Liquid Chromatography in Environmental Analysis

Contemporary Instrumentation and Analysis

Gary M. Hieftje, Editor Editorial Board

Bernard J. Bulkin R. Graham Cooks Leo de Galan Merle A. Evenson Tomas Hirschfield

Gary Horlick Gordon F. Kirkhright Bruce R. Kowalski Milos V. Novotny 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·1 3: 978·14612·53()6.8 DOl: IO. IOO7/978-1-46 12-53()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 , or transmitted in any fonn or by any means, electronic, mechanical, phototopying, microfilming, m:ording, or otherwise without written pennission from Ihe Publisher.

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 envi­ronment. 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 chroma­tography (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 deter­minative 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 environ­mental trace analysis and is concerned with all activities that have an im­portant effect on the quality of the environmental measurements. Quality assurance is becoming more important, especially in regulatory or com­mercial 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 hydrocar­bons (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 in­cludes discussions of state-of-the-art HPLC techniques applied to inor­ganics. 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 con­siderable growth since the mid-1970s and has been proven to be ex­tremely useful for environmental applications.

The last two chapters present the advantages of using HPLC in a spe­cialized way to improve analysis even if the final determination is made by some other analytical technique. Column switching and trace enrich­ment are both of much interest at present, especially to environmental an­alysts, 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 organ­ics, inorganics, and ionic substances in a wide variety of sample materi­als, and the use of novel arrangements and applications of HPLC systems to improve or simplify analysis. This information should provide the ana­lyst 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. Objectives of a Quality Assurance Program ..... . 1.2. Elements Evaluated by the Quality Assurance

Program ................................ . l.3. Management of the Quality Assurance Program .. 1.4. Documentation ............................ .

2. Quality Control Procedures in the Quality Assurance Program ........................................ .

2.1. Role of Quality Control Procedures ........... . 2.2. Blanks, Replicates, and Spiked Samples ....... . 2.3. Evaluation of Results ....................... .

3. Operation of a Quality Assurance Program .............. .

3. 1. Feedback to the Analyst. .................... . 3.2. Corrective Actions ......................... . 3.3. Quality Assurance Program Changes .......... .

References ................................ .

ix

1

2

3 5 8

11

11 12 12

14

15 16 16 17

x CONTENTS

Chapter 2 Applications of HPLC to the Analysis of Polycyclic

Aromatic Hydrocarbons in Environmental Samples

Bejoy s. 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

CONTENTS xi

2.5. Solvents........................ .. ......... 90 2.6. Preparation of Derivatives. . . . . . . . . . . . . . . . . . . . 92

3. Applications... ... .................................. 92

3.1. Water..................................... 92 3.2. Examples.. .. ... .. ......................... 93 3.3. Soil.. .. ........... . ...................... 96 3.4. Examples .. .......... . ........ . ........ . .. . 98 3.5. Hydrosoil................................. 102 3.6. Example.......... .. . . ........ .. .......... 102 3.7. Plant Material. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 3.8. Examples............................. . .... 104 3.9. Animal Tissue. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107

3.10. Example.................................. 107

4. Conclusions.............. .. .. .. .. . . .. .............. 107

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 108

Chapter 4 HPLC Determination of Surfactants and Related

Compounds Pavel Jandera

1. Anionic Surfactants and Related Compounds. . . . . . . . . . . .. 117

I . 1 . General Methods .............. .. ........... 117 1.2. Analysis of Anionic Surfactants in Environmental

Samples by Means of HPLC . . . . . . . . . . . . . . . . 137

2. Nonionic Surfactants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 140

2.1. General Methods .. .. .. ................. .. .. 140 2.2. Analysis of Nonionic Surfactants in

Environmental Samples by Means of HPLC . . . 154

3. Cationic and Amphoteric Surfactants and Related Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 157

3.1. General Methods ........................... 157 3.2. Analysis of Cationic Surfactants in Environmental

Samples by Means of HPLC . . . . . . . . . . . . . . . . 162

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 162

xii CONTENTS

Chapter 5 Trace Metal Analysis by High Performance Liquid

Chromatography I. S. Krull

1. Introduction........................................ 169 2. HPLC-Ultraviolet, -Visible, and/or -Fluorescence Detection

of Metal Species.................................. 173 3. HPLC-Mass Spectrometric Detection of Metal Species. . . .. 191 4. HPLC-Atomic Absorption Spectroscopic Detection of Metal

Species. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 193 5. HPLC-Atomic Fluorescence Spectroscopic Detection of

Metal Species ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 211 6. HPLC-Inductively Coupled or -Direct-Current Plasma

Emission Spectroscopic Detection of Metal Species ..... 214 6.1 HPLC-Direct-Current Plasma Emission

Spectroscopic Detection of Metal Species . . . . . 229 7. HPLC-Electrochemical and -Conductivity Detection of

Metal Species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 231 8. Ion Chromatography-Conductivity Detection of Metal

Species. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 243 9. Conclusions........................................ 251

References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 255

Chapter 6 Anion Analysis by Ion Chromatography E. L. Johnson and K. K. Haak

1. Introduction........................................ 263

2. Separation Modes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 266

2.1. High Performance Ion Chromatography (HPIC) . . 266 2.2. Mobile-Phase Ion Chromatography (MPIC). . . . . . 271 2.3. High Performance Ion Chromatography Exclusion

(HPICE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274 2.4. Summary of Separation Techniques. . . . . . . . . . . . 275

3. Detection Modes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277

3.1. Fiber Suppressors. . . . . . . . . . . . . . . . . . . . . . . . . . . 277

CONTENTS xiii

3.2. Suppression via Precipitation. . . . . . . . . . . . . . . . . . 280 3.3. Other Detection Modes . . . . . . . . . . . . . . . . . . . . . . 281

4. New Applications in Anion Ion Chromatography. . . . . . . . .. 283

4.1. Cyanide and Cyanide Complexes. . . . . . . . . . . . . . 283 4.2. Acid Rain Analysis. . . . . . . . . . . . . . . . . . . . . . . . . 283 4.3. Trace Iodide Determination. . . . . . . . . . . . . . . . . . . 284 4.4. Chromate Determination. . . . . . . . . . . . . . . . . . . . . 286 4.5. Trace Analysis of Bulk Chemicals. . . . . . . . . . . . . 287 4.6. Trace Determination of Nitrate. . . . . . . . . . . . . . . . 290 4.7. Brine Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292 4.8. Miscellaneous Anion Separations. . . . . . . . . . . . . . 293

5. Summary.......................................... 298

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 299

Chapter 7 HPLC Sample Injection and Column Switching Mack C. Harvey and Stanley D. Stearns

1. HPLC Sample Injection Using Valves. . . . . . . . . . . . . . . . . .. 301

1.1. Sample Injection onto 2 mm id or Larger HPLC Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303

1.2. Injection onto Small Bore «2 mm id) HPLC Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306

2. HPLC Column Switching. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 311

2.1. Sample Injection and Backflushing by Column Reversal ................................ 312

2.2. Sample Injection and Two-Column Sequence Reversal and Backflush of Column One to the Detector. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315

2.3. Sample Injection and Column Switching for HPLC Fraction Selection. . . . . . . . . . . . . . . . . . . 317

2.4. HPLC Column Selection. . . . . . . . . . . . . . . . . . . . . 326 2.5. HPLC Instrument Selection. . . . . . . . . . . . . . . . . . . 329 2.6. HPLC On-Line Trace Enrichment. . . . . . . . . . . . . . 330

References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 339

xiv CONTENTS

Chapter 8 High Performance Liquid Chromatography as a

Cleanup Technique John J. Ryan

1. Introduction........................................ 341 2. Cleanup for Gas Chromatography (GC) with Electron

Capture (EC) or Flame Detection. . . . . . . . . . . . . . . . .. 343 3. Cleanup for GC-Mass Spectrometry (MS) . . . . . . . . . . . . . .. 346 4. HPLC-HPLC....................................... 350 5. Cleanup for Radioimmunoassay (RIA) . . . . . . . . . . . . . . . . .. 355 6. Radioisotope Fractionation. . . . . . . . . . . . . . . . . . . . . . . . . . .. 359 7. Summary.......................................... 361

References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 361

Index. ...... . ... . ... . ... . .. . .. ..... ... . .. . ... . . ... 363

Liquid Chromatography in Environmental Analysis