. STEARNS • Valco Instruments, Houston, Texas
Contents
Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
List of Contributors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII
Chapter 1
Quality Assurance in Environmental Trace Analysis
Jack R. Hall
1. The Quality Assurance Program 1
1.1. Objectives of a Quality Assurance Program ..... . 2
1.2. Elements Evaluated by the Quality Assurance
Program ................................ . 3
l.3. Management of the Quality Assurance Program .. 5
1.4. Documentation ............................ . 8
2. Quality Control Procedures in the Quality Assurance
Program ........................................ . 11
2.1. Role of Quality Control Procedures ........... . 11
2.2. Blanks, Replicates, and Spiked Samples ....... . 12
2.3. Evaluation of Results ....................... . 12
3. Operation of a Quality Assurance Program .............. . 14
3. 1. Feedback to the Analyst. .................... . 15
3.2. Corrective Actions ......................... . 16
3.3. Quality Assurance Program Changes .......... . 16
References ................................ . 17
ix
x CONTENTS
Chapter 2
Applications of HPLC to the Analysis of Polycyclic
Aromatic Hydrocarbons in Environmental
Samples
s.
Bejoy Das
1. Introduction............ ...... ... ....... ............ 19
2. Nomenclature, Structure, and Carcinogenicity. . . . . . . . . . . . 20
3. Origin and Formation in the Environment. . . . . . . . . . . . . . . . 21
4. Methods of Analysis for Polycyclic Hydrocarbons. . . . . . . . . 30
4.1. Nonpolar Chemically Bonded Stationary Phase. . . 31
4.2. Polar Chemically Bonded Stationary Phase. . . . . . 36
4.3. Separation of PANH, PASH, and Nitro-PAH . . . . 38
4.4. Detection and Identification. . . . . . . . . . . . . . . . . . . 41
5. HPLC Applications in PAH Analysis. . . . . . . . . . . . . . . . . . . 50
5.1. Air Particulates, Fly Ash, Carbon Black, and
Coal Tar Pitch .. . . . . . . . . . . . . . . . . . . . . . . . . . 50
5.2. Water and Waste Water. . . . . . . . . . . . . . . . . . . . . . 55
5.3. Sediments, Fish, Mussels, and Meat. . . . . . . . . . . 56
5.4. Petroleum and Synthetic Fuels. . . . . . . . . . . . . . . . 56
6. Conclusions............. .... ......... .. .... .. ...... 58
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
Chapter 3
HPLC of Pesticide Residues in Environmental
Samples
E.G. Cotterill and T. H. Byast
1. Introduction................. ..... ... .. ..... ... .. .. . 77
2. Instrumentation and Methodology . . . . . . . . . . . . . . . . . . . . . . 80
2.1. Pumps............. ....................... 80
2.2. Injection Systems. . . . . . . . . . . . . . . . . . . . . . . . . . . 85
2.3. Columns and Column Packing. . . . . . . . . . . . . . . . 86
2.4. Detectors.................................. 87
